Compound, composition, surface treatment agent, article and method for manufacturing article

Abstract

Provided are: a novel compound capable of forming a surface treatment layer having excellent wear resistance; and the like. The compound according to the present invention contains the following group P and a fluoropolyether chain. And a group P:-[Si (R1) 2-X] n1-Si (R1) 3. Wherein each X independently represents an oxygen atom or a carbon atom, each R1 independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group, at least four of the R1 represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n1 represents an integer of 1-3.

Description

TECHNICAL FIELD

[0001] The present application relates to a compound, a composition, a surface treatment agent, an article, and a method for manufacturing an article. BACKGROUND

[0002] A fluorine-containing ether compound having a fluorine atom is excellent in various properties such as low refractive index, low dielectric constant, water / oil repellency, heat resistance, chemical resistance, chemical stability, transparency, and the like, and is used in a wide variety of fields such as electrical and electronic materials, semiconductor materials, optical materials, surface treatment agents, and the like.

[0003] Patent Document 1 discloses surface treatment using a surface treatment agent containing a silane compound containing a perfluoropolyether group.

[0004] Patent Document 2 discloses surface treatment using a surface treatment agent containing a fluorine-containing silane compound and a metal compound containing a transition metal such as tantalum (Ta).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT DOCUMENT

[0007] Patent Document 1: Japanese Patent Application Publication No. 2014-218639

[0008] Patent Document 2: International Publication No. 2021 / 010105 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] From the viewpoint of abrasion resistance and the like, surface treatment agents are required to be further improved.

[0011] The present application was completed in view of such circumstances, and aims to provide a novel compound and the like capable of forming a surface treatment layer excellent in abrasion resistance.

[0012] SOLUTION TO PROBLEM

[0013] The present application includes the following modes. [1]

[0015] A compound containing the following group P and a fluoropolyether chain,

[0016] Group P: -[Si(R 1 )2-X] n1 -Si(R 1 )3,

[0017] wherein each X is independently an oxygen atom or a carbon atom,

[0018] R 1Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0019] R 1 At least 4 Rs in 1 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0020] n1 is an integer from 1 to 3. [2]

[0022] According to the compound described above [1], wherein n1 is 1. [3]

[0024] According to the compound described above [1], wherein the group P is -[Si(OR)] 2 )2-O] n1 -Si(OR) 2 3,

[0025] Among them, R 2 Each is an independent hydrocarbon group. [4]

[0027] According to the compound described above [2], wherein the group P is -Si(OR) 2 )2-O-Si(OR 2 3,

[0028] Among them, R 2 Each is an independent hydrocarbon group. [5]

[0030] The compounds represented by formula (1) or formula (2) below,

[0031] (R) f1 ) n3 -Q 1 -(J 1 ) n2 …Formula (1)

[0032] (J) 1 ) n2 -Q 2 -R f2 -Q 2 -(J 1 ) n2 …Formula (2)

[0033] Among them, J 1 Each of them independently represents the following group P,

[0034] Group P:-[Si(R) 1 )2-X] n1 -Si(R) 1 3,

[0035] X can be an oxygen atom or a carbon atom independently.

[0036] R 1 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0037] R 1 At least 4 Rs in 1 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.

[0038] n1 is an integer from 1 to 3.

[0039] R f1 It is a monovalent fluorinated polyether chain.

[0040] R f2 It is a divalent fluorinated polyether chain.

[0041] Q 1 It is a (n3+n2) valence linking group.

[0042] Q 2 It is a (1+n2) valence linking group.

[0043] n2 are each an independent integer greater than or equal to 1.

[0044] n3 is an integer greater than or equal to 1. [6]

[0046] According to the compound described above [5], wherein n2 is 1 to 6. [7]

[0048] According to the compounds described above [5] or [6], wherein the R f1 It is represented by the following formula (3),

[0049] R f11 - (OR) f12 ) m1 - …Formula (3)

[0050] Among them, R f11 It is a fluoroalkyl group with 1 to 20 carbon atoms, and contains multiple R groups. f11 At that time, multiple existing R f11 Choose either the same or different from each other.

[0051] R f12 It is a fluoroalkylene group with 1 to 6 carbon atoms, and contains multiple R groups. f12 At that time, multiple existing R f12 Choose either the same or different from each other.

[0052] m1 is an integer from 0 to 500. [8]

[0054] According to any one of the preceding [5] to [7] compounds, wherein the R f2 It is represented by the following formula (4),

[0055] -R f21 - (OR) f22 ) m2 - …Formula (4)

[0056] in,

[0057] R f21 It is a fluoroalkylene group with 1 to 6 carbon atoms, and contains multiple R groups. f21 At that time, multiple existing R f21 Choose either the same or different from each other.

[0058] R f22 It is a fluoroalkylene group with 1 to 6 carbon atoms, and contains multiple R groups. f22 At that time, multiple existing R f22 Choose either the same or different from each other.

[0059] m2 is an integer from 0 to 500. [9]

[0061] A composition comprising any one of the compounds described in any one of [1] to [8] above and a liquid medium.

[10]

[0063] A surface treatment agent comprising any one of the compounds described in any of [1] to [8].

[11]

[0065] A surface treatment agent comprising any one of the compounds described in any one of [1] to [8] above and a liquid medium.

[12]

[0067] A method for manufacturing an article, wherein a surface treatment agent comprising any one of the compounds described in any one of [1] to [8] is used to surface treat a substrate to manufacture an article having a surface treatment layer formed on the substrate.

[13]

[0069] An article comprising a substrate and a surface treatment layer disposed on the substrate and surface-treated with a surface treatment agent comprising any one of the compounds described in any one of [1] to [8].

[14]

[0071] According to the aforementioned

[13] , it is an optical component.

[15]

[0073] According to the aforementioned

[13] , it is a display or touch panel.

[0074] The effects of the invention

[0075] According to the present invention, novel compounds and the like can be provided that can form surface treatment layers with excellent wear resistance. Detailed Implementation

[0076] In this specification, the numerical range represented by "~" contains the minimum and maximum values ​​before and after "~".

[0077] In the numerical ranges described in this specification, the upper or lower limit of one numerical range can be replaced with the upper or lower limit of another numerical range described in other stages. Furthermore, the upper or lower limit of the numerical range described in this specification can also be replaced with the values ​​shown in the embodiments.

[0078] In this specification, "surface treatment layer" refers to a layer formed on the surface of a substrate through surface treatment.

[0079] In this specification, "Me" sometimes refers to methyl.

[0080] In this specification, when a compound or group is represented by a specific formula (X), the compound or group represented by the formula (X) is sometimes referred to as compound (X) or compound X, and group (X) or group X, respectively.

[0081] It should be noted that when the same symbol exists in a chemical formula, the same symbol can be the same structure as each other, or it can be a structure that is different from each other within a specified range.

[0082] Unless otherwise specified, the bonding direction of the divalent groups described in this specification is not limited. For example, when Y in a compound represented by the formula "XYZ" is -COO-, Y can be -CO-O- or -O-CO-. In addition, the above compound can be "X-CO-OZ" or "XO-CO-Z".

[0083] In this specification, fluoroalkyl refers to a general term encompassing both perfluoroalkyl and partially fluoroalkyl groups. A perfluoroalkyl group is a group in which all hydrogen atoms of an alkyl group are replaced by fluorine atoms. Conversely, a partially fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are replaced by fluorine atoms and it has one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group having one or more fluorine atoms.

[0084] The "molecular weight" of fluorinated polyether chains is determined by... 1 H-NMR and 19The number-average molecular weight is calculated by using F-NMR to determine the number (average value) of oxyfluoroalkyl units based on the terminal groups.

[0085] [Compound]

[0086] The compounds of this invention are compounds comprising the following groups P and fluorinated polyether chains.

[0087] Group P:-[Si(R) 1 )2-X] n1 -Si(R) 1 3,

[0088] In this context, X is independently either an oxygen atom or a carbon atom, and R... 1 Each is independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group, R 1 At least 4 Rs in 1 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, where n1 is an integer from 1 to 3.

[0089] When the compounds of the present invention are used as surface treatment agents, a surface treatment layer with excellent liquid repellency can be formed. The reason for this is not yet clear, but it is speculated as follows.

[0090] The compound containing the aforementioned group P exhibits high adhesion to the substrate, enabling the formation of a surface treatment layer with excellent wear resistance on the substrate.

[0091] <group P>

[0092] The compounds of the present invention comprise the aforementioned group P. The compound may contain only one group P, or it may contain two or more groups P. For example, it may contain 1 to 18 groups, 2 to 12 groups, or 2 to 8 groups. Furthermore, group P is a monovalent group and therefore is located at the end of the compound.

[0093] When multiple groups P exist in a single molecule, these groups P can be identical or distinct. From the viewpoint of ease of obtaining raw materials and ease of manufacturing the compound, it is preferable that the multiple groups P are identical.

[0094] R 1 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group.

[0095] Hydrolyzable groups are groups that become hydroxyl groups through hydrolysis. That is, groups formed by Si-R... 1The hydrolyzable silane group represents a silanol group represented by Si-OH, which undergoes a hydrolysis reaction. The silanol groups further react with each other to form Si-O-Si bonds. Alternatively, the silanol groups can undergo a dehydration condensation reaction with silanol groups derived from oxides present on the substrate surface to form Si-O-Si bonds.

[0096] Examples of hydrolyzable groups include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, isocyanate groups (-NCO), and alkylene oxide-modified alkoxy groups.

[0097] The alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. The aryloxy group is preferably an aryloxy group with 3 to 10 carbon atoms. The aryl group of the aryloxy group may also be a heteroaryl group. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group with 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group with 1 to 6 carbon atoms.

[0098] The group having a hydrolyzable group can be, for example, the group having a hydrolyzable group illustrated above. The preferred group having a hydrolyzable group is -OL. A -L B L A It is an alkylene group, L B It is a hydrolyzable group. The alkylene group preferably has 1 to 10 carbon atoms. B The hydrolyzable group shown is related to the above R 1 The hydrolyzable groups shown have the same meaning and are preferred in the same way. A specific example of a group having a hydrolyzable group is -O-CH2CH2-OCH3.

[0099] From the perspective of the ease of compound preparation, R 1 The hydrolyzable groups or groups containing hydrolyzable groups are preferably alkoxy groups with 1 to 4 carbon atoms, alkylene oxide-modified alkoxy groups, or halogen atoms. From the viewpoint of less degassing during coating and better storage stability of the compound, R... 1 Preferably, it is an alkoxy group with 1 to 4 carbon atoms, more preferably an ethoxy or methoxy group.

[0100] As R 1 The hydrocarbon group can be alkyl, cycloalkyl, alkenyl, allyl, etc., and from the viewpoint of ease of synthesis, a saturated hydrocarbon group is preferred, and an alkyl group is more preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0101] n1 is an integer from 1 to 3. From the viewpoint of ease of synthesis, it is preferably 1 to 2, and more preferably 1.

[0102] A group P possesses multiple R 1At least four of the groups in group P are hydrolyzable groups, groups having hydrolyzable groups, or hydroxyl groups. This allows group P to bond more firmly to the substrate, resulting in a surface treatment layer with excellent wear resistance. From this perspective, the number of hydrolyzable groups, groups having hydrolyzable groups, and hydroxyl groups in group P is preferably 4 to 9, more preferably 4 to 7, and even more preferably 4 to 5. It should be noted that multiple R groups present in one molecule... 1 Choose either the same or all different. For example, multiple R... 1 They can be the same hydrolyzable groups.

[0103] X can be an oxygen atom or a carbon atom. Here, the carbon atom in X refers to a divalent carbon atom, where Si is connected to each other by one carbon atom. X can be -CH2-, -C(CH3)2-, etc. From the viewpoint of the wear resistance of the surface treatment layer, X is preferably an oxygen atom, -CH2-, or -C(CH3)2-, more preferably an oxygen atom or -CH2-, and even more preferably an oxygen atom.

[0104] From the perspective of excellent wear resistance of the surface treatment layer, the P group is preferably -[Si(OR)] 2 )2-O] n1 -Si(OR) 2 )3, wherein, particularly preferred is -Si(OR) with n1=1. 2 )2-O-Si(OR 2 3. Among them, R 2 Each is independently a hydrocarbon group. Examples of such hydrocarbon groups include alkyl, cycloalkyl, alkenyl, and allyl groups; from the viewpoint of ease of synthesis, saturated hydrocarbon groups are preferred, and alkyl groups are more preferred. R 2 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0105] Specific examples of the group P include -Si(OCH3)2-O-Si(OCH3)3, -Si(OCH3)2-CH2-Si(OCH3)3, -Si(OCH3)2-C(CH3)2-Si(OCH3)3, -Si(OCH2CH3)2-O-Si(OCH3)3, -Si(OCH3)2-O-Si(OCH2CH3) 3. -Si(OCH2CH3)2-O-Si(OCH2CH3)3, -Si(OCH2CH3)2-CH2-Si(OCH3)3, -Si(OCH3)2-CH2-Si(OCH2CH3)3, -Si(OCH2CH3)2-CH2-Si(OCH2CH3)3, -Si(OCH2CH3)2-C(CH3)2-S i(OCH3)3, -Si(OCH3)2-C(CH3)2-Si(OCH2CH3)3, -Si(OCH2CH3)2-C(CH3)2-Si(OCH2CH3)3, -Si(OH)2-O-Si(OH)3, -Si(OH)2-O-Si(OCH3)3, -Si(OCH3)2-O-Si(OH)3, -Si( OH)2-CH2-Si(OH)3, -Si(OH)2-CH2-Si(OCH3)3, -Si(OCH3)2-CH2-Si(OH)3, -Si(OH)2-C(CH3)2-Si(OH)3, -Si(OH)2-C(CH3)2-Si(OCH3)3, -Si(OCH3)2-C(CH3)2-Si(OH)3.

[0106] <Fluoropolyether chain>

[0107] The compounds of this invention, by having fluorinated polyether chains, are capable of forming surface treatment layers with excellent wear resistance. Examples of fluorinated polyether chains include those described below. f1 Or R f2 The same chain.

[0108] <Compound (1), Compound (2)>

[0109] The compounds of the present invention are compounds represented by formula (1) or formula (2) below.

[0110] (R) f1 ) n2 -Q 1 -(J 1 ) n2 …Formula (1)

[0111] (J) 1 ) n2 -Q 2 -R f2 -Q 2-(J 1 ) n2 …Formula (2)

[0112] Among them, J 1 Each of these is independently represented by the aforementioned group P, and repeated descriptions are omitted.

[0113] Additionally, R f1 R is a monovalent fluorinated polyether chain. f2 It is a divalent fluorinated polyether chain, Q 1 and Q 2 Each of the connecting groups is independently a (1+n2) valence group, where n2 is an integer greater than or equal to 1.

[0114] R, as a monovalent fluorinated polyether chain f1 and R as a divalent fluorinated polyether chain f2 It is a group having two or more oxyfluoroalkyl units.

[0115] R f1 and R f2 It can have hydrogen atoms, but Q 1 Or Q 2 The carbon atoms at the side ends have fluorine atoms.

[0116] In the surface treatment layer using the compounds of the present invention, from the viewpoint of excellent wear resistance, the molecular weight of each fluoropolyether chain is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, and even more preferably 3,000 to 10,000. If the molecular weight of the fluoropolyether chain is 20,000 or less, a surface treatment layer with excellent wear resistance can be obtained.

[0117] As R f1 The following structure (A1) is preferred.

[0118] R f11 - (OR) f12 ) m1 - … (A1)

[0119] Among them, R f11 It is a fluoroalkyl group with 1 to 20 carbon atoms, and contains multiple R groups. f11 At that time, multiple existing R f11 Choose either the same or different from each other.

[0120] R f12 It is a fluoroalkylene group with 1 to 6 carbon atoms, and contains multiple R groups. f12 At that time, multiple existing R f12 Choose either the same or different from each other.

[0121] m1 is an integer from 0 to 500. m1 is preferably an integer from 1 to 500, more preferably an integer from 2 to 500, even more preferably an integer from 10 to 200, and particularly preferably an integer from 10 to 100.

[0122] Similarly, R, as a divalent fluorinated polyether chain f2 The following structure (A2) is preferred.

[0123] -R f21 - (OR) f22 ) m2 - …(A2)

[0124] Among them, R f21 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0125] R f22 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0126] In the existence of multiple R f22 At that time, multiple existing R f22 Choose either the same or different from each other.

[0127] m2 is an integer from 0 to 500.

[0128] (OR) f12 ) and (OR f22 It preferably has the following structure (f2).

[0129] -[(OG) f1 ) m11 (OG) f2 ) m12 (OG) f3 ) m13 (OG) f4 ) m14 (OG) f5 ) m15 (OG) f6 ) m16 ]- …(f2)

[0130] in,

[0131] G f1 It is a fluorinated alkylene group with 1 carbon atom.

[0132] G f2 It is a fluorinated alkylene group with 2 carbon atoms.

[0133] G f3 It is a fluorinated alkylene group with 3 carbon atoms.

[0134] G f4 It is a fluoroalkylene group with 4 carbon atoms.

[0135] G f5It is a fluoroalkylene group with 5 carbon atoms.

[0136] G f6 It is a fluorinated alkylene group with 6 carbon atoms.

[0137] m11, m12, m13, m14, m15, and m16 each independently represent integers greater than or equal to 0 or 1, and m11+m12+m13+m14+m15+m16 is preferably an integer between 2 and 200.

[0138] It should be noted that in structure (f2) (OG f1 )~(OG f6 The bonding order of ) is arbitrary. m11~m16 of structure (f2) represent (OG) f1 )~(OG f6 The number of ) does not indicate configuration. For example, (OG f5 ) m15 OG f5 The quantity is m15, which does not represent (OG) f5 ) m15 The block configuration structure. Similarly, (OG f1 )~(OG f6 The order in which these are recorded does not indicate the bonding order of the units.

[0139] In addition, the aforementioned fluoroalkyl groups with 3 to 6 carbon atoms can be straight-chain fluoroalkyl groups or fluoroalkyl groups with branched or cyclic structures.

[0140] As G f1 Specific examples include -CF2- and -CHF-.

[0141] As G f2 Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, and -CH2CHF-.

[0142] As G f3Specific examples include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CH F-, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH 2F) -CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, -CH(CH2F)-CH2-.

[0143] As G f4 Specific examples include -CF2CF2CF2CF2-, -CHFCF2CF2CF2-, -CH2CF2CF2CF2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, - CF2CHFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2- , -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, -cycloC4F6-.

[0144] As G f5Specific examples include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, and -cycloC5F8-.

[0145] As G f6 Specific examples include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, and -cycloC6F. 10 -

[0146] Here, -cycloC4F6- refers to a perfluorocyclobutane dieryl, and specific examples include perfluorocyclobutane-1,2-diyl and perfluorocyclobutane-1,3-diyl. -cycloC5F8- refers to a perfluorocyclopentane dieryl, and specific examples include perfluorocyclopentane-1,3-diyl. -cycloC6F 10 - refers to perfluorocyclohexane dimethyl, and as a specific example, perfluorocyclohexane-1,4-dimethyl can be listed.

[0147] From the perspective of superior wear resistance, among which, - (OR f12 ) m1 - and - (OR f22 ) m2 - Preferably, the structure has any one of the structures shown in (f3) to (f5) below. From the viewpoint of superior alkali resistance, the structure shown in (f3) is more preferred, and (OCF2) is even more preferred. m11 (OCF2CF2) m12 The structure shown is (OCF2). m11 (OCF2CF2) m12 From the viewpoint of superior abrasion resistance and fingerprint stain removal of the surface layer, m12 / m11 is preferably 0.1~10, more preferably 0.2~5.0, further preferably 0.2~2.0, particularly preferably 0.2~1.5, and most preferably 0.2~0.85.

[0148] -(OG f1 ) m11 · (OG) f2 ) m12 - …(f3)

[0149] -(OG f2 ) m12 · (OG) f4 ) m14 - …(f4)

[0150] -(OG f3 ) m13 - …(f5)

[0151] The symbols of structures (f3) to (f5) are the same as those of structure (f2) above.

[0152] In structures (f3) and (f4), (OG f1 ) and (OG f2 ), (OG f2 ) and (OG f4 The bonding order of (OG) is arbitrary. For example, in equation (G2), (OG) f1 ) and (OG f2 (OG) can be configured alternately. f1 ) and (OG f2 It can also be configured in segments, and it can also be random. The same applies to the structure (f5).

[0153] In structure (f3), m11 is preferably 1 to 30, more preferably 1 to 20. Additionally, m12 is preferably 1 to 30, more preferably 1 to 20.

[0154] In structure (f4), m12 is preferably 1 to 30, more preferably 1 to 20. Additionally, m14 is preferably 1 to 30, more preferably 1 to 20.

[0155] In structure (f5), m13 is preferably 1 to 30, and more preferably 1 to 20.

[0156] From the perspective of abrasion resistance, the above-mentioned fluorinated polyether chain-(OR) f12 ) m1 - and - (OR f22 ) m2 The proportion of fluorine atoms in the - [{number of fluorine atoms / (number of fluorine atoms + number of hydrogen atoms)} × 100 (%)] is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.

[0157] Furthermore, from the perspective of abrasion resistance, fluorinated polyether chains-(OR) f12 ) m1 - and - (ORf22 ) m2 The molecular weight of the fraction is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, and even more preferably 3,000 to 10,000.

[0158] Q 1 Q is a (n3+n2) valence linking group. 2 It is a (1+n²) valence linker. Hereinafter, Q will be used as the valence group. 1 To provide an explanation on behalf of the representative.

[0159] Q 1 Any group that does not impair the effects of the present invention may be used. For example, examples include alkylene groups having an ether-like oxygen atom or a divalent organopolysiloxane, carbon atoms, nitrogen atoms, silicon atoms, divalent to octvalent organopolysiloxanes, and groups (3-1A), (3-1B), (3-1A-1) to (3-1A-7) removed from the groups described below. 1 (i.e., group P) and the resulting group.

[0160] In addition, Q 1 It can be the group (g2-1) to group (g2-14) described later.

[0161] n2 is an integer greater than or equal to 1. From the viewpoint of superior wear resistance of the surface treatment layer, n2 is preferably 1 to 15, more preferably 1 to 6, even more preferably 2 to 4, and especially preferably 2 or 3.

[0162] n3 is an integer greater than or equal to 1. From the viewpoint of superior wear resistance of the surface treatment layer, n3 is preferably 1 to 3, and more preferably 1.

[0163] -Q in equation (1) 1 -(J 1 ) n2 The indicated group is preferably the group (3-1A) or (3-1B) described below, and more preferably the group (3-1A).

[0164] -Q a -X 31 (-Q) b -J 1 ) h (-R) 31 ) i …(3-1A)

[0165] -Q c -[CH2C(R) 32 (-Q) d -J 1 )] y -R 33 …(3-1B)

[0166] Q a It is a single bond or a divalent linker.

[0167] Examples of divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO2-, and -N(R) groups. d -, -C(O)-, -Si(R) a )2- and groups formed by combining two or more of them.

[0168] The aforementioned divalent hydrocarbon group can be a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenyl group, or an alkyne group. The divalent saturated hydrocarbon group can be linear, branched, or cyclic; for example, alkylene groups are listed. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, even more preferably 4 to 20, and particularly preferably 5 to 15. Furthermore, as a divalent aromatic hydrocarbon group, it is preferable to have 5 to 20 carbon atoms; for example, phenylene groups are listed. In addition, it can also be an alkenyl group or an alkyne group with 2 to 20 carbon atoms.

[0169] The above R a It is an alkyl group (preferably with 1 to 10 carbon atoms) or a phenyl group. The above R... d It is a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms).

[0170] It should be noted that, for example, groups consisting of two or more of these combinations can be categorized as having -OC(O)-, -C(O)O-, -C(O)S-, or -C(O)N(R)-. d )-、-N(R d C(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, -C(O)N(R) d )-alkylene groups, having -N(R d )C(O)- alkylene groups, having -OC(O)N(R d Alkylenes with - ether oxygen atoms, alkylenes with -S-, alkylenes with -OC(O)-, alkylenes with -C(O)O-, alkylenes with -C(O)S-, alkylenes with -N(R) d )-alkylene groups, having -N(R d C(O)N(R) d )-alkylene groups, having -SO2N(R d)-alkylene, alkylene-Si(R a )2-Phenylidene-Si(R a 2.

[0171] Among them, Q a Preferably, it is a divalent hydrocarbon group other than an alkylene group, a divalent heterocyclic group, or a group having -O-, -S-, -SO2-, or -N(R) groups. d -, -C(O)-, -Si(R) a )2-, -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R d )-、-N(R d C(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, -C(O)N(R) d )-alkylene groups, having -N(R d )C(O)- alkylene groups, having -OC(O)N(R d Alkylenes with - ether oxygen atoms, alkylenes with -S-, alkylenes with -OC(O)-, alkylenes with -C(O)O-, alkylenes with -C(O)S-, alkylenes with -N(R) d )-alkylene groups, having -N(R d C(O)N(R) d )-alkylene groups, or those having -SO2N(R d Alkylene groups having -OC(O)- or -C(O)N(R)- are preferred. d )-alkylene groups, having -OC(O)N(R d Alkylenes with -S-, alkylenes with -C(O)O-, alkylenes with -C(O)S-, alkylenes with -N(R) d )-alkylene groups, or those having -N(R d C(O)N(R) d Alkylenes having -C(O)O-, or alkylenes having -C(O)N(R)- d )-alkylene.

[0172] In equation (3-1A), X 31 It can be a single bond, alkylene group, carbon atom, nitrogen atom, silicon atom, organopolysiloxane group with 2 to 8 valences, or a ring group with (h+i+1) valences.

[0173] It should be noted that the aforementioned alkylene groups may have -O-, silylene skeleton groups, divalent organopolysiloxane groups, or dialkylsilylene groups between carbon atoms. Alkylene groups may have multiple groups selected from the group consisting of -O-, silylene skeleton groups, divalent organopolysiloxane groups, and dialkylsilylene groups.

[0174] X 31 The alkylene group represented preferably has 1 to 20 carbon atoms, more preferably 1 to 10.

[0175] As 2 to 8 valent organopolysiloxanes, examples include divalent organopolysiloxanes and (w2+1) valent organopolysiloxanes, which will be discussed later.

[0176] In equation (3-1A), X 31 When Q is a group with a ring having a valence of (h+i+1), a 、(-Q b -J 1 ) and R 31 It is directly bonded to the atoms that make up the ring. This ring is a ring other than the organopolysiloxane ring.

[0177] X 31 The ring in the ring can be any of the following: monocyclic, fused polycyclic, bridged, spirocyclic, and aggregated polycyclic. The atoms constituting the ring can be a carbon ring composed solely of carbon atoms, or a heterocycle composed of heteroatoms with valences of 2 or higher and carbon atoms. Furthermore, the bonds between the atoms constituting the ring can be single bonds or multiple bonds. Moreover, the ring can be aromatic or non-aromatic.

[0178] As a monocyclic ring, 4-membered to 8-membered rings are preferred, and 5-membered and 6-membered rings are more preferred. As a fused polycyclic ring, a fused polycyclic ring consisting of two or more 4-membered to 8-membered rings is preferred, a fused polycyclic ring consisting of two or three rings selected from 5-membered and 6-membered rings bonded together, and a fused polycyclic ring consisting of one or two rings selected from 5-membered and 6-membered rings bonded to one 4-membered ring. As a bridging ring, a bridging ring with a 5-membered or 6-membered ring as the largest ring is preferred, and a spiro ring consisting of two 4-membered to 6-membered rings is preferred. As an aggregated polycyclic ring, an aggregated polycyclic ring consisting of two or three rings selected from 5-membered and 6-membered rings bonded together by single bonds, one to three carbon atoms, or one heteroatom with a valence of 2 or 3 is preferred. It should be noted that in aggregated polycyclic rings, it is preferred that each ring is bonded with a Q. a 、(-Q b -J 1 ) and R 31 Any one of (i=1 or higher).

[0179] Nitrogen, oxygen, and sulfur atoms are preferred as heteroatoms constituting the aforementioned ring, and nitrogen and oxygen atoms are more preferred. The number of heteroatoms constituting the ring is preferably three or less. Furthermore, when the number of heteroatoms constituting the ring is two or more, these heteroatoms can be different.

[0180] As X 31 From the viewpoint that the compound is easy to manufacture and the surface treatment layer has better wear resistance, the preferred ring is one of the following: aliphatic rings with 3 to 8 members, benzene rings, heterocyclic rings with 3 to 8 members, fused rings formed by 2 or 3 of these rings, bridged rings with 5 or 6 members as the largest ring, and polycyclic rings consisting of 2 or more of these rings with single bonds as the connecting groups and alkylene groups, oxygen atoms or sulfur atoms with 3 or fewer carbon atoms.

[0181] Preferred rings are benzene rings, 5- or 6-membered aliphatic rings, 5- or 6-membered heterocycles having nitrogen or oxygen atoms, and fused rings consisting of 5- or 6-membered carbon rings and 4- to 6-membered heterocycles.

[0182] Specific examples of rings include the following rings, as well as 1,3-cyclohexadiene rings, 1,4-cyclohexadiene rings, anthracene rings, cyclopropane rings, decahydronaphthalene rings, norbornene rings, norbornadiene rings, furan rings, pyrrole rings, thiophene rings, pyrazine rings, morpholine rings, aziridine rings, isoquinoline rings, oxazole rings, isoxazole rings, thiazole rings, imidazole rings, pyrazole rings, pyran rings, pyridazine rings, pyrimidine rings, and indene rings. It should be noted that rings with an oxygen group (=O) are also shown below.

[0183]

[0184] Composition of X 31 The non-ring-forming connecting bonds between the atoms of the ring in the middle are with Q. a 、(-Q b -J 1 ) or R 31 Linking bonds. In the presence of remaining linking bonds, these bonds are bonded to hydrogen atoms or substituents. Examples of such substituents include halogen atoms, alkyl groups (optionally containing an ether-like oxygen atom between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, and oxo groups (=O).

[0185] In addition, one of the carbon atoms forming the ring has two atoms related to Q. a 、(-Q b -J 1 ) or R 31 In the case of a bonded linkage, Q can be bonded to this single carbon atom. a and (-Q b -J 1 ), or you can bond two (-Q)b -J 1 ). Preferred Q a With (-Q) b -J 1 ) or R 31 Bonded to different ring-forming atoms. h (-Q) b -J 1 () can bond to different cyclic atoms, and two of them can bond to one cyclic carbon atom, thus the two (-Q) bonds can bond to each other. b -J 1 A ring-shaped carbon atom formed by bonding can consist of more than two R atoms. 31 They can bond to different cyclic atoms, with two of them bonding to one cyclic carbon atom, thus forming two R atoms. 31 There can be more than two carbon atoms in a cyclic ring formed by bonding.

[0186] From the perspective of improving the wear resistance of the surface treatment layer, X 31 Preferably, the group consists of carbon atoms, nitrogen atoms, silicon atoms, organopolysiloxane groups with 4 to 8 valences, or groups with a ring having a (h+i+1) valence, and more preferably carbon atoms.

[0187] In formula (3-1A), Q b It is a single bond or a divalent linker. The definition of a divalent linker is the same as that of Q above. a The definitions described herein are the same.

[0188] Among them, Q b Preferably, the alkylene group has an ether-like oxygen atom. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, even more preferably 2 to 20, but can be 2 to 10, 2 to 6, or 2 to 5. Examples include 2, 3, 8, 9, and 11. Alternatively, the number of carbon atoms can be 1 to 10.

[0189] In equation (3-1A), R 31 It can be a hydrogen atom, a hydroxyl group, or an alkyl group. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3, and even more preferably 1.

[0190] X 31 When the bond is a single bond or an alkylene group, h is 1 and i is 0.

[0191] X 31 When the atom is nitrogen, h is an integer from 1 to 2, and i is an integer from 0 to 1, satisfying h + i = 2.

[0192] X 31 When the atoms are carbon or silicon, h is an integer from 1 to 3, and i is an integer from 0 to 2, satisfying h + i = 3.

[0193] X31 When the alkyl group is a 2-8 valent organopolysiloxane, h is an integer from 1 to 7, and i is an integer from 0 to 6, satisfying h+i=1~7.

[0194] X 31 When the group is a ring with a valence of (h+i+1), h is an integer from 1 to 7 and i is an integer from 0 to 6, satisfying h+i=1~7.

[0195] (-Q) b -J 1 When there are two or more (-Q) b -J 1 (They can be either the same as or different from each other.)

[0196] R 31 When there are two or more, the two or more (-R) 31 (They can be either the same as or different from each other.)

[0197] From the perspective of improving the wear resistance of the surface treatment layer, i is preferably 0.

[0198] In formula (3-1A), Q a X 31 and Q b When it is a single bond, J 1 With R f1 Direct bonding.

[0199] In equation (3-1B), Q c It is a single bond or a divalent linker.

[0200] Q c The definition of the divalent linker in Q is the same as that in Q above. a The definitions described herein are the same.

[0201] In equation (3-1B), R 32 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; from the viewpoint of easy compound production, a hydrogen atom is preferred.

[0202] As an alkyl group, methyl is preferred.

[0203] In equation (3-1B), Q d It is a single bond or an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6. From the viewpoint of easy compound preparation, Q... d Preferably, it is a single bond or CH2-.

[0204] In equation (3-1B), R 33 It can be a hydrogen atom or a halogen atom; from the viewpoint of easily making compounds, a hydrogen atom is preferred.

[0205] y is an integer from 1 to 10, preferably an integer from 1 to 6.

[0206] Two or more [CH2C(R)] 32 (-Q) d -J 1 [Optional: can be the same as or different from each other.]

[0207] As a group (3-1A), the following groups (3-1A-1) to (3-1A-7) are preferred.

[0208] -Z 1 -(X) 32 ) s1 -Q b1 -J 1 …(3-1A-1)

[0209] -Z 1 -(X) 33 ) s2 -Q a2 -N[-Q b2 -J 1 ]2 …(3-1A-2)

[0210] -Q a3 -Si(R) g )[-Q b3 -J 1 ]2 …(3-1A-3)

[0211] -Z 1 -[Q e ] s4 -Q a4 -(O) t4 -C[-(O) u4 -Q b4 -J 1 ] 3-w1 (-R) 31 ) w1 …(3-1A-4)

[0212] -Q a5 -Si[-Q b5 -J 1 ]3 …(3-1A-5)

[0213] -Z 1 -[Q e ] v -Q a6 -Z a [-Q b6 -J 1 ] w2 …(3-1A-6)

[0214] -Z1 -[Q e ] s4 -Q a4 -(O) t4 -Z c [-(OQ b4 ) u4 -J 1 ] w3 (-OH) w4 …(3-1A-7)

[0215] Wherein, the group (3-1A) is preferably the group (3-1A-4).

[0216] In equations (3-1A-1), (3-1A-2), (3-1A-4), (3-1A-6), and (3-1A-7), Z 1 It is a single bond, or optionally an alkylene group having an oxygen atom between carbon atoms. Examples of such alkylene groups include Q. a The alkylene groups illustrated with the divalent linking group are also preferred in the same manner.

[0217] In group (3-1A-1), X 32 -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d )-(where N and Q in the formula b1 (bonding).

[0218] R d The definition is as described above.

[0219] s1 is either 0 or 1.

[0220] Among them, X 32 Preferably -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d- or -C(O)N(R) d -, more preferably -O-, -S-, -N(R) d )-, -C(O)O-, -C(O)S-, -N(R d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d -, more preferably -C(O)O- or -C(O)N(R) d )-.

[0221] Q b1 It can be a single bond or an alkylene group. It should be noted that the alkylene group can have -O-, a silylene skeleton group, or a dialkylsilyl group. The alkylene group can have multiple groups selected from the group consisting of -O-, silylene skeleton groups, divalent organopolysiloxane groups, and dialkylsilyl groups.

[0222] It should be noted that, in the case where the alkylene group has -O-, silylene skeleton groups, divalent organopolysiloxane, or dialkylsilylene, these groups are preferably present between carbon atoms.

[0223] Q b1 The alkylene group represented preferably has 1 to 30 carbon atoms, more preferably 1 to 20, even more preferably 2 to 20, and particularly preferably 2 to 6. Alternatively, the number of carbon atoms can be 1 to 10.

[0224] Among them, Q b1 Preferably, it is an alkylene group having 2 to 6 carbon atoms.

[0225] As a group (3-1A-1) -(X 32 ) s1 -Q b1 -J 1 Specific examples can be listed below, including the following groups. In the following formulas, * indicates a group related to Z. 1 The bonding positions.

[0226]

[0227] In group (3-1A-2), X 33 -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d-, -OC(O)N(R) d - or -C(O)N(R) d )-.

[0228] R d The definition is as described above.

[0229] s2 is either 0 or 1. From the viewpoint of easily manufacturing compounds, s2 is preferably 0.

[0230] Among them, X 33 Preferably -O-, -S-, -N(R) d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)-, -N(R) d C(O)N(R) d -, -OC(O)N(R) d - or -C(O)N(R) d -, more preferably -C(O)O-, -C(O)S-, -SO2N(R) d - or -C(O)N(R) d )-.

[0231] Q a2 It is a single bond, alkylene, -C(O)-, or an etheric oxygen atom between carbon atoms of alkylene with more than 2 carbon atoms, -C(O)-, -C(O)O-, -OC(O)-, -C(O)N(R) d )-、-N(R d C(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, -C(O)N(R) d () or -NH- groups.

[0232] Q a2 The alkylene group represented preferably has 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 3.

[0233] Q a2 The carbon-carbon atoms of alkylene groups with 2 or more carbon atoms are separated by ether-type oxygen atoms, -C(O)-, -C(O)O-, -OC(O)-, or -C(O)N(R).d )-、-N(R d C(O)-, -N(R) d C(O)N(R) d )-、-N(R d )C(O)O-, -OC(O)N(R d -, -SO2N(R) d )-、-N(R d SO2-, -C(O)N(R) d The number of carbon atoms in the group with -NH or -NH is preferably 2 to 10, more preferably 2 to 6.

[0234] From the perspective of easily manufacturing compounds, Q a2 Single bonds are preferred.

[0235] Q b2 It is an alkylene group, or an organopolysiloxane group having a divalent oxygen atom or -NH- between carbon atoms in an alkylene group having two or more carbon atoms.

[0236] Q b2 The alkylene group represented preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. Alternatively, the number of carbon atoms mentioned above can be 1 to 10.

[0237] Q b2 The alkylene group representing 2 or more carbon atoms has a divalent organopolysiloxane alkyl group, an ether oxygen atom, or a -NH- group between carbon atoms, preferably 2 to 10, more preferably 2 to 6.

[0238] As Q b2 From the viewpoint of easy compound preparation, -CH2CH2CH2- and -CH2CH2OCH2CH2CH2- (where the right side is bonded to Si) are preferred.

[0239] 2 [-Q] b2 -J 1 They can be either the same as or different from each other.

[0240] -(X) as a group (3-1A-2) 33 ) s2 -Q a2 -N[-Q b2 -J 1 Specific examples of ]2 can be listed below, including the following groups. In the following formulas, * indicates a group related to Z. 1 The bonding position. Additionally, in the formula, with J... 1 Bonded (CH2) αIn this context, α is an integer representing the number of methylene groups, preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 can be listed. Additionally, the number of carbon atoms can be 1 to 10. The multiple α groups contained in the same compound may be the same or different from each other, but are preferably the same. For example, all the multiple α groups contained in the same compound may be 2, 3, 8, 9, and 11. The same applies below.

[0241]

[0242] In group (3-1A-3), Q a3 It is a single bond, or may have an alkylene group with an ether-like oxygen atom. From the viewpoint of easy compound preparation, Q a3 Single bonds are preferred.

[0243] The number of carbon atoms in the alkylene group that may have ether-like oxygen atoms is preferably 1 to 10, and particularly preferably 2 to 6.

[0244] R g It can be a hydrogen atom, a hydroxyl group, or an alkyl group.

[0245] As R g From the viewpoint of easy compound production, hydrogen atoms or alkyl groups are preferred. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4, and even more preferably methyl.

[0246] Q b3 It is an alkylene group, or an alkylene group having an ether oxygen atom or a divalent organopolysiloxane between carbon atoms.

[0247] Q b3 The alkylene group represented preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are examples. In addition, the number of carbon atoms mentioned above can be 1 to 10.

[0248] Q b3 The carbon number of the alkylene group with 2 or more carbon atoms having an ether oxygen atom or a divalent organopolysiloxane group between carbon atoms is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0249] From the perspective of easily manufacturing compounds, Q b3 Preferably, it is -CH2CH2-, -CH2CH2CH2-, or -CH2CH2CH2CH2CH2CH2CH2CH2-.

[0250] 2 [-Q] b3 -J1 They can be either the same as or different from each other.

[0251] -Si(R) as a group (3-1A-3) g )[-Q b3 -J 1 Specific examples of ]2 can be listed below, including the following groups. In the following formulas, * indicates a group related to Q. a3 The bonding positions.

[0252]

[0253] In group (3-1A-4), Q e is -C(O)O-, -SO2N(R d )-、-N(R d SO2-, -N(R) d C(O)- or -C(O)N(R) d )-.

[0254] R 31 The definition is as described above. When w1 is 1 or 2, R... 31 Hydrogen atoms are preferred.

[0255] s4 is either 0 or 1.

[0256] Q a4 It is a single bond, or an alkylene group that may have an ether-like oxygen atom.

[0257] The number of carbon atoms in the alkylene group that may have ether-like oxygen atoms is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 3.

[0258] t4 is 0 or 1 (where Q is 0 or 1). a4 (0 when it is a single bond).

[0259] As -Q a4 -(O) t4 From the viewpoint of easy compound preparation, when s4 is 0, single bonds, -CH2O-, -CH2OCH2-, -CH2OCH2CH2O-, -CH2OCH2CH2OCH2-, and -CH2OCH2CH2CH2CH2OCH2- are preferred (where the left side is related to Q). e (For bonding), when s4 is 1, single bonds, -CH2-, and -CH2CH2- are preferred.

[0260] Q b4 It is an alkylene group, and the alkylene group may have -O-, -C(O)N(R) d )-(R d(as defined above), silymine skeleton group, divalent organopolysiloxane or dialkylsilyl group.

[0261] It should be noted that when the alkylene group has an -O- or silanine skeleton group, it is preferable that the -O- or silanine skeleton group is present between carbon atoms. Additionally, the alkylene group has a -C(O)N(R) skeleton. d When it is a dialkylmethylenesilyl or divalent organopolysiloxane, it is preferably located between carbon atoms or with (O). u4 These groups are located at the end of the bonded side.

[0262] Q b4 The alkylene group represented preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are examples. In addition, the number of carbon atoms mentioned above can be 1 to 10.

[0263] u4 is either 0 or 1.

[0264] As - (O) u4 -Q b4 - From the viewpoint of easy compound preparation, the preferred compounds are -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2CH2-, -CH2OCH2CH2CH2CH2CH2-, -OCH2CH2CH2-, -OSi(CH3)2CH2CH2CH2-, -OSi(CH3)2OSi(CH3)2CH2CH2CH2-, and -CH2CH2CH2Si(CH3)2PhSi(CH3)2CH2CH2- (where the right side is bonded to Si).

[0265] w1 is an integer from 0 to 2, preferably 0 or 1, and especially preferably 0.

[0266] There are more than two [-(O)] u4 -Q b4 -J 1 In the case of ], more than 2 [-(O) u4 -Q b4 -J 1 They can be either the same as or different from each other.

[0267] R 31 When there are two or more, the two or more (-R) 31 (They can be either the same as or different from each other.)

[0268] [Q] as a group (3-1A-4) e ] s4 -Q a4 -(O)t4 -C[-(O) u4 -Q b4 -J 1 ] 3-w1 (-R) 31 ) w1 Specific examples of [ ] can be listed below, including the following groups. In the following formulas, * indicates a group related to Z. 1 The bonding positions.

[0269]

[0270] In group (3-1A-5), Q a5 It can be an alkylene group that optionally has an ether-like oxygen atom.

[0271] The number of carbon atoms in the alkylene group that may have ether-like oxygen atoms is preferably 1 to 10, and particularly preferably 2 to 6.

[0272] As Q a5 From the viewpoint of easy compound preparation, -OCH2CH2CH2-, -OCH2CH2OCH2CH2CH2-, -CH2CH2-, and -CH2CH2CH2- (where the right side is bonded to Si) are preferred.

[0273] Q b5 It is an alkylene group, or an alkylene group having an ether oxygen atom or a divalent organopolysiloxane between carbon atoms.

[0274] Q b5 The alkylene group represented preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are examples. In addition, the number of carbon atoms mentioned above can be 1 to 10.

[0275] Q b5 The carbon number of the alkylene group with 2 or more carbon atoms having an ether oxygen atom or a divalent organopolysiloxane group between carbon atoms is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0276] As Q b5 From the viewpoint of easy compound preparation, -CH2CH2CH2- and -CH2CH2OCH2CH2CH2- are preferred (wherein, the right side is the same as J). 1 (bonding).

[0277] 3 [-Q] b5 -J 1 They can be either the same as or different from each other.

[0278] Specific examples of the group (3-1A-5) can be listed below. In the following formulas, * indicates a group related to R. f1 The bonding positions.

[0279]

[0280] Q in group (3-1A-6) e The definition is as defined in the group (3-1A-4) above.

[0281] v is 0 or 1.

[0282] Q a6 It can be an alkylene group that optionally has an ether-like oxygen atom.

[0283] The number of carbon atoms in the alkylene group that may have ether-like oxygen atoms is preferably 1 to 10, and particularly preferably 2 to 6.

[0284] As Q a6 From the viewpoint of easy compound preparation, the preferred compounds are -CH2OCH2CH2CH2-, -CH2OCH2CH2OCH2CH2CH2-, -CH2CH2-, and -CH2CH2CH2- (where the right side is the same as Z). a (bonding).

[0285] Z a It is an organopolysiloxane group with a (w2+1) valence, or a (w2+1) valence group having an alkylene group between two organopolysiloxane groups.

[0286] w2 is an integer between 2 and 7.

[0287] The following groups can be listed as (w2+1) valence organopolysiloxane groups and (w2+1) valence groups having an alkylene group between organopolysiloxane groups. Wherein, R in the following formula... a As described above. * indicates the bonding site.

[0288]

[0289] Q b6 It is an alkylene group, or an alkylene group having an ether oxygen atom or a divalent organopolysiloxane between carbon atoms.

[0290] Q b6 The alkylene group represented preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are examples. In addition, the number of carbon atoms mentioned above can be 1 to 10.

[0291] Qb6 The carbon number of the alkylene group with 2 or more carbon atoms having an ether oxygen atom or a divalent organopolysiloxane group between carbon atoms is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0292] As Q b6 From the viewpoint of easy compound production, -CH2CH2- and -CH2CH2CH2- are preferred.

[0293] w2 of [-Q] b6 -J 1 They can be either the same as or different from each other.

[0294] -[Q, as a group (3-1A-6) e ] v -Q a6 -Z a [-Q b6 -J 1 ] w2 Specific examples can be listed below, including the following groups. In the following formulas, * indicates a group related to Z. 1 The bonding positions.

[0295]

[0296] In group (3-1A-7), Z c Hydrocarbon groups with a valence of (w3+w4+1).

[0297] w3 is an integer greater than or equal to 4.

[0298] w4 is an integer greater than or equal to 0.

[0299] Q e s4, Q a4 t4, Q b4 The definition and preferred range of u4 are the same as those of the symbols in group (3-1A-4).

[0300] Z c It can be composed of hydrocarbon chains, or it can have ether-like oxygen atoms between carbon atoms in the hydrocarbon chain, preferably composed of hydrocarbon chains.

[0301] Z c The valence is preferably 5 to 20, more preferably 5 to 10, even more preferably 5 to 8, and particularly preferably 5 to 6.

[0302] Z c The number of carbon atoms is preferably 3 to 50, more preferably 4 to 40, and even more preferably 5 to 30.

[0303] w3 is preferably 4~20, more preferably 4~16, even more preferably 4~8, and particularly preferably 4~5.

[0304] w4 is preferably 0~10, more preferably 0~8, further preferably 0~6, particularly preferably 0~3, and most preferably 0~1.

[0305] When there are more than 2 [-(OQ) b4 ) u4 -J 1 In the case of ], more than 2 [- (OQ) b4 ) u4 -J 1 They can be either the same as or different from each other.

[0306] -[Q, as a group (3-1A-7) e ] s4 -Q a4 -(O) t4 -Z c [-(OQ b4 ) u4 -J 1 ] w3 Specific examples can be listed below, including the following groups. In the following formulas, * indicates a group related to Z. 1 The bonding positions.

[0307]

[0308] Q 1 It can be group (g2-1) (where n3=d1+d3, n2=d2+d4), group (g2-2) (where n3=e1, n2=e2), group (g2-3) (where n3=1, n2=2), group (g2-4) (where n3=h1, n2=h2), group (g2-5) (where n3=i1, n2=i2), group (g2-6) (where n3=1, n2=1), or group (g2-7) (where n3=1, n2=i3).

[0309]

[0310] (-A) 1 -Q 12 -) e1 C(R) e2 ) 4-e1-e2 (-Q) 22 -) e2 …(g2-2)

[0311] -A 1 -Q 13 -N(-Q 23-)2 …(g2-3)

[0312] (-A) 1 -Q 14 -) h1 Z(-Q) 24 -) h2 …(g2-4)

[0313] (-A) 1 -Q 15 -) i1 Si(R) e3 ) 4-i1-i2 (-Q) 25 -) i2 …(g2-5)

[0314] -A 1 -Q 26 - …(g2-6)

[0315] -A 1 -Q 12 -CH (-Q) 22 -)-Si(R e3 ) 3-i3 (-Q) 25 -) i3 …(g2-7)

[0316] In equations (g2-1) to (g2-7), A 1 Side and R f1 Bonding, Q 22 Q 23 Q 24 Q 25 Or Q 26 Side and J 1 Bonding.

[0317] A 1 For single bond, -C(O)NR e6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR e6 -、-O- or SO2NR e6 -

[0318] Q 12 It is a single bond, an alkylene group, or an alkylene group having a -C(O)NR bond between carbon atoms. 6 -、-C(O)-、-NR 6 - or O- groups, with more than 2 Q groups present. 12 At that time, more than 2 Qs 12 Choose whether they are the same or different from each other.

[0319] Q13 For a single bond (where Q is a single bond) 1 For -C(O)-, alkylene groups, and alkylene groups with more than 2 carbon atoms having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 A group with - or O-, or a group having -C(O)- at the N-side end of an alkylene group.

[0320] Q 14 In Q 14 When the atom in the bonded Z is a carbon atom, it is Q. 12 In Q 14 When the atom in the bonded Z is a nitrogen atom, it is Q. 13 In Q 14 In the case of two or more, two or more Q 14 Choose whether they are the same or different from each other.

[0321] Q 15 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 - or O- groups, with more than 2 Q groups present. 15 At that time, more than 2 Qs 15 Choose whether they are the same or different from each other.

[0322] Q 22 Alkylenes, wherein the carbon atoms of alkylenes having two or more carbon atoms have a -C(O)NR bond. 6 -、-C(O)-、-NR 6 - or O- groups, alkyl groups with -C(O)NR at the end of the side not connected to Si. 6 -、-C(O)-、-NR 6 - or O- groups, or alkylene groups having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 - or O- and the end of the side not connected to Si has -C(O)NR 6 -、-C(O)-、-NR 6 - or O- groups, with more than 2 Q groups present. 22 At that time, more than 2 Qs 22 Choose whether they are the same or different from each other.

[0323] Q 23 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR6 - or O- groups, 2 Q 23 Choose whether they are the same or different from each other.

[0324] Q 24 In Q 24 When the atom in the bonded Z is a carbon atom, it is Q. 22 In Q 24 When the atom in the bonded Z is a nitrogen atom, it is Q. 23 In Q 24 In the case of two or more, two or more Q 24 Choose whether they are the same or different from each other.

[0325] Q 25 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 - or O- groups, with more than 2 Q groups present. 25 At that time, more than 2 Qs 25 Choose whether they are the same or different from each other.

[0326] Q 26 It is an alkylene group, or an alkylene group having -C(O)NR between carbon atoms. 6 -、-C(O)-、-NR 6 - or O- groups.

[0327] Q 22 Q 23 Q 24 Q 25 Q 26 When it is an alkylene group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0328] Z is a (h1+h2) valence group with a ring structure, and the group has Q 14 Directly bonded carbon or nitrogen atoms, and possessing Q 24 Directly bonded carbon or nitrogen atoms.

[0329] R e1 It is a hydrogen atom or an alkyl group, and contains more than 2 R atoms. e1 At that time, more than 2 R e1 Choose whether they are the same or different from each other.

[0330] R e2 It can be a hydrogen atom, hydroxyl group, alkyl group or acyloxy group.

[0331] R e3 It is an alkyl group. R 6It consists of hydrogen atoms and alkyl or phenyl groups having 1 to 6 carbon atoms.

[0332] d1 is an integer from 0 to 3, preferably 1 or 2.

[0333] d2 is an integer from 0 to 3, preferably 1 or 2.

[0334] d1+d2 are integers from 1 to 3.

[0335] d3 is an integer from 0 to 3, preferably 0 or 1.

[0336] d4 is an integer from 0 to 3, preferably 2 or 3.

[0337] d3+d4 is an integer from 1 to 3.

[0338] d1+d3 is an integer from 1 to 5, preferably 1 or 2.

[0339] d2+d4 is an integer from 1 to 5, preferably 2 or 3.

[0340] e1+e2 is 3 or 4.

[0341] e1 is an integer from 1 to 3, preferably 1 or 2.

[0342] e2 is an integer from 1 to 3, preferably 2 or 3.

[0343] h1 is an integer greater than or equal to 1, preferably 1 or 2.

[0344] h2 is an integer greater than or equal to 1, preferably 2 or 3.

[0345] i1+i2 is 3 or 4.

[0346] i1 is an integer from 1 to 3, preferably 1 or 2.

[0347] i2 is an integer from 1 to 3, preferably 2 or 3.

[0348] i3 is 2 or 3.

[0349] From the perspective of ease of compound manufacturing and superior wear resistance of the surface treatment layer, Q 12 Q 13 Q 14 Q 15 Q 22 Q 23 Q 24 Q 25 and Q 26The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can also have 2 to 10 or 2 to 6 carbon atoms. Examples include 2, 3, 8, 9, and 11. Alternatively, the number of carbon atoms can be 1 to 10, 1 to 6, or 1 to 4. The lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0350] As ring structures in Z, the above-mentioned ring structures can be listed, and the preferred method is also the same.

[0351] It should be noted that, due to Q 14 Q 24 It is directly bonded to the ring structure in Z; therefore, for example, there is no alkylene group connected to the ring structure and Q... 14 Q 24 The case of connection with the alkylene group.

[0352] From the perspective of easily manufacturing compounds, R e1 R e2 Or R e3 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and especially preferably 1 to 2.

[0353] From the perspective of easily manufacturing compounds, R e2 The number of carbon atoms in the alkyl portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and especially preferably 1 to 2.

[0354] From the viewpoint of ease of compound manufacturing and superior wear resistance of the surface treatment layer, h1 is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and especially preferably 1.

[0355] From the viewpoint of ease of compound manufacturing and superior wear resistance of the surface treatment layer, h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.

[0356] As Q 1 Other forms can be listed as group (g2-8) (where n3=d1+d3, n2=d2×k3+d4×k3), group (g2-9) (where n3=e1, n2=e2×k3), group (g2-10) (where n3=1, n2=2×k3), group (g2-11) (where n3=h1, n2=h2×k3), group (g2-12) (where n3=i1, n2=i2×k3), group (g2-13) (where n3=1, n2=k3), or group (g2-14) (where n3=1, n2=i3×k3).

[0357]

[0358] (-A) 1 -Q 12 -) e1 C(R) e2 ) 4-e1-e2 (-Q) 22 -G 1 ) e2 …(g2-9)

[0359] -A 1 -Q 13 -N(-Q 23 -G 1 )2 …(g2-10)

[0360] (-A) 1 -Q 14 -) h1 Z(-Q) 24 -G 1 ) h2 …(g2-11)

[0361] (-A) 1 -Q 15 -) i1 Si(R) e3 ) 4-i1-i2 (-Q) 25 -G 1 ) i2 …(g2-12)

[0362] -A 1 -Q 26 -G 1 …(g2-13)

[0363] -A 1 -Q 12 -CH (-Q) 22 -G 1 )-Si(R e3 ) 3-i3 (-Q) 25 -G 1 ) i3 …(g2-14)

[0364] In equations (g2-8) to (g2-14), A 1 Side and R f1 Bonding, G 1 Side and J 1 Bonding.

[0365] G 1 For the following group (g3), Q 1 Having more than 2 Gs 1Choose either the same as or different from each other. G 1 The symbols other than those in equations (g2-1) to (g2-7) are the same.

[0366] -Si(R) 8 ) 3-k3 (-Q) 3 -) k3 …(g3)

[0367] In group (g3), the Si side is related to Q. 22 Q 23 Q 24 Q 25 and Q 26 Connection, Q 3 Side and J 1 Connection. R 8 It is an alkyl group. Q 3 Alkylenes, wherein the carbon atoms of alkylenes having two or more carbon atoms have a -C(O)NR bond. 6 -、-C(O)-、-NR 6 - or -O- groups, or (OSi(R) 9 )2) p -O-, 2 or more Qs 3 They can be the same or different. k3 is 2 or 3. R 6 It is an alkyl or phenyl group with 1 to 6 carbon atoms and hydrogen atoms. R 9 It is an alkyl, phenyl, or alkoxy group, with two Rs. 9 Choose any two that are the same or different. p is an integer from 0 to 5. When p is 2 or higher, there are two or more (OSi(R)). 9 2) Choose either the same or different from each other.

[0368] From the perspective of ease of compound manufacturing and superior wear resistance of the surface treatment layer, Q 3 The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 2 to 20. It can also have 2 to 10 or 2 to 6 carbon atoms. Examples include 2, 3, 8, 9, and 11. Alternatively, the number of carbon atoms can be 1 to 10, 1 to 6, or 1 to 4. The lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0369] From the perspective of easily manufacturing compounds, R 8 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0370] From the perspective of easily manufacturing compounds, R 9The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0371] From the perspective of the excellent storage stability of compounds, R 9 The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and especially preferably 1 to 2.

[0372] p is preferably 0 or 1.

[0373] Examples of compounds according to the present invention include those with the following formula. From the viewpoint of ease of industrial manufacture, ease of processing, and superior water repellency and abrasion resistance of the surface treatment layer, compounds with the following formula are preferred. In the compounds with the following formula, R... t With equation (1) (R) f1 The same applies to both, and the preferred selection method is also the same.

[0374] Q in equation (1) 1 Compounds with a group (g2-1) can be listed, for example, compounds with the following formula.

[0375]

[0376] Q in equation (1) 1 Compounds with a group (g2-2) are listed, for example, compounds with the following formula. In the following formula, Ak refers to an alkyl group (e.g., an alkyl group with 1 to 15 carbon atoms).

[0377]

[0378]

[0379] Q in equation (1) 1 Compounds with a group (g2-3) can be listed as examples of compounds with the following formula.

[0380]

[0381] Q in equation (1) 1 Compounds with a group (g2-4) can be listed as examples of compounds with the following formula.

[0382]

[0383] Q in equation (1) 1 Compounds with a group (g2-5) can be listed as examples of compounds with the following formula.

[0384]

[0385] Q in equation (1) 1Compounds with a group (g2-6) can be listed as examples of compounds with the following formula.

[0386]

[0387] Q in equation (1) 1 Compounds with a group (g2-7) can be listed as examples of compounds with the following formula.

[0388]

[0389] Q in equation (1) 1 Compounds with a group (g2-8) can be listed as examples of compounds with the following formula.

[0390]

[0391] Q in equation (1) 1 Compounds with a group (g2-9) can be listed as examples of compounds with the following formula.

[0392]

[0393] Q in equation (1) 1 Compounds with a group (g2-10) can be listed as examples of compounds with the following formula.

[0394]

[0395] Q in equation (1) 1 Compounds with a group (g2-11) can be listed, for example, compounds with the following formula.

[0396]

[0397] Q in equation (1) 1 Compounds with a group (g2-12) can be listed as examples of compounds with the following formula.

[0398]

[0399] Q in equation (1) 1 Compounds with a group (g2-13) can be listed as examples of compounds with the following formula.

[0400]

[0401] Q in equation (1) 1 Compounds with a group (g2-14) can be listed as examples of compounds with the following formula.

[0402]

[0403] Specific examples of compounds of the present invention can be listed below, but are not limited to these compounds. It should be noted that n in the formula is preferably an integer from 1 to 250, more preferably an integer from 5 to 250, and even more preferably an integer from 5 to 50. It can be an integer from 1 to 50, or an integer from 5 to 30. For example, 10, 14, 15, 20, 23, and 25 can be listed.

[0404]

[0405]

[0406] [Composition]

[0407] The composition of the present invention may contain at least one of the compounds shown in formula (1) and formula (2), and there is no particular limitation on the components other than the compounds of the present invention (hereinafter also referred to as "other components"). It should be noted that the surface treatment agent of the present invention may contain both the compounds shown in formula (1) and the compounds shown in formula (2).

[0408] Specific examples of other components include fluorinated compounds other than those of the present invention, at least one of the following impurities, liquid media, etc.

[0409] Other fluorinated compounds include fluorinated compounds that are byproducts of the manufacture of this compound (hereinafter also referred to as "byproduct fluorinated compounds"), and known fluorinated compounds used for the same purposes as the aforementioned fluorinated ether compounds.

[0410] As for other fluorinated compounds, those that are less likely to reduce the properties of the compound are preferred.

[0411] From the viewpoint of fully utilizing the properties of the compound, the content of other fluorinated compounds is preferably less than 70% by mass, more preferably less than 50% by mass, further preferably less than 20% by mass, especially preferably less than 10% by mass, and most preferably less than 5% by mass relative to the total mass of the surface treatment agent.

[0412] Examples of byproduct fluorinated compounds include unreacted fluorinated compounds generated during the synthesis of this compound. When the composition of the present invention contains a byproduct fluorinated compound, the purification process for removing or reducing the amount of this byproduct fluorinated compound can be simplified.

[0413] Fluorine-containing compounds are well-known examples, such as those described in the following documents.

[0414] The perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No. 11-029585,

[0415] The silicon-containing organic fluoropolymer described in Japanese Patent No. 2874715

[0416] Organosilicon compounds described in Japanese Patent Application Publication No. 2000-144097

[0417] The perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No. 2000-327772,

[0418] Fluorinated siloxanes as described in Japanese Patent Publication No. 2002-506887

[0419] Organosilicone compounds described in Japanese Patent Publication No. 2008-534696

[0420] Fluorinated modified hydrogen-containing polymers described in Japanese Patent No. 4138936

[0421] The compounds described in U.S. Patent Application Publication No. 2010 / 0129672, International Publication No. 2014 / 126064, and Japanese Patent Application Publication No. 2014-070163,

[0422] Organosilicon compounds described in International Publication No. 2011 / 060047 and International Publication No. 2011 / 059430,

[0423] Fluorinated organosilane compounds described in International Publication No. 2012 / 064649

[0424] The polymers containing fluorinated alkylene oxides described in Japanese Patent Application Publication No. 2012-72272

[0425] Fluorinated ether compounds described in International Publication Nos. 2013 / 042732, 2013 / 121984, 2013 / 121985, 2013 / 121986, 2014 / 163004, Japanese Patent Application Publication No. 2014-080473, 2015 / 087902, 2017 / 038830, 2017 / 038832, and 2017 / 187775.

[0426] Silane compounds containing perfluoro(poly)ethers as described in Japanese Patent Application Publication No. 2014-218639, International Publication No. 2017 / 022437, International Publication No. 2018 / 079743, and International Publication No. 2018 / 143433

[0427] Fluorinated polyether-based polymer-modified silanes described in Japanese Patent Application Publication Nos. 2015-199906, 2016-204656, 2016-210854, and 2016-222859

[0428] Fluorinated ether compounds described in International Publication No. 2018 / 216630, International Publication No. 2019 / 039226, International Publication No. 2019 / 039341, International Publication No. 2019 / 039186, International Publication No. 2019 / 044479, Japanese Patent Application Publication No. 2019-44158, International Publication No. 2019 / 044479, and International Publication No. 2019 / 163282.

[0429] In addition, commercially available fluorinated compounds include Shin-Etsu Chemical Co., Ltd.'s KY-100 series (KY-178, KY-185, KY-195, etc.), AGC's SURECO AF series (such as SURECO 2101S), and DAIKIN INDUSTRIES, LTD.'s OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, OPTOOL (registered trademark) UD509, OPTOOL (registered trademark) UD120, etc.

[0430] When the surface treatment agent contains other fluorinated compounds, the content of the other fluorinated compounds is preferably 60% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less, relative to the total content of the fluorinated ether compounds and other fluorinated compounds in the surface treatment agent.

[0431] The total content of the above-mentioned fluorinated ether compounds and other fluorinated compounds in this surface treatment agent is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more.

[0432] When the content of the aforementioned fluorinated ether compounds and other fluorinated compounds is within the above range, the surface layer exhibits excellent water and oil repellency, abrasion resistance, fingerprint removal, lubricity, and appearance.

[0433] The content of the compound of the present invention is preferably 0.01 to 50% by mass, more preferably 0.03 to 40% by mass, and even more preferably 0.05 to 30% by mass, relative to the total mass of the composition of the present invention. When the content of the compound of the present invention is within the above range, the surface treatment layer has better water and oil repellency, abrasion resistance, fingerprint removal, lubricity, and appearance.

[0434] The liquid medium contained in the composition of the present invention may be only one type or may be two or more types.

[0435] As a liquid medium, an organic solvent is preferred. The organic solvent can be a fluorinated organic solvent, a non-fluorinated organic solvent, or a mixture of both.

[0436] Fluorinated organic solvents include fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, fluoroalkylamines, fluoroalcohols, and hydrofluoroolefins.

[0437] As fluoroalkanes, compounds with 4 to 8 carbon atoms are preferred. Commercially available examples include C6F... 13 H (AGC Corporation, ASAHIKLIN (registered trademark) AC-2000), C6F 13 C2H5 (manufactured by AGC Corporation, ASAHIKLIN (registered trademark) AC-6000), C2F5CHFCHFCF3 (manufactured by Chemours Corporation, Vertrel (registered trademark) XF), etc.

[0438] Specific examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.

[0439] As fluoroalkyl ethers, compounds with 4 to 12 carbon atoms are preferred. Examples of commercially available products include CF3CH2OCF2CF2H (manufactured by AGC, ASAHIKLIN (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, NOVEC (registered trademark (7100)), C4F9OC2H5 (manufactured by 3M, NOVEC (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, NOVEC (registered trademark) 7300).

[0440] Specific examples of fluoroalkylamines include perfluorotripropylamine and perfluorotributylamine.

[0441] Specific examples of fluorinated alcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0442] Specific examples of hydrofluoroolefins include 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd). Commercially available examples include AMOLEA (registered trademark) AS-300 manufactured by AGC.

[0443] As a non-fluorinated organic solvent, compounds containing only hydrogen and carbon atoms and compounds containing only hydrogen, carbon and oxygen atoms are preferred. Examples include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents and ester organic solvents.

[0444] When the surface treatment agent contains a liquid medium, the surface treatment agent preferably contains 60 to 99.999% by mass of the liquid medium, more preferably 85 to 99.99% by mass, and more preferably 90 to 99.9% by mass.

[0445] This surface treatment agent may further contain known additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reactions of the P group.

[0446] The content of the additive relative to the total mass of the surface treatment agent is preferably 10% by mass or less, more preferably 1% by mass or less.

[0447] [Surface treatment agent]

[0448] In one embodiment, the surface treatment agent of the present invention comprises the compound of the present invention. Alternatively, the surface treatment agent of the present invention may comprise the compound of the present invention and a liquid medium. The surface treatment agent of the present invention may be a composition of the present invention. The preferred manner in which the liquid medium is included in the surface treatment agent is the same as the preferred manner in which the liquid medium is included in the composition of the present invention.

[0449] The compounds of the present invention contain alkyl groups having two or more carbon atoms, organopolysiloxane alkyl groups, and the P group. Therefore, by using a surface treatment agent containing the compounds of the present invention, a surface treatment layer with excellent water repellency and abrasion resistance can be formed.

[0450] The surface treatment agent of the present invention only needs to contain at least one of the compounds shown in formula (1) and formula (2). It should be noted that the surface treatment agent of the present invention may contain both the compound shown in formula (1) and the compound shown in formula (2).

[0451] The surface treatment agent of the present invention is particularly preferred for use in optical components.

[0452] [thing]

[0453] In one embodiment, the article of the present invention comprises a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent of the present invention.

[0454] The surface treatment layer can be formed on a portion of the substrate surface or on the entire substrate surface. The surface treatment layer can be spread into a film on the substrate surface or distributed in a dotted pattern.

[0455] In the surface treatment layer, the compound of the present invention is contained in a state in which part or all of the group P has been hydrolyzed and the silanol group has undergone a dehydration condensation reaction.

[0456] The thickness of the surface treatment layer is preferably 1~100 nm, more preferably 1~50 nm. If the thickness of the surface treatment layer is 1 nm or more, the effects brought by the surface treatment can be easily and fully obtained. If the thickness of the surface treatment layer is less than 100 nm, the utilization efficiency is high. The thickness of the surface treatment layer can be calculated using a thin film analysis X-ray diffractometer (product name "ATX-G", manufactured by RIGAKU) and by obtaining the interference pattern of reflected X-rays through the X-ray reflectivity method, and then calculating the thickness from the vibration period of the interference pattern.

[0457] There is no particular limitation on the type of substrate, but substrates that are required to be water-repellent can be listed. Examples of substrates include those that are sometimes used when other articles (e.g., styluses) or human fingers come into contact with them; substrates that are sometimes held by human fingers during operation; and substrates that are sometimes placed on other articles (e.g., a platform).

[0458] Materials that can be used as substrates include metals, resins, glass, sapphire, ceramics, semiconductors, stone, fibers, nonwovens, paper, wood, fur, natural leather, artificial leather, ceramics, and their composites. Glass can also be chemically strengthened.

[0459] Examples of substrates include building materials, decorative building materials, interior furnishings, transportation equipment (e.g., automobiles), billboards, signs, drinking utensils, tableware, sinks, decorative items (e.g., picture frames, boxes), laboratory equipment, furniture, textile products, and packaging containers; glass or resin used in art, sports, and games; and glass or resin used in the outer casing (excluding the display) of devices such as mobile phones (e.g., smartphones), portable information terminals, game consoles, and remote controls. The substrate can be in the form of a sheet or a film.

[0460] As a substrate, preferred materials include substrates for touch panels, substrates for displays, and eyeglass lenses, with substrates for touch panels being particularly preferred. The preferred material for a substrate for a touch panel is glass or transparent resin.

[0461] The substrate can be a substrate with surface treatments such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment applied to one or both surfaces. Surface-treated substrates exhibit better adhesion to the surface-treated layer, and the wear resistance of the surface-treated layer is further improved. Therefore, it is preferable to perform surface treatment on the surface of the substrate that contacts the surface-treated layer. Furthermore, when a base layer (described later) is provided, the surface-treated substrate exhibits better adhesion to the base layer, and the wear resistance of the surface-treated layer is further improved. Therefore, when a base layer is provided, it is preferable to perform surface treatment on the surface of the substrate that contacts the base layer.

[0462] The surface treatment layer can be directly applied to the surface of the substrate, or a base layer can be disposed between the substrate and the surface treatment layer. From the viewpoint of further improving the water repellency and abrasion resistance of the surface treatment layer, the article of the present invention preferably comprises a substrate, a base layer disposed on the substrate, and a surface treatment layer disposed on the base layer that has been surface-treated with the surface treatment agent of the present invention.

[0463] The substrate layer is preferably a layer containing an oxide of silicon and at least one specific element selected from the group consisting of elements from group 1, group 2, group 4, group 5, group 13 and group 15 of the periodic table.

[0464] Group 1 elements of the periodic table (hereinafter also referred to as "Group 1 elements") refer to lithium, sodium, potassium, rubidium, and cesium. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing deviations in the composition of the substrate layer between samples, lithium, sodium, and potassium are preferred as Group 1 elements, and sodium and potassium are more preferred. The substrate layer may contain two or more Group 1 elements.

[0465] The Group 2 elements of the periodic table (hereinafter also referred to as "Group 2 elements") refer to beryllium, magnesium, calcium, strontium, and barium. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing deviations in the composition of the substrate layer between samples, magnesium, calcium, and barium are preferred as Group 2 elements, and magnesium and calcium are more preferred. The substrate layer may contain two or more Group 2 elements.

[0466] The Group 4 elements of the periodic table (hereinafter also referred to as "Group 4 elements") refer to titanium, zirconium, and hafnium. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing deviations in the composition of the substrate layer between samples, titanium and zirconium are preferred as Group 4 elements, with titanium being more preferred. The substrate layer may contain two or more Group 4 elements.

[0467] The elements in Group 5 of the periodic table (hereinafter also referred to as "Group 5 elements") are vanadium, niobium, and tantalum. Vanadium is particularly preferred as a Group 5 element from the viewpoint of superior wear resistance in surface-treated layers. The base layer may contain two or more Group 5 elements.

[0468] The elements in Group 13 of the periodic table (hereinafter also referred to as "Group 13 elements") refer to boron, aluminum, gallium, and indium. From the viewpoint of enabling the surface treatment layer to be formed more uniformly and without defects on the substrate layer, or from the viewpoint of further suppressing deviations in the composition of the substrate layer between samples, boron, aluminum, and gallium are preferred as Group 13 elements, and boron and aluminum are more preferred. The substrate layer may contain two or more Group 13 elements.

[0469] The elements in Group 15 of the periodic table (hereinafter also referred to as "Group 15 elements") refer to nitrogen, phosphorus, arsenic, antimony, and bismuth. From the viewpoint of enabling the formation of a surface treatment layer on the substrate layer without defects and with greater uniformity, or from the viewpoint of further suppressing deviations in the composition of the substrate layer between samples, phosphorus, antimony, and bismuth are preferred as Group 15 elements, and phosphorus and bismuth are more preferred. The substrate layer may contain two or more Group 15 elements.

[0470] As specific elements contained in the base layer, elements from Group 1, Group 2, and Group 13 are preferred because the surface treatment layer has better wear resistance. Elements from Group 1 and Group 2 are more preferred, and elements from Group 1 are even more preferred.

[0471] As a specific element, it can contain only one type of element or two or more types of elements.

[0472] The oxide contained in the substrate layer can be a mixture of oxides of the above-mentioned elements (silicon and specific elements) individually (e.g., a mixture of silicon oxide and oxides of specific elements), a composite oxide containing two or more of the above-mentioned elements, or a mixture of oxides of the above-mentioned elements individually and composite oxides.

[0473] From the viewpoint of having better wear resistance of the surface treatment layer, the ratio of the total molar concentration of the specific element in the substrate layer to the molar concentration of silicon in the substrate layer (specific element / silicon) is preferably 0.02 to 2.90, more preferably 0.10 to 2.00, and even more preferably 0.20 to 1.80.

[0474] The molar concentration (mol%) of each element in the substrate can be determined, for example, by depth-direction analysis based on X-ray photoelectron spectroscopy (XPS) using ion sputtering.

[0475] The base layer can be a single layer or multiple layers. The base layer can also have uneven surfaces.

[0476] The thickness of the substrate layer is preferably 1~100 nm, more preferably 1~50 nm, and even more preferably 2~20 nm. If the thickness of the substrate layer is above the lower limit mentioned above, the adhesion of the surface treatment layer based on the substrate layer is further improved, and the wear resistance of the surface treatment layer is more excellent. If the thickness of the substrate layer is below the upper limit mentioned above, the wear resistance of the substrate layer itself is excellent.

[0477] The thickness of the basal layer was determined by cross-sectional observation of the basal layer based on transmission electron microscopy (TEM).

[0478] The substrate layer can be formed, for example, by vapor deposition using vapor deposition materials or by wet coating.

[0479] The vapor deposition material used in the vapor deposition method preferably contains oxides containing silicon and specific elements.

[0480] Specific examples of vapor deposition materials include powder, melt, sintered body, granulated body, and broken body. From an operational point of view, melt, sintered body, and granulated body are preferred.

[0481] Here, "molten body" refers to a solid obtained by melting the powder of vapor-deposited material at high temperature and then cooling and solidifying it. "Sintered body" refers to a solid obtained by sintering the powder of vapor-deposited material. Depending on the need, it can also replace the powder of vapor-deposited material by pressing it into a molded body. "Granulated body" refers to a solid obtained by mixing the powder of vapor-deposited material with a liquid medium (such as water or organic solvent) to obtain granules, and then drying the granules.

[0482] Vaporized materials can be manufactured, for example, by the following methods.

[0483] • A method of mixing silicon oxide powder with powder of oxides of specific elements to obtain powder of vapor deposition material.

[0484] • A method for obtaining granules by mixing the powder of the above-mentioned vapor deposition material with water, and then drying the granules to obtain granulated vapor deposition material.

[0485] A method for obtaining a sintered body by drying a mixture of silicon-containing powder (e.g., powder composed of silicon oxide, silica sand, silica gel) and powder containing a specific element (e.g., powder of oxide of a specific element, carbonate, sulfate, nitrate, oxalate, hydroxide) with water, and then firing the dried mixture or a molded body formed by pressing it.

[0486] • A method of obtaining a melt by melting a silicon-containing powder (e.g., powder composed of silicon oxide, silica sand, silica gel) with a powder containing a specific element (e.g., powder of oxide of a specific element, carbonate, sulfate, nitrate, oxalate, hydroxide) at a high temperature and then cooling and solidifying the melt.

[0487] As a specific example of a vapor deposition method that uses vapor deposition materials, vacuum vapor deposition can be cited. Vacuum vapor deposition is a method in which the vapor deposition material evaporates in a vacuum tank and adheres to the surface of a substrate.

[0488] The temperature during vapor deposition (for example, the temperature of the vessel in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 100°C to 3,000°C, and more preferably 500°C to 3,000°C.

[0489] The pressure during vapor deposition (for example, the pressure inside the tank where the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 1 Pa or less, and more preferably 0.1 Pa or less.

[0490] When using vapor deposition materials to form the base layer, one vapor deposition material can be used, or two or more vapor deposition materials containing different elements can be used.

[0491] Specific examples of evaporation methods for vapor-deposited materials include the resistance heating method, in which the vapor-deposited material is melted and evaporated on a boat made of a high-melting-point metal; and the electron gun method, in which the vapor-deposited material is irradiated with an electron beam to directly heat the material, causing its surface to melt and evaporate. From the viewpoint that localized heating is possible, allowing even high-melting-point substances to evaporate, and that the areas not irradiated by the electron beam are at low temperatures, eliminating concerns about reactions with the container or the introduction of impurities, the electron gun method is preferred as an evaporation method.

[0492] Evaporation methods for depositing materials can utilize multiple boats or a single boat containing all the depositing materials. Deposition methods can include co-deposition and alternating deposition. Specifically, examples include mixing silicon dioxide and a specific source in the same boat, co-deposition of silicon dioxide and a specific element source in different boats, and alternating deposition in different boats. The deposition conditions and sequence are appropriately selected based on the composition of the substrate.

[0493] In wet coating methods, it is preferable to form a base layer on a substrate by using a coating liquid containing a silicon-containing compound, a compound containing a specific element, and a liquid medium.

[0494] Specific examples of silicon compounds include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partial hydrolysis condensates of alkoxysilanes.

[0495] Specific examples of compounds containing a particular element include oxides of a particular element, alkoxides of a particular element, carbonates of a particular element, sulfates of a particular element, nitrates of a particular element, oxalates of a particular element, and hydroxides of a particular element.

[0496] Examples of liquid media include those identical to those contained in the compositions of the present invention.

[0497] The content of the liquid medium relative to the total amount of the coating liquid used to form the substrate layer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.

[0498] Specific examples of wet coating methods used to form a substrate include spin coating, wipe coating, spray coating, scraper coating, dip coating, mold coating, inkjet coating, flow coating, roller coating, tape casting, Langmuir-Blodgett method, and gravure coating.

[0499] Preferably, the coating film is dried after the coating liquid is wet-applied. The drying temperature of the coating film is preferably 20~200°C, more preferably 80~160°C.

[0500] The article of the present invention can be an optical material having a surface treatment layer on the outermost layer.

[0501] As optical materials, in addition to optical materials related to displays, a wide variety of optical materials can be preferred.

[0502] As optical materials, examples include cathode ray tubes (CRTs); such as computer monitors, liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent tubes (VFDs), field emission displays (FEDs), and other displays or protective plates for these displays, or materials on which anti-reflective coatings are applied to their surfaces.

[0503] The articles of the present invention are preferably optical components. Examples of optical components include car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs, portable audio players, car stereos, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, endoscopes and other medical instruments, copiers, PCs, displays (e.g., liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and anti-reflective films.

[0504] In addition, as optical components, examples include the front surface protection plate, anti-reflective plate, polarizing plate, and anti-glare plate of displays such as PDP and LCD; the disc surface of Blu-ray (registered trademark) discs, DVD discs, CD-R, MO and other optical discs; optical fibers; and the display surface of clocks and watches.

[0505] In particular, the articles of the present invention are preferably displays or touch panels.

[0506] The articles of this invention can be medical devices or medical materials. Additionally, the articles of this invention can be automotive interior and exterior components. Examples of exterior components include vehicle windows, lamp covers, and exterior camera covers. Examples of interior components include dashboard covers, navigation system touch panels, and decorative interior materials.

[0507] When the article of the present invention is an optical component, the material constituting the surface of the substrate is a material for optical components, such as glass or transparent plastic. Furthermore, when the article of the present invention is an optical component, functional layers such as a hard coating or an anti-reflective layer can be formed on the surface (outermost layer) of the substrate. The anti-reflective layer can be either a single-layer anti-reflective layer or a multi-layer anti-reflective layer.

[0508] Examples of inorganic materials that can be used in antireflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials can be used alone or in combination of two or more (e.g., as a mixture). When fabricating a multilayer antireflective layer, the outermost layer preferably uses SiO2 and / or SiO. In the case of an optical glass component for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, can be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate can have insulating layers, adhesive layers, protective layers, decorative frame layers (I-CON), atomizing film layers, hard coating layers, polarizing films, phase difference films, and liquid crystal display modules, depending on its specific specifications.

[0509] [Item crafting method]

[0510] The method for manufacturing the article of the present invention is, for example, to perform surface treatment on a substrate using the surface treatment agent of the present invention, thereby manufacturing an article on which a surface treatment layer is formed. Examples of surface treatments include dry coating and wet coating.

[0511] Examples of dry coating methods include vacuum evaporation, CVD, and sputtering. From the viewpoints of suppressing compound decomposition and the simplicity of the apparatus, vacuum evaporation is preferred as a dry coating method. During vacuum evaporation, granular materials containing the compound of the present invention impregnated in porous metals such as iron or steel can be used. Alternatively, granular materials containing the compound of the present invention can be impregnated in porous metals such as iron or steel by impregnating a composition comprising the compound of the present invention and a liquid medium, followed by drying the liquid medium.

[0512] Examples of wet coating methods include spin coating, wipe coating, spray coating, scraper coating, dip coating, mold coating, inkjet coating, flow coating, roller coating, tape casting, Langmuir-Blodgett coating, and gravure coating.

[0513] To improve the wear resistance of the surface treatment layer, operations can be performed as needed to promote the reaction between the compound of the present invention and the substrate. Examples of such operations include heating, humidification, and light irradiation.

[0514] For example, heating a substrate with a surface-treated layer in a humid atmosphere can promote reactions such as hydrolysis of hydrolytic groups, reaction of hydroxyl groups on the substrate surface with silanol groups, and formation of siloxane bonds based on condensation reactions of silanol groups.

[0515] After surface treatment, compounds that are part of the surface treatment layer and are not chemically bonded to other compounds or the substrate can be removed as needed. Examples of removal methods include pouring solvent onto the surface treatment layer or wiping with a cloth soaked in solvent.

[0516] Example

[0517] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. It should be noted that Examples 1 and 2 are comparative examples, and Examples 3 to 7 are exemplary examples.

[0518] [Synthesis of compound (11)]

[0519] Compound (11) was obtained by following the method described in Synthesis Examples 1-2 of International Publication No. 2017 / 022437. The average number of repeating units x2 was 21, and the average number of repeating units x3 was 19.

[0520]

[0521] [Synthesis of compound (12)]

[0522] Compound (12) was obtained by following the method described in Synthesis Examples 1-3 of International Publication No. 2017 / 022437. The average number of repeating units x2 was 21, and the average number of repeating units x3 was 19.

[0523]

[0524] [Synthesis of compound (13)]

[0525] Compound (13) was obtained by following the method described in the synthesis of compound (7-2) in International Publication No. 2021 / 251396. The average number of repeating units x1 was 14. The structure of compound (13) was confirmed by the following NMR data.

[0526]

[0527] 1 H-NMR (400MHz, CDCl3) δ (ppm): 5.85-5.69 (1H), 5.29-5.04 (2H), 4.08-3.98 (2H), 3.94-3.81 (2H).

[0528] 19 F-NMR (376MHz, CDCl3) δ (ppm): -54.85, -82.34, -86.24, -87.57, -89.70, -118.86, -124.67, -125.97.

[0529] [Synthesis of compound (14)]

[0530] Compound (14) was obtained by following the method described in International Publication No. 2021 / 251396 for the synthesis of compound (7-3). The average number of repeating units x1 was 14.

[0531]

[0532] [Synthesis of compound (15)]

[0533] Tris(triphenylphosphine)rhodium chloride (I) (0.05 g), toluene (30 g), and molecular sieve 5A (20 g) were heated under reflux at 110 °C for 24 hours in trimethoxysilane (10 g). After removing the molecular sieve by filtration, the mixture was purified by distillation to obtain 2.5 g of compound (15). The structure of compound (15) was confirmed by the following NMR data.

[0534]

[0535] 1H-NMR (400MHz, CDCl3) δ (ppm): 4.31 (s, 1H), 3.68-3.55 (m, 15H).

[0536] [Synthesis of compound (16)]

[0537] AC-2000 (1.8 g), compound (11) (1.0 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 12.9 mg), aniline (2.6 mg), and compound (15) (0.6 g) were stirred at 40 °C, and low-boiling components were removed by vacuum distillation to obtain 1.2 g of compound (16). The average value of the number of repeating units x2 was 21, and the average value of the number of repeating units x3 was 19. The structure of compound (16) was confirmed by the following NMR data.

[0538]

[0539] 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.97 (t, J=13.0Hz, 2H), 3.65-3.24 (m, 63H), 1.73-1.47 (m, 10H), 0.78 (t, J=9.4Hz, 6H).

[0540] [Synthesis of compound (17)]

[0541] AC-2000 (1.8 g), compound (13) (1.0 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 12.9 mg), aniline (2.6 mg), and compound (15) (0.4 g) were stirred at 40 °C, and low-boiling components were removed by vacuum distillation to obtain 1.1 g of compound (17). The average value of the number of repeating units x1 was 14. The structure of compound (17) was confirmed by the following NMR data.

[0542]

[0543] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.08 (tt, J=13.0, 2.8Hz, 2H), 3.70-3.34 (m, 17H), 1.70-1.41 (m, 2H), 0.78 (t, J=9.4Hz, 2H).

[0544] [Synthesis of compound (18)]

[0545] Compound (18) was obtained according to the method described in Example 3 of International Publication No. 2018 / 056413.

[0546]

[0547] [Synthesis of compound (19)]

[0548] AC-2000 (1.8 g), compound (18) (1.0 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 12.9 mg), aniline (2.6 mg), and compound (15) (0.5 g) were stirred at 40 °C, and low-boiling components were removed by vacuum distillation to obtain 1.1 g of compound (19). The structure of compound (19) was confirmed by the following NMR data.

[0549]

[0550] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.69 (tt, J=12.8, 2.6Hz, 2H), 4.01-3.38 (m, 34H), 1.83-1.50 (m, 4H), 0.80 (t, J=9.3Hz, 4H).

[0551] [Synthesis of compound (20)]

[0552] Compound (20) was obtained by following the method described in Synthesis Example 6 of International Publication No. 2018 / 079743.

[0553]

[0554] [Synthesis of compound (21)]

[0555] AC-2000 (1.8 g), compound (20) (1.0 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 12.9 mg), aniline (2.6 mg), and compound (15) (0.5 g) were stirred at 40 °C, and low-boiling components were removed by vacuum distillation to obtain 1.1 g of compound (21). The structure of compound (21) was confirmed by the following NMR data.

[0556]

[0557] 1H-NMR (400MHz, CDCl3) δ (ppm): 3.56 (d, J=16.1Hz, 45H), 2.11 (tt, J=14.2, 8.6Hz, 2H), 1.57-1.24 (m, 8H), 0.81-0.26 (m, 14H).

[0558] [Synthesis of compound (22)]

[0559] Compound (22) was obtained according to the method described in Examples 6-5 of International Publication No. 2020 / 162371.

[0560]

[0561] [Synthesis of compound (23)]

[0562] AC-2000 (1.8 g), compound (22) (1.0 g), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3%, 12.9 mg), aniline (2.6 mg), and compound (15) (0.5 g) were stirred at 40 °C, and low-boiling components were removed by vacuum distillation to obtain 1.2 g of compound (23). The structure of compound (23) was confirmed by the following NMR data.

[0563]

[0564] 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.79-3.18 (m, 94H), 1.61-1.20 (m, 24H), 0.74 (t, J=9.0Hz, 12H).

[0565] [Item crafting]

[0566] Articles of Examples 1 to 7 were obtained by surface treatment of a substrate using compounds (12), (14), (16), (17), (19), (21), and (23) using the following method. Dry coating was used as the surface treatment method.

[0567] 30g of silicon dioxide was placed in a copper furnace cylinder within a vacuum evaporation apparatus (ULVAC KIKO, Inc. VTR-350M) as the evaporation source. A glass substrate was placed inside the vacuum evaporation apparatus, and the air inside the apparatus was evaporated to a pressure of 5×10⁻⁶. -3 Pressure below Pa. The furnace cylinder is heated to about 2,000°C, and silicon oxide is vacuum-deposited on the surface of the substrate to produce a substrate with a silicon oxide layer having a thickness of about 20 nm.

[0568] Next, 0.5 g of each compound was filled into a molybdenum boat dish inside a vacuum evaporation apparatus (ULVAC, VTR350M), and the vacuum evaporation apparatus was evacuated to 1×10⁻⁶. -3 Pa below. The boat containing the compound is heated at a heating rate of less than 10 °C / min. When the evaporation rate measured by a quartz oscillating film thickness gauge exceeds 1 nm / s, the baffle is opened to begin film deposition on the surface of the substrate on the silicon oxide layer side.

[0569] The baffle was closed when the film thickness reached approximately 50 nm, thus ending the film deposition on the substrate surface. The substrate with the deposited compound was heated at 200°C for 30 minutes and cleaned with AC-2000 (manufactured by AGC Corporation) to obtain the evaluation samples (articles) of Examples 1 to 4, which are sequentially stacked with a substrate, a silicon oxide layer, and a surface treatment layer.

[0570] [evaluate]

[0571] Water repellency

[0572] Approximately 2 μL of distilled water was dropped onto the surface treatment layer of the article, and the initial water contact angle was measured using a contact angle measuring device (product name "DM-500", manufactured by Kyowa Interface Science Co., Ltd.). The average value of the measurements taken at 5 points on the surface treatment layer was taken as the water contact angle. The water repellency of the surface treatment layer was evaluated based on the following criteria. It should be noted that the water contact angle was calculated using the 2θ method. The results are shown in Table 1.

[0573] A: The initial water contact angle is above 110°.

[0574] C: The initial water contact angle is less than 110°

[0575] <Abrasion Resistance (Steel Wool)>

[0576] For the surface treatment layer, according to JIS L0849:2013 (ISO 105-X12:2001), a reciprocating traverse testing machine (manufactured by KNT) was used to reciprocate the steel wool Bonstar (#0000) 10,000 times at a pressure of 98.07 kPa and a speed of 320 cm / min, and then the water contact angle was measured. The method for measuring the water contact angle after the friction test is the same as the method for measuring the initial water contact angle in the evaluation method of water repellency. The smaller the decrease in water repellency (water contact angle) after friction, the smaller the decrease in performance caused by friction, and the better the wear resistance. The evaluation criteria are as follows. The results are shown in Table 1.

[0577] The decrease in water contact angle = (initial water contact angle) - (water contact angle after friction)

[0578] A: After 100,000 cycles, the water contact angle decreases to below 10°.

[0579] C: The water contact angle decreases by more than 10° after 100,000 cycles.

[0580] Fingerprint Removal

[0581] Prepare a 1kg weight with a 2cm diameter red rubber stopper for the fingerprint imprinting part. Next, add 70μL of artificial fingerprint liquid (manufactured by Isehisa Co., Ltd.) to a wiping cloth and allow the fingerprint to adhere in the artificial fingerprint liquid for 1 minute. To remove excess artificial fingerprint liquid adhering to the fingerprint, allow the fingerprint to adhere to a new wiping cloth for 20 seconds. Then, place an item with a surface treatment layer on a hot plate with the temperature set to 23°C. Imprint a fingerprint onto the surface treatment layer. Place the item with the artificial fingerprint liquid attached onto the sliding device (product name "HHS-2000", manufactured by Shinto Science Co., Ltd.). Use double-sided tape to attach a flat indenter with a 1cm square area to a wiping cloth (manufactured by KB Seiren Co., Ltd. SavinaMinnimax) and place it on the sliding device. Wipe the attached artificial fingerprint liquid in one direction with a load of 100g relative to the surface treatment layer using the wiping cloth. The haze of the wiped area was measured using a haze meter (product name "NDH7000SP", manufactured by Nippon Denshoku Co., Ltd.). The evaluation criteria are as follows. The results are shown in Table 1.

[0582] A: Haze value is below 0.1%

[0583] B: Haze value is above 0.1% and below 1%.

[0584] C: Haze value above 1%

[0585] <Lightfastness>

[0586] For the surface treatment layer, a benchtop xenon arc lamp accelerated lightfastness testing machine (SUNTEST XLS+: product name, manufactured by Toyo Seiki Co., Ltd.) was used. The black panel temperature was 63°C, and light (650W / m²) was applied. 2 After 500 hours (300~700nm), the water contact angle of the surface treatment layer was measured using the method described above. The smaller the decrease in water contact angle after the lightfastness test, the smaller the decrease in performance caused by light, and the better the lightfastness of the surface treatment layer. The evaluation criteria are as follows. The results are shown in Table 1.

[0587] The reduction in water contact angle = (initial water contact angle) - (water contact angle after lightfastness test)

[0588] A: Promotes a reduction in the water contact angle to below 3° after the lightfastness test.

[0589] B: Promotes a reduction in the water contact angle after lightfastness testing by more than 3° and less than 5°.

[0590] C: Promotes a reduction of more than 5° in the water contact angle after lightfastness testing.

[0591] [Table 1]

[0592]

[0593] As shown in Table 1, it was confirmed that the compounds of Examples 3-7, which have the group P, can form a surface treatment layer with excellent wear resistance compared to the compounds of Examples 1 and 2, which have the same structure but do not have the group P. Furthermore, it was also confirmed that the compounds of Examples 3-7 can form a surface treatment layer with excellent lightfastness compared to the compounds of Examples 1 and 2.

[0594] Industrial availability

[0595] The compounds of this invention are useful as surface treatment agents. For example, they can be used as substrates in display devices such as touch panel displays, optical components, semiconductor components, building materials, automotive components, and nanoimprint technology. Furthermore, they can be used in the bodies, windows (front, side, and rear windows), mirrors, and bumpers of transportation equipment such as trams, automobiles, ships, and aircraft. Moreover, they can be used in outdoor items such as building exteriors, tents, solar power modules, sound insulation panels, and concrete; fishing nets, insect nets, and sinks. Additionally, they can be used in kitchens, bathrooms, washbasins, mirrors, and toilet perimeter components; chandeliers, ceramics such as tiles; artificial marble, air conditioners, and various indoor equipment. Furthermore, they can be used as antifouling treatments for jigs, interior walls, and piping in factories. Additionally, they can be used in goggles, eyeglasses, helmets, marbles, fibers, umbrellas, toys, and soccer balls. Finally, they can be used as anti-adhesion agents in various packaging materials such as food packaging materials, cosmetic packaging materials, and the interior of jugs. In addition, surface treatment agents can be used in medical devices such as car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastroscopes, as well as in copiers, PCs, displays (such as liquid crystal displays, organic EL displays, plasma displays, and touch panel displays), touch panels, protective films, and anti-reflective films.

[0596] The application claims priority based on Japanese Special Application No. 2023-166269 filed on September 27, 2023, and includes all of its disclosures therein.

Claims

1. A compound comprising the group P and a fluoropolyether chain, Group P:-[Si(R) 1 )2-X] n1 -Si(R) 1 3, in, X can be an oxygen atom or a carbon atom independently. R 1 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. R 1 At least 4 Rs in 1 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. n1 is an integer from 1 to 3.

2. The compound according to claim 1, wherein, The value of n1 is 1.

3. The compound according to claim 1, wherein, The group P is -[Si(OR)] 2 )2-O] n1 -Si(OR) 2 3, Among them, R 2 Each is an independent hydrocarbon group.

4. The compound according to claim 2, wherein, The group P is -Si(OR) 2 )2-O-Si(OR 2 3, Among them, R 2 Each is an independent hydrocarbon group.

5. The compound represented by formula (1) or formula (2) below, (R) f1 ) n3 -Q 1 -(J 1 ) n2 …Formula (1) (J) 1 ) n2 -Q 2 -R f2 -Q 2 -(J 1 ) n2 …Formula (2) in, J 1 Each of them independently represents the following group P, Group P:-[Si(R) 1 )2-X] n1 -Si(R) 1 3, X can be an oxygen atom or a carbon atom independently. R 1 Each can be independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. R 1 At least 4 Rs in 1 It is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. n1 is an integer from 1 to 3. R f1 It is a monovalent fluorinated polyether chain. R f2 It is a divalent fluorinated polyether chain. Q 1 It is a (n3+n2) valence linking group. Q 2 It is a (1+n2) valence linking group. n2 are each an independent integer greater than or equal to 1. n3 is an integer greater than or equal to 1.

6. The compound according to claim 5, wherein, The value of n2 is 1 to 6.

7. The compound according to claim 5, wherein, The R f1 It is represented by the following formula (3), R f11 -(OR f12 ) m1 -... Formula (3) Among them, R f11 It is a fluoroalkyl group with 1 to 20 carbon atoms, and contains multiple R groups. f11 At that time, multiple existing R f11 Choose either the same or different from each other. R f12 It is a fluoroalkylene group with 1 to 6 carbon atoms, and contains multiple R groups. f12 At that time, multiple existing R f12 Choose either the same or different from each other. m1 is an integer from 0 to 500.

8. The compound according to claim 5, wherein, The R f2 It is represented by the following formula (4), -R f21 -(OR f22 ) m2 -... Formula (4) Among them, R f21 It is a fluoroalkylene group having 1 to 6 carbon atoms. R f22 It is a fluoroalkylene group with 1 to 6 carbon atoms, and contains multiple R groups. f22 At that time, multiple existing R f22 Choose either the same or different from each other. m2 is an integer from 0 to 500.

9. A composition comprising the compound of any one of claims 1 to 8 and a liquid medium.

10. A surface treatment agent comprising the compound according to any one of claims 1 to 8.

11. A surface treatment agent comprising the compound of any one of claims 1 to 8 and a liquid medium.

12. A method for manufacturing an article, wherein, An article having a surface-treated layer formed on the substrate is manufactured by surface-treating a substrate with a surface-treated agent comprising any one of claims 1 to 8.

13. An article comprising a substrate and a surface treatment layer disposed on the substrate and surface-treated with a surface treatment agent comprising any one of claims 1 to 8.

14. The article according to claim 13, wherein it is an optical component.

15. The article of claim 13, wherein it is a display or a touch panel.

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