Article and method of manufacturing an article

Abstract

An article and use thereof, the article comprising a substrate, and a surface layer and a metal disposed on the substrate, the surface layer comprising a compound having a (poly)oxyfluoroalkylene chain and having a primary or secondary amino group, the metal being a metal having an electronegativity of 0.8 to 2.54.

Description

Technical Field

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

[0002] In recent years, the performance requirements for surface layers formed using fluorinated ether compounds have been increasing. For example, when surface layers are applied to components that form surfaces that fingers may come into contact with, surface layers with excellent abrasion resistance that do not easily degrade in performance (e.g., water repellency) even with repeated abrasion are required.

[0003] For example, Patent Document 1 describes a surface treatment agent comprising a fluorinated compound having a (poly)oxyfluoroalkylene chain.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2022 / 209502 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] The surface treatment agent described in Patent Document 1 can form a surface layer with excellent durability because the fluorine-containing compound contained in the surface treatment agent is closely bonded to various substrates through hydrogen bonds or chemical bonds.

[0009] However, depending on the substrate used, there are instances of heat-induced warping observed, requiring articles with a surface layer that has excellent abrasion resistance and where warping is suppressed.

[0010] This disclosure was made in view of the following situation, and one embodiment of the present invention aims to solve the problem of providing an article having a surface layer with excellent wear resistance and suppressed warping, as well as a method for manufacturing the article.

[0011] Solution for solving the problem

[0012] This disclosure includes the following methods.

[0013] <1>

[0014] An article comprising a substrate, a surface layer disposed on the substrate, and a metal.

[0015] The surface layer contains compounds having (poly)oxyfluoroalkyl chains and having primary or secondary amino groups.

[0016] Metals are those with an electronegativity of 0.8 to 2.54.

[0017] <2>

[0018] An article comprising a substrate, a surface layer disposed on the substrate, and a metal.

[0019] The surface layer is formed using a surface treatment agent containing a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amino group.

[0020] Metals are those with an electronegativity of 0.8 to 2.54.

[0021] <3>

[0022] According to <1> or <2>, the compound is at least one selected from the group consisting of fluorine-containing compounds represented by formula (A1) and formula (A2).

[0023] (G 1 -) a1 Q 1 (-NHR A ) b1 …(A1)

[0024] (R B HN-) b2 Q 2 -G 2 -Q 3 (-NHR C ) b3 …(A2)

[0025] in,

[0026] G 1 It is a (poly)fluoroalkyl group, in the presence of multiple G 1 In the case of multiple Gs 1 Choose either the same or different from each other.

[0027] G 2 It is a (poly)oxyfluorine alkyl group.

[0028] Q 1 It is a linking group with a single bond or an a1+b1 valence.

[0029] Q 2 It is a single bond or a linker group with a b2+1 valence.

[0030] Q 3 It is a linker group with a single bond or a b3+1 valence.

[0031] a1 is an integer greater than or equal to 1.

[0032] b1 is an integer greater than or equal to 1.

[0033] b2 is an integer greater than or equal to 1.

[0034] b3 is an integer greater than or equal to 1.

[0035] R A R B and R C Each is independently a hydrogen atom or an alkyl group.

[0036] R A Optional and Q 1 Connect to form a ring,

[0037] R B Optional and Q 2 Connect to form a ring,

[0038] R C Optional and Q 3 They connect to form a ring.

[0039] <4>

[0040] The article according to any one of <1> to <3>, wherein the metal is at least one selected from the group consisting of Li, Na, K, Mg, Ca, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Cr, Mn, Fe, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Sn, Pb, Bi, Te, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

[0041] <5>

[0042] The article according to any one of <1> to <4>, wherein the mass of the metal per unit area on the surface of the side of the substrate on which the metal is disposed is 0.0001 to 270 μg / cm³. 2 .

[0043] <6>

[0044] The article according to any one of <1> to <5>, wherein the substrate comprises at least one selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, acrylonitrile / styrene copolymer, polyacrylonitrile, polymethyl methacrylate, polycarbonate and polyethylene terephthalate.

[0045] <7>

[0046] The article according to any one of <1> to <6> further comprises a structure that connects the substrate and the surface layer and has a structure derived from the compound.

[0047] <8>

[0048] The article according to any one of <1> to <7>, wherein the molar ratio of the metal to the (poly)oxyfluoroalkyl chain is 0.01 to 150,000 mol%.

[0049] <9>

[0050] A method for manufacturing an article, wherein the substrate is subjected to any of the following pretreatments: coating with a solution containing Brønsted acid, coating with a solution containing Lewis acid, or coating with a solution containing Brønsted acid followed by coating with a solution containing Lewis acid.

[0051] A surface treatment agent comprising a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amino group is applied to a pretreated substrate; or

[0052] After applying a surface treatment agent to the substrate, a solution containing Lewis acid is applied; or

[0053] A solution containing a surface treatment agent and Lewis acid is applied to a substrate.

[0054] <10>

[0055] According to the method of manufacturing the article described in <9>, the Brønsted acid is at least one selected from the group consisting of ascorbic acid, acetic acid, citric acid, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid and phosphoric acid.

[0056] <11>

[0057] According to the method of manufacturing the article described in <9> or <10>, the metal constituting the Lewis acid is a metal with an electronegativity of 0.8 to 2.54.

[0058] <12>

[0059] According to the method of manufacturing the article described in <11>, the metal is selected from at least one of the following groups: Li, Na, K, Mg, Ca, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Cr, Mn, Fe, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Sn, Pb, Bi, Te, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0060] <13>

[0061] The method for manufacturing an article according to any one of <9> to <12>, wherein the Lewis acid is selected from at least one of the group consisting of La(OTf)3, Nd(OTf)3 and LiCl.

[0062] <14>

[0063] The method for manufacturing an article according to any one of <9> to <13>, wherein the concentration of the Lewis acid in the solution containing the Lewis acid is 1 ppb by mass to 5 ppb by mass.

[0064] <15>

[0065] The method of manufacturing an article according to any one of <9> to <14>, wherein the compound is at least one selected from the group consisting of fluorine-containing compounds represented by the following formula (A1) and the following formula (A2).

[0066] (G 1 -) a1 Q 1 (-NHR A ) b1 …(A1)

[0067] (R B HN-) b2 Q 2 -G 2 -Q 3 (-NHR C ) b3 …(A2)

[0068] in,

[0069] G 1 It is a (poly)fluoroalkyl group, in the presence of multiple G 1 In the case of multiple Gs 1 Choose either the same or different from each other.

[0070] G 2 It is a (poly)oxyfluorine alkyl group.

[0071] Q 1 It is a linking group with a single bond or an a1+b1 valence.

[0072] Q 2 It is a single bond or a linker group with a b2+1 valence.

[0073] Q 3 It is a linker group with a single bond or a b3+1 valence.

[0074] a1 is an integer greater than or equal to 1.

[0075] b1 is an integer greater than or equal to 1.

[0076] b2 is an integer greater than or equal to 1.

[0077] b3 is an integer greater than or equal to 1.

[0078] R A R B and RC Each is independently a hydrogen atom or an alkyl group.

[0079] R A Optional and Q 1 Connect to form a ring,

[0080] R B Optional and Q 2 Connect to form a ring,

[0081] R C Optional and Q 3 They connect to form a ring.

[0082] <16>

[0083] according to <9> ~ <15> The method of manufacturing an article according to any one of the following, wherein the substrate comprises at least one selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, acrylonitrile / styrene copolymer, polyacrylonitrile, polymethyl methacrylate, polycarbonate and polyethylene terephthalate.

[0084] Invention Effects

[0085] According to one embodiment of the present invention, an article having a surface layer with excellent abrasion resistance and warping suppression, and a method for manufacturing the article are provided. Detailed Implementation

[0086] In this disclosure, the numerical range represented by “~” includes the minimum and maximum values ​​recorded before and after “~”, respectively.

[0087] In the numerical ranges described in this disclosure in stages, the upper or lower limit value described in one numerical range can also be replaced by the upper or lower limit value of other numerical ranges described in stages. Furthermore, the upper or lower limit value of the numerical ranges described in this disclosure can also be replaced by the values ​​shown in the embodiments.

[0088] The following terms in this invention have the following meanings.

[0089] In this disclosure, the compound represented by formula (A1) is designated as compound (A1). Compounds, groups, etc., represented by other formulas are also referred to accordingly.

[0090] Perfluoroalkyl groups are alkyl groups in which all hydrogen atoms are replaced by fluorine atoms. Additionally, fluoroalkyl groups are a general term encompassing both partially fluoroalkyl and perfluoroalkyl groups. Partially fluoroalkyl groups are alkyl groups in which one or more hydrogen atoms are replaced by fluorine atoms and which have one or more hydrogen atoms. In other words, fluoroalkyl groups are alkyl groups with one or more fluorine atoms.

[0091] (Poly)fluoroalkyl refers to a fluoroalkyl group having one or two or more oxygen groups in its chain, and (poly)fluoroalkylene is also defined in this way.

[0092] "Surface layer" refers to a layer formed on the surface of a substrate.

[0093] [thing]

[0094] The first aspect of the article disclosed herein includes a substrate, a surface layer disposed on the substrate, and a metal, the surface layer comprising a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amino group, and the metal being a metal with an electronegativity of 0.8 to 2.54.

[0095] The second aspect of the article disclosed herein includes a substrate, a surface layer disposed on the substrate, and a metal. The surface layer is formed using a surface treatment agent comprising a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amine. The metal is a metal with an electronegativity of 0.8 to 2.54. Hereinafter, both the first and second aspects of the article disclosed herein will also be referred to as "the article".

[0096] This product has a surface layer and a metal on a substrate. The surface layer contains a compound having a (poly)oxyfluoroalkyl chain and a primary or secondary amino group, thus providing a surface layer with excellent wear resistance and inhibiting warping.

[0097] The following is a description of the components of this item.

[0098] <Substrate>

[0099] The material of the substrate can be selected appropriately according to the intended use of the product, and can be either a transparent or opaque substrate, and its shape is also arbitrary. When the substrate is in the form of a film or a plate, it can be a rigid material without flexibility or a flexible material with flexibility.

[0100] Specific examples of materials used as substrates include glass; acetylcellulose resins such as triacetylcellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; olefin resins such as polyethylene and polymethylpentene; acrylic resins such as polymethyl methacrylate; polyurethane resins; resins such as polyethersulfone, polycarbonate, polysulfone, polyether, polyetherketone, polyimide, polyacrylonitrile, polymethyl methacrylate, cyclic olefin polymers, and cyclic olefin copolymers; metals such as gold, platinum, and copper; metal oxides such as silicon dioxide (SiO2), aluminum oxide (Al2O3), indium tin oxide (ITO), lead zirconate titanate (PLT), silver oxide, and copper oxide; and sapphire, stone, paper, and cloth.

[0101] It should be noted that a transparent substrate refers to a visible light transmittance of 25% or more under vertical incidence, according to JIS R3106:1998 (ISO 9050:1990).

[0102] Additionally, the substrate can be a substrate with a hard coating formed on its surface, a so-called substrate with a hard coating. In this disclosure, a substrate with a hard coating is included in the concept of a substrate.

[0103] Examples of hard coatings include acrylate-based hard coatings, urethane-acrylate-based hard coatings, and epoxy-based hard coatings. Among these, acrylate-based hard coatings or urethane-acrylate-based hard coatings are preferred.

[0104] The thickness of the hard coating is preferably 0.01 μm to 2000 μm, and particularly preferably 0.02 μm to 500 μm. Methods for measuring the thickness of the hard coating include those based on observing the cross-section of the hard coating using an electron microscope (SEM, TEM, etc.) and / or using an optical interferometer, a spectrophotometer, an ellipsometer, an altimeter, etc.

[0105] From the viewpoint of reactivity with the primary or secondary amino groups contained in a particular compound, the substrate preferably comprises a resin, and more preferably a resin comprising at least one group selected from the group consisting of ester, cyano, amide, imide, carbonate and urethane groups.

[0106] Specifically, as a base material, examples include resins having functional groups in the side chain that can react with the aforementioned amino group, and resins having functional groups in the main chain that can react with the aforementioned amino group.

[0107] Examples of resins having functional groups in their side chains that can react with the aforementioned amino groups include ABS resin (acrylonitrile / butadiene / styrene copolymer), AS resin (acrylonitrile / styrene copolymer), PAN (polyacrylonitrile), and PMMA (polymethyl methacrylate).

[0108] Examples of resins having functional groups in the main chain that can react with the aforementioned amino groups include polyesters (e.g., PET (polyethylene terephthalate)), polycarbonates, polyurethanes, polyamides (e.g., nylon 6) and urethane acrylates.

[0109] From the viewpoint of obtaining a stronger bond between the substrate and the aforementioned amino group, the substrate is preferably a resin having functional groups in its side chains that are capable of reacting with the aforementioned amino group, and more preferably includes at least one selected from the group consisting of ABS resin, AS resin, PAN, PMMA, polycarbonate and PET.

[0110] In addition, when the substrate is a substrate with a hard coating, the hard coating preferably includes at least one selected from the group consisting of ABS resin, AS resin, PAN, PMMA, polycarbonate and PET.

[0111] <Surface Layer>

[0112] This article has a surface layer and a metal on a substrate. The metal may be contained within the surface layer, or it may be disposed on the surface layer without being contained within the surface layer, or it may be disposed between the substrate and the surface layer. The surface layer may be formed on a portion of the surface of the substrate, or it may be formed on the entire surface of the substrate. The surface layer may be spread in a film-like manner on the surface of the substrate, or it may be distributed in a dotted manner.

[0113] In a first aspect of the articles disclosed herein, the surface layer comprises a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amino group (hereinafter also referred to as the “specific compound”).

[0114] In a specific compound, the number of (poly)oxyfluoroalkyl chains is not particularly limited; it can be only one or more than two.

[0115] In a specific compound, the number of primary or secondary amino groups is not particularly limited; it can be only one or more than two.

[0116] In certain compounds, (poly)oxyfluoroalkyl chains can be directly bonded to primary or secondary amino groups, or they can be bonded with the help of linking groups.

[0117] (Poly)oxyfluoroalkylene chains may contain hydrogen atoms, but from the viewpoint of further improving wear resistance, (poly)oxyperfluoroalkylene chains are preferred.

[0118] From the viewpoint of obtaining a surface layer with superior wear resistance, the specific compound is preferably selected from at least one of the groups consisting of fluorinated compounds represented by the following formulas (A1) and (A2).

[0119] (G 1 -) a1 Q 1 (-NHR A ) b1 …(A1)

[0120] (R B HN-) b2 Q 2 -G 2 -Q 3 (-NHR C ) b3 …(A2)

[0121] in,

[0122] G 1 It is a (poly)fluoroalkyl group, in the presence of multiple G 1 In the case of multiple Gs 1 Choose either the same or different from each other.

[0123] G 2 It is a (poly)oxyfluorine alkyl group.

[0124] Q 1 It is a linking group with a single bond or an a1+b1 valence.

[0125] Q 2 It is a single bond or a linker group with a b2+1 valence.

[0126] Q 3 It is a linker group with a single bond or a b3+1 valence.

[0127] a1 is an integer greater than or equal to 1.

[0128] b1 is an integer greater than or equal to 1.

[0129] b2 is an integer greater than or equal to 1.

[0130] b3 is an integer greater than or equal to 1.

[0131] R A R B and R C Each is independently a hydrogen atom or an alkyl group.

[0132] R A Optional and Q 1 Connect to form a ring,

[0133] R B Optional and Q 2 Connect to form a ring,

[0134] R C Optional and Q 3 They connect to form a ring.

[0135] [G] 1 ]

[0136] G 1 It is a (poly)oxyfluoroalkyl group.

[0137] G 1 The (poly)fluoroalkyl group in Q is in conjunction with Q 1 The bond ends with -O-, or has -O- between carbon atoms in a carbon chain with more than 2 carbon atoms, or is a fluoroalkyl group containing both of these.

[0138] From the perspective of ease of manufacture, G 1 The structure shown in formula (G1-1) is preferred.

[0139] R f0 O-[(R f1 O) m1 (R f2 O) m2 (Rf3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-R f7 - Equation (G1-1)

[0140] in,

[0141] R f0 It is a fluoroalkyl group with 1 to 20 carbon atoms.

[0142] R f1 It is a fluoroalkylene group with 1 carbon atom.

[0143] R f2 It is a 2-carbon fluoroalkylene group.

[0144] R f3 It is a 3-carbon fluoroalkylene group.

[0145] R f4 It is a fluoroalkylene group with 4 carbon atoms.

[0146] R f5 It is a 5-carbon fluoroalkylene group.

[0147] R f6 It is a 6-carbon fluoroalkylene group.

[0148] R f7 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0149] m1, m2, m3, m4, m5, and m6 each independently represent integers greater than or equal to 0 or 1, and m1+m2+m3+m4+m5+m6 represents integers from 0 to 500.

[0150] From the viewpoint of forming a surface layer with excellent durability, water and oil repellency, and fingerprint and dirt removal properties, it is preferable that m1+m2+m3+m4+m5+m6 be an integer from 1 to 500, i.e., it is preferable that G is an integer from 1 to 500. 1 It is a polyoxyfluoroalkyl group. In addition, from the viewpoint of forming a surface layer with excellent durability, water and oil repellency and fingerprint and dirt removal properties, m1+m2+m3+m4+m5+m6 is more preferably an integer from 1 to 300, more preferably an integer from 5 to 200, and particularly preferably an integer from 10 to 150.

[0151] It should be noted that in equation (G1-1), (R) f1 O)~(R f6 The bonding order of O is arbitrary.

[0152] In equation (G1-1), m1 to m6 respectively represent (R f1 O)~(R f6 The number of O's does not indicate the configuration. For example, (R) f5 O) m5 Represents (R) f5 The quantity of O is m5, which does not mean that (R) f5 O) m5 The block configuration structure. Similarly, (R f1 O)~(R f6 The order in which O is recorded does not indicate the bonding order of the individual units.

[0153] In R f0 In this context, fluoroalkyl groups can be straight-chain fluoroalkyl groups, branched fluoroalkyl groups, or fluoroalkyl groups with cyclic structures.

[0154] In R f3 ~R f6 In this context, the fluoroalkylene group can be a straight-chain fluoroalkylene group, a branched-chain fluoroalkylene group, or a fluoroalkylene group with a cyclic structure.

[0155] As R f1 Specific examples include -CF2- and -CHF-.

[0156] As R f2 Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, and -CH2CHF-.

[0157] As R 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-, and -CH(CH2F)-CH2-.

[0158] As R 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-, and -cycloC4F6-.

[0159] As R f5Specific examples include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, and -cycloC5F8-.

[0160] As R f6 Specific examples include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, and -cycloC6F 10 -

[0161] Additionally, as R f0 Specific examples can be listed that are related to the above R. f1 ~R f6 The same examples are listed in the text.

[0162] Here, -cycloC4F6- refers to a perfluorocyclobutane diester, and as a specific example, perfluorocyclobutane-1,2-diyl can be listed. -cycloC5F8- refers to a perfluorocyclopentane diester, and as a specific example, perfluorocyclopentane-1,3-diyl can be listed. -cycloC6F 10 - refers to perfluorocyclohexane dimethyl, and as a specific example, perfluorocyclohexane-1,4-dimethyl can be listed.

[0163] From the perspective of improving wear resistance, R is preferred. f0 It is a perfluoroalkyl group, preferably R. f1 ~R f6 It is a perfluoroalkylene group.

[0164] From the perspective of forming a surface layer with superior durability, G 1 Preferably, it includes at least one of the groups consisting of structures selected from the following formulas (F1) to (F3).

[0165] (R f1 O) m1 -(R f2 O) m2Formula (F1)

[0166] (R f2 O) m2 -(R f4 O) m4 Formula (F2)

[0167] (R f3 O) m3 Formula (F3)

[0168] The symbols in equations (F1) to (F3) are the same as those in equation (G1-1) above.

[0169] In equations (F1) and (F2), (R) f1 O) and (R) f2 O), (R) f2 O) and (R) f4 The bonding order of O) is arbitrary. For example, (R) f1 O) and (R) f2 O) can be configured alternately, (R) f1 O) and (R) f2 O) can be configured in separate segments, or it can be random. The same applies to equation (F3).

[0170] In formula (F1), m1 is preferably 1 to 30, more preferably 1 to 20. Additionally, m2 is preferably 1 to 30, more preferably 1 to 20.

[0171] In formula (F2), m2 is preferably 1 to 30, more preferably 1 to 20. Additionally, m4 is preferably 1 to 30, more preferably 1 to 20.

[0172] In formula (F3), m3 is preferably 1 to 30, and more preferably 1 to 20.

[0173] From the perspective of ease of synthesis, G 1 Preferably, it contains the group represented by the following formula (B1).

[0174] R f11 O-(R f12 O) c1 -R f13 -Formula (B1)

[0175] in,

[0176] R f0 It is a fluoroalkyl group with 1 to 20 carbon atoms.

[0177] R f12 and R f13 Each is independently a fluoroalkylene group having 1 to 6 carbon atoms, and multiple Rs are present. f12 In the case of multiple Rf12 Choose any two numbers that are the same or different from each other, where c1 is an integer from 0 to 500.

[0178] It should be noted that R f11 Specific examples are the same as those mentioned above. f0 Same. R f12 Specific examples are the same as those mentioned above. f1 ~R f6 The same as those listed in R. f13 Specific examples are the same as those mentioned above. f7 same.

[0179] [G] 2 ]

[0180] G 2 It is a (poly)oxyfluorine alkylene group.

[0181] G 2 The (poly)oxyfluorine alkyl group in formula (A2) is related to Q. 2 Or Q 3 The two bonded ends each have -O- independently, or have -O- between carbon atoms in a carbon chain with more than 2 carbon atoms, or are fluoroalkylene groups as a combination of these.

[0182] From the perspective of ease of manufacture, G 2 The structure shown in formula (G2-1) is preferred.

[0183] -(O) m10 -[(R f1 O) m11 (R f2 O) m12 (R f3 O) m13 (R f4 O) m14 (R f5 O) m15 (R f6 O) m16 ]-R f7 Equation (G2-1)

[0184] Wherein, m10 is 0 or 1, m11, m12, m13, m14, m15, and m16 are each independently an integer greater than or equal to 0 or 1, and m11+m12+m13+m14+m15+m16 is preferably an integer from 1 to 500, more preferably an integer from 1 to 300, even more preferably an integer from 5 to 200, and particularly preferably an integer from 10 to 150. R f1 R f2 R f3 R f4 R f5 R f6 and Rf7 With the above G 1 The same as in [the previous sentence]. It should be noted that in equation (G2-1), (R) f1 O)~(R f6 The bonding order of O is arbitrary, as explained in equation (G1-1) above.

[0185] From the perspective of water and oil repellency and / or fingerprint removal, it is preferable that m10 is 1 and m11+m12+m13+m14+m15+m16 are integers from 1 to 500, that is, it is preferable that G is 1. 2 It is a polyoxyfluoroalkylene group.

[0186] From the perspective of forming a surface layer with superior durability, G 2 Preferably, it includes at least one of the structures selected from the group consisting of the structures shown in the following formulas (F4) to (F6).

[0187] -O-(R f1 O) m11 -(R f2 O) m12 Formula (F4)

[0188] -O-(R f2 O) m12 -(R f4 O) m14 Formula (F5)

[0189] -O-(R f3 O) m13 Formula (F6)

[0190] The symbols in equations (F4) to (F6) are the same as those in equation (G2-1) above.

[0191] In equations (F4) and (F5), (R) f1 O) and (R) f2 O), (R) f2 O) and (R) f4 The bonding order of O) is arbitrary. For example, (R) f1 O) and (R) f2 O) can be configured alternately, (R) f1 O) and (R) f2 O) can be configured in separate segments, or it can be random. The same applies in equation (F6).

[0192] In formula (F4), m11 is more preferably an integer from 1 to 150, further preferably an integer from 2 to 100, and particularly preferably an integer from 5 to 75. Additionally, m12 is more preferably an integer from 1 to 150, further preferably an integer from 2 to 100, and particularly preferably an integer from 5 to 75.

[0193] In formula (F5), m12 is more preferably an integer from 1 to 150, further preferably an integer from 2 to 100, and particularly preferably an integer from 5 to 75. Additionally, m14 is more preferably an integer from 1 to 150, further preferably an integer from 2 to 100, and particularly preferably an integer from 5 to 75.

[0194] In formula (F6), m13 is more preferably an integer from 1 to 300, even more preferably an integer from 5 to 200, and particularly preferably an integer from 10 to 150.

[0195] From the perspective of ease of synthesis, G is preferred. 2 The polyfluoropolyether chain in formula (G2-1) has m10 as 1, that is, preferably G 2 It is the group shown in formula (B1).

[0196] -O-(R f21 O) c2 -R f22 -Formula (B2)

[0197] in,

[0198] R f21 and R f22 Each is independently a fluoroalkylene group having 1 to 6 carbon atoms, in the presence of multiple R f21 In the case of multiple R f21 Choose either the same or different from each other.

[0199] c2 is an integer from 1 to 500.

[0200] It should be noted that R f21 Specific examples are the same as those mentioned above. f1 ~R f6 The same as those listed in R. f22 Specific examples are the same as those mentioned above. f7 same.

[0201] From the perspective of excellent water and oil repellency and fingerprint removal properties, G 1 (poly)fluoroalkyl and G 2 The proportion of fluorine atoms in the (poly)oxyfluoroalkyl group [{number of fluorine atoms / (number of fluorine atoms + number of hydrogen atoms)}×100 (%)] is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.

[0202] Furthermore, from the viewpoint of wear resistance, the molecular weight of (poly)fluoroalkyl and (poly)fluoroalkylene is preferably 200 to 30,000, more preferably 600 to 25,000, and even more preferably 1,000 to 20,000.

[0203] [Q]1 Q 2 Q 3 ]

[0204] Q 1 It is a linking group with a single bond or an a1+b1 valence.

[0205] Q 2 It is a single bond or a linker group with a b2+1 valence.

[0206] Q 3 It is a single bond or a linker group with a b3+1 valence.

[0207] Q in compounds (A1) and (A2) 1 Q 2 and Q 3 They can have the same structure or different structures. Q 1 Q 2 and Q 3 The specific structure is the same, therefore, Q will be used below. 1 To provide an explanation on behalf of [the representative], unless otherwise specified, Q 2 and Q 3 Let's take Q as an example. 1 As the standard.

[0208] In Q 1 When the linking group is trivalent or higher, it is preferable to have at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of organopolysiloxane residues with C, N, Si, ring structures and (a1+b1) valence.

[0209] From the viewpoint of easily manufacturing compound (A1) or compound (A2) and of superior wear resistance of the surface layer, the ring structure constituting the branch point P is preferably selected from one of the following groups: aliphatic rings of 3 to 8 members, aromatic rings of 3 to 8 members, heterocyclic rings of 3 to 8 members, and fused rings composed of two or more of these rings. The ring structure listed in the following formula is particularly preferred. The ring structure may optionally have halogen atoms, alkyl groups (which may contain ether-type oxygen atoms between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, oxo groups (=O), etc., as substituents.

[0210]

[0211] The organopolysiloxane residues constituting the branch point P can be exemplified by the following groups. Wherein, R in the following formula... 25 It can be a hydrogen atom, alkyl group, alkoxy group, or phenyl group. R 25 The alkyl and alkoxy groups preferably have 1 to 10 carbon atoms, more preferably 1.

[0212]

[0213] Q with a valence of 2 or higher 1 Optional with selectable -C(O)NR 26 -、-CO(O)NR 26 -、-NR 26 C(O)-、-NR 26 CO(O)-、-NR 26 C(O)NR 26 -, -C(O)O-, -OC(O)-, -C(O)-, -O-, -NR 26 -, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 26 -、-SO2NR 26 -、-Si(R 26 )2-、-OSi(R 26 At least one bond (hereinafter referred to as "bond B") is formed from the group consisting of )2-, -Si(CH3)2-Ph-Si(CH3)2- and divalent organopolysiloxane residues. Wherein, R 26 It consists of hydrogen atoms, an alkyl group or a phenyl group having 1 to 6 carbon atoms, and Ph is a phenylene group. From the viewpoint of easily producing compounds (A1) or (A2), R... 26 The alkyl group preferably has 1 to 3 carbon atoms, more preferably 1 to 2.

[0214] Examples of divalent organopolysiloxane residues include groups of the following formula. Wherein, R in the following formula... 27 It can be a hydrogen atom, alkyl group, alkoxy group, or phenyl group. R 27 The alkyl and alkoxy groups preferably have 1 to 10 carbon atoms, more preferably 1.

[0215]

[0216] From the viewpoint of easily creating compound (A1) or compound (A2), the following are preferred as bond B: -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, and -C(O)NR. 26 -、-C(O)ONR 26 -、-NR 26 C(O)-、-NR 26 C(O)O-、-NR 26 C(O)NR 26 -、-O- or -SO2NR 26 From the viewpoint of further improving the wear resistance of the surface layer, -C(O)NR is preferred. 26 -、-C(O)-、-NR 26 -or -O-, further preferably -C(O)NR 26-or -C(O)-.

[0217] As a trivalent or higher Q 1 Two or more divalent hydrocarbon groups R can be listed. 28 Combinations with one or more branch points P (e.g., {P-(R)} 28 -) n1}), two or more hydrocarbon groups R 28 Combinations of one or more branch points P and one or more keys B (e.g., {P-(BR)} 28 -) n1}), etc. Where n1 is an integer greater than or equal to 3.

[0218] In addition, Q, as a divalent... 1 Examples of divalent hydrocarbon groups R can be listed. 28 One or two divalent hydrocarbon groups R 28 Combinations with bond B (e.g., -R) 28 -B-、-BR 28 -B-) etc.

[0219] As mentioned above, R 28 The divalent hydrocarbon group in the form of the divalent hydrocarbon group can be exemplified by, for example, divalent aliphatic hydrocarbon groups (alkylene, cycloalkylene, etc.) and divalent aromatic hydrocarbon groups (phenylene, etc.). The number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. It should be noted that R... 28 It can be substituted with fluorine at will.

[0220] In Q 1 When the valence is divalent, the compound (A1) is represented by the following formula (A1a).

[0221] G 1 -Q 1 -NHR A Equation (A1a)

[0222] Among them, G 1 and Q 1 Same as compound (A1).

[0223] As Q 1 From the viewpoint of easily manufacturing compound (A1) or compound (A2), groups represented by any of the following formulas (g2-1) to (g2-7) are preferred.

[0224]

[0225] (-AQ 12 -) e1 C(R 2 ) 4-e1-e2 (-Q 22 -) e2Formula g2-2

[0226] -AQ 13 -N(-Q 23 -)2 g2-3

[0227] (-AQ 14 -) h1 Z(-Q 24 -) h2 Formula g2-4

[0228] (-AQ 15 -) i1 Si(R 3 ) 4-i1-i2 (-Q 25 -) i2 Formula g2-5

[0229] -AQ 26 -Form g2-6

[0230] -AQ 12 -CH(-Q 22 -)-Si(R 3 ) 3-i3 (-Q 25 -) i3 Formula g2-7

[0231] In equations g2-1 to g2-7, side A and G 1 or G 2 Connection, Q 22 Q 23 Q 24 Q 25 Or Q 26 It is connected to a nitrogen atom on the side.

[0232] A is a single bond, an alkylene group, or an alkylene group with two or more carbon atoms having the following carbon-carbon inter-atom relationships: -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, -C(O)NR. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 -A group, in the presence of multiple A groups, the multiple A groups can be the same or different.

[0233] Q 11 For single bonds, -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, -C(O)NR 6-、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 - Alkylenes, or alkylenes having two or more carbon atoms, have carbon-carbon inter-carbon atoms with the following configurations: -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, -C(O)NR. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 - group.

[0234] Q 12 It is a single bond, an alkylene group, or an alkylene group having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 - groups, in the presence of multiple Q groups 12 In the case of multiple Qs 12 They can be the same or different.

[0235] Q 13 It is a single bond (where A is -C(O)-), an alkylene group, or an alkylene group with more than 2 carbon atoms having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 - or a group having a -C(O)- at the N-side end of an alkylene group.

[0236] In Q 14 When the atoms in the bonded Z are carbon atoms, Q14 For Q 12 In Q 14 When the atoms in the bonded Z are nitrogen atoms, Q 14 For Q 13 When there are multiple Q 14 In the case of multiple Qs 14 They can be the same or different.

[0237] Q 15 It is a single bond, an alkylene group, or an alkylene group having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 - groups, in the presence of multiple Q groups 15 In the case of multiple Qs 15 They can be the same or different.

[0238] Q 22 It is a single bond, an alkylene group, or an alkylene group having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 - groups, or -C(O)NR at the end of the alkylene group on the side not connected to NH2. 6 -、-C(O)-、-NR 6 A group with - or -O-, or a -C(O)NR group between carbon atoms of an alkylene group having two or more carbon atoms. 6 -、-C(O)-、-NR 6 -or -O- and has -C(O)NR at the end on the side not connected to NH2. 6 -、-C(O)-、-NR 6 - or -O- groups, in the presence of multiple Q 22 In the case of multiple Qs 22 They can be the same or different.

[0239] Q23 It is a single bond, an alkylene group, or an alkylene group having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 - group, 2 Q 23 They can be the same or different.

[0240] In Q 24 When the atoms in the bonded Z are carbon atoms, Q 24 For Q 22 In Q 24 When the atoms in the bonded Z are nitrogen atoms, Q 24 For Q 23 When there are multiple Q 24 In the case of multiple Qs 24 They can be the same or different.

[0241] Q 25 It is a single bond, an alkylene group, or an alkylene group having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR 6 - groups, in the presence of multiple Q groups 25 In the case of multiple Qs 25 They can be the same or different.

[0242] Q 26 It is a single bond, an alkylene group, or an alkylene group having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms. 6 -、-C(O)ONR 6 -、-NR 6 C(O)-、-NR 6 C(O)O-、-NR 6 C(O)NR 6 -、-O- or -SO2NR6 - group.

[0243] Z is a component with Q. 14 Directly bonded carbon or nitrogen atoms and having Q 24 A group with a ring structure containing carbon or nitrogen atoms in the h1+h2 valences that are directly bonded.

[0244] R 1 It is a hydrogen atom or an alkyl group, in the presence of multiple R 1 In the case of multiple R 1 They can be the same or different.

[0245] R 2 It can be a hydrogen atom, hydroxyl group, alkyl group or acyloxy group, in the presence of multiple R 2 In the case of multiple R 2 They can be the same or different.

[0246] R 3 It is an alkyl group, in the presence of multiple R 3 In the case of multiple R 3 They can be the same or different.

[0247] R 6 It is a hydrogen atom, an alkyl or phenyl group having 1 to 6 carbon atoms, and in the presence of multiple R atoms 6 In the case of multiple R 6 They can be the same or different.

[0248] d1 is an integer from 0 to 3, preferably 1 or 2.

[0249] d2 is an integer from 0 to 3, preferably 1 or 2.

[0250] d1+d2 is an integer from 1 to 3.

[0251] d3 is an integer from 0 to 3, preferably 0 or 1.

[0252] d4 is an integer from 0 to 3, preferably 2 or 3.

[0253] d3+d4 is an integer from 1 to 3.

[0254] d1+d3 is an integer from 1 to 5, preferably 1 or 2.

[0255] d2+d4 is an integer from 1 to 5, preferably 4 or 5.

[0256] e1 is an integer from 1 to 3, preferably 1 or 2.

[0257] e2 is an integer from 1 to 3, preferably 2 or 3.

[0258] e1+e2 is an integer from 2 to 4, preferably 1 or 2.

[0259] h1 is an integer greater than or equal to 1, preferably 1 or 2.

[0260] h2 is an integer greater than or equal to 1, preferably 2 or 3.

[0261] i1 is an integer from 1 to 3, preferably 1 or 2.

[0262] i2 is an integer from 1 to 3, preferably 2 or 3.

[0263] i1+i2 is an integer from 2 to 4, preferably 3 or 4.

[0264] i3 is an integer from 1 to 3, preferably 2 or 3.

[0265] Regarding Q 11 Q 12 Q 13 Q 14 Q 15 Q 22 Q 23 Q 24 Q 25 Or Q 26 From the viewpoint of facilitating the manufacture of compound (A1) or compound (A2) and forming a surface layer with superior durability, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. Where a specific bond exists between carbon atoms, the lower limit for the number of carbon atoms in the alkylene group is 2.

[0266] As ring structures in Z, the above-mentioned ring structures can be listed, and the preferred method is also the same. It should be noted that Q... 14 and / or Q 24 The ring structure is directly bonded to Z, therefore, for example, an alkylene group is attached to the ring structure, and Q will not be attached to that alkylene group. 14 and / or Q 24 .

[0267] From the perspective of easily producing compound (A1) or compound (A2), R 1 R 2 or R 3 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and particularly preferably 1 to 2.

[0268] From the perspective of easily producing compound (A1) or compound (A2), R 2 The alkyl moiety of the acyloxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and particularly preferably 1 to 2.

[0269] From the viewpoint of easily manufacturing compound (A1) or compound (A2) and forming a surface layer with superior durability, h1 is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0270] From the viewpoint of easily manufacturing compound (A1) or compound (A2) and forming a surface layer with superior durability, h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.

[0271] Q in equation (A2) 2 and Q 3 With the above Q 1 The methods are the same, and the preferred methods are also the same. Specifically, in the above Q... 1 In the description, a1 is replaced with 1, and b1 is in Q. 2 The middle is replaced by b2, in Q 3 Replace b3 with b3.

[0272] It should be noted that in Q 2 and Q 3 When the valence is divalent, the compound (A2) is represented by the following formula (A2a).

[0273] R B HN-Q 2 -G 2 -Q 3 -NHR C Equation (A2a)

[0274] Among them, Q 2 G 2 and Q 3 Same as compound (A2).

[0275] From the viewpoint of forming a surface layer with superior durability, Q is preferred for either compound (A1) or compound (A2) contained in this surface treatment agent. 1 Q 2 and Q 3 At least one of them is a group represented by the following formula (C1).

[0276] (-A 11 -) a2 Q 21 (-R 11 -R 12 -) b4 Formula (C1)

[0277] in,

[0278] A in equation (C1) 11 Side and G 1 or G 2 Connection, R12 The side is connected to a nitrogen atom.

[0279] A 11 It is a single bond, an alkylene group, or an alkylene group having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, or -C(O)NR between carbon atoms. 13 -、-C(O)ONR 13 -、-NR 13 C(O)-、-NR 13 C(O)O-、-NR 13 C(O)NR 13 -、-O- or -SO2NR 13 - groups, in the presence of multiple A groups 11 In the case of multiple A's 11 They can be the same or different.

[0280] R 11 For single key, -R 14 -C(O)O-、-R 14 -OC(O)-、-R 14 -C(O)-、-R 14 -OC(O)O-、-R 14 -C(O)NR 13 -、-R 14 -C(O)ONR 13 -、-R 14 -NR 13 C(O)-、-R 14 -NR 13 C(O)O-、-R 14 -NR 13 C(O)NR 13 -、-R 14 -O- or -SO2NR 13 - groups, in the presence of multiple R groups 11 In the case of multiple R 11 They can be the same or different.

[0281] R 12 It is an alkylene group having 1 to 10 carbon atoms that may have substituents; in alkylene groups having 2 or more carbon atoms, -O- or -NR may be present between carbon atoms. D -, R D It is a hydrogen atom or an alkyl group.

[0282] In the existence of multiple R 12 In the case of multiple R 12 They can be the same or different.

[0283] R 13It is a hydrogen atom, an alkyl or phenyl group having 1 to 6 carbon atoms, and in the presence of multiple R atoms 13 In the case of multiple R 13 They can be the same or different.

[0284] R 14 It is an alkylene group having 1 to 10 carbon atoms.

[0285] R 11 R 13 and R 14 The alkyl or alkylene groups may be substituted with fluorine.

[0286] Q 21 It is an a2+b4 valence group.

[0287] a2 is an integer greater than or equal to 1.

[0288] b4 is an integer greater than or equal to 1.

[0289] For either compound (A1) or compound (A2), from the viewpoint of forming a surface layer with superior wear resistance, Q is preferred. 1 Q 2 and Q 3 At least one of them is a group represented by the following formula (C2).

[0290] -Q 21 -R 12 - Equation (C2)

[0291] in,

[0292] Q 21 It is a group represented by any one of the following formulas (1) to (15).

[0293] In equations (1) to (15), *1 and G 1 or G 2 Connect, *2 and R 12 connect,

[0294] T N Each is independently a hydrogen atom or an alkyl group, optionally with R. 12 Connect to form a ring,

[0295] T C Represents a hydrogen atom or a substituent.

[0296] R 12 It is an alkylene group having 1 to 10 carbon atoms that may have substituents; in alkylene groups having 2 or more carbon atoms, -O- or -NR may be present between carbon atoms. D -, R D It can be a hydrogen atom or an alkyl group.

[0297]

[0298] Q 21 It is any one of the following formulas (1) to (15), preferably formulas (1), (2), (8), (12) or (15).

[0299] T N Each is independently a hydrogen atom or an alkyl group, preferably a hydrogen atom.

[0300] In T N When the alkyl group is alkyl, it can be a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group. Preferably, the alkyl group is a straight-chain alkyl group. Furthermore, the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 or 2.

[0301] T C It can be a hydrogen atom or a substituent.

[0302] In T C In the case of a substituent, examples of substituents include hydroxyl groups, optionally substituted alkyl groups, alkoxy groups, tertiary amino groups, halogen atoms, and imide groups. In the case of a substituent on an alkyl group, examples of substituents include tertiary amino groups, quaternary ammonium groups, hydroxyl groups, alkoxy groups, polyepoxyalkyl groups, halogen atoms, imide groups, and amino carbonyl groups optionally substituted with alkyl groups.

[0303] R 12 It is an alkylene group having 1 to 10 carbon atoms that may have substituents; in alkylene groups having 2 or more carbon atoms, -O- or -NR may be present between carbon atoms. D -, R D The alkylene group can be a hydrogen atom or an alkyl group. The alkylene group can be a straight-chain alkylene group, a branched alkylene group, or a cyclic alkylene group. Preferably, the alkylene group is a straight-chain alkylene group. The alkylene group preferably has 2 to 10 carbon atoms, more preferably 2 to 6. Examples of substituents that may be present in the alkylene group include carboxyl, hydroxyl, tertiary amino, quaternary ammonium, alkoxy, polyepoxyalkyl, halogen, imide, and optionally alkyl-substituted amino carbonyl groups.

[0304] [R] A R B R C ]

[0305] R A R B and R C Each is independently a hydrogen atom or an alkyl group.

[0306] R A Optional and Q 1 They connect to form a ring.

[0307] R B Optional and Q 2They connect to form a ring.

[0308] R C Optional and Q 3 They connect to form a ring.

[0309] By R A R B and R C The alkyl group can be a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group. Preferably, the alkyl group is a straight-chain alkyl group. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 or 2.

[0310] The molecular weights of compounds (A1) and (A2) are preferably 3000 or more, more preferably 5000 to 20000. The molecular weights of compounds (A1) and (A2) can be determined by gel permeation chromatography or nuclear magnetic resonance spectroscopy (NMR). Specifically, molecular weight determination using NMR spectroscopy is performed by... 1 H-NMR and 19 The molecular weight is determined by F-NMR, using an internal standard (e.g., 1,4-bis(trifluoromethyl)benzene) or terminal groups as a reference, based on the number (average) of oxyfluoroalkyl units. That is, the molecular weight mentioned above refers to the "number-average molecular weight".

[0311] Compounds (A1) and (A2) preferably contain a ring structure. In compound (A1), G 1 It may contain ring structures, Q 1 It may contain a ring structure, R A Optional and Q 1 They connect to form a ring. Additionally, in compound (A2), G... 2 It may contain ring structures, Q 2 and Q 3 It may contain a ring structure, R B Optional and Q 2 Connect to form a loop, R C Optional and Q 3 They connect to form a ring.

[0312] In particular, in compound (A1), Q is preferred. 1 Includes ring structure, or R A With Q 1 Connect to form a loop. If Q 1 Includes ring structure, or R A With Q 1 When linked to form rings, intramolecular cyclization reactions are less likely to occur. Therefore, it is considered to have excellent reactivity with the substrate surface. Through the reaction of amino groups with the substrate surface, a surface layer with excellent durability can be formed.

[0313] For the same reason, in compound (A2), Q is preferred. 2 and Q 3 Includes ring structure, or R B With Q 2 Connect to form a loop, and R C With Q 3 They connect to form a ring.

[0314] The compound (A1) is preferably represented by any one of the following formulas (A11) to (A14).

[0315] in,

[0316] Ring A indicates a heterocycle containing at least one nitrogen atom.

[0317] Ring B indicates a heterocycle containing two nitrogen atoms.

[0318] The C ring indicates a hydrocarbon ring or a heterocycle.

[0319] Ring D indicates a heterocycle containing at least one nitrogen atom.

[0320] R 21 ~R 24 Each is an independent single bond or connecting group.

[0321] R 31 R 32 R A1 and R A2 Each is independently a hydrogen atom or an alkyl group.

[0322] n1 and n2 are each independently 1 or 2.

[0323]

[0324] Examples of ring A include pyrrole rings, pyrrolidine rings, pyridine rings, piperidine rings, pyrazolidine rings, imidazoline rings, and piperazine rings. Among these, ring A is preferably a pyrrolidine ring, a piperidine ring, or a piperazine ring.

[0325] Examples of ring B include pyrazolidine rings, imidazolidine rings, and piperazine rings. Among these, piperazine rings are preferred.

[0326] Examples of aliphatic hydrocarbon rings represented by the C ring include cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornene, and adamantane rings; and aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, and fluorene rings. Examples of heterocycles represented by the C ring include pyrrole, furan, thiophene, pyrrolidine, imidazole, pyrazole, oxazole, imidazoleidine, pyrazolidine, oxazolidine, pyridine, piperazine, pyran, piperazine, and morpholine rings. The C ring is preferably a hydrocarbon ring, more preferably an aliphatic hydrocarbon ring, and even more preferably a cyclohexane ring.

[0327] Examples of ring D include pyrrole rings, pyrrolidine rings, pyridine rings, piperidine rings, pyrazolidine rings, imidazoline rings, and piperazine rings. Among these, pyrroleidine rings or piperidine rings are preferred.

[0328] R 21 ~R 24 Each component is preferably a single bond or an alkylene group. The alkylene group preferably has 1 to 6 carbon atoms. The alkylene group may optionally contain -O- or -NH-.

[0329] R 31 R 32 R A1 and R A2 Each is preferably a hydrogen atom or a methyl group.

[0330] In the aforementioned compound (A1), from the viewpoints of surface layer abrasion resistance, fingerprint removal, and water and oil repellency, b1 is preferably an integer of 2 or more. Having 2 or more amino groups further improves adhesion to the substrate. On the other hand, from the viewpoints of ease of manufacture, b1 is preferably 10 or less, more preferably 6 or less.

[0331] In the above compound (A1), from the viewpoint of fingerprint removal properties of the surface layer, water and oil repellency, and ease of compound manufacturing, a1 is preferably an integer from 1 to 10, and more preferably an integer from 1 to 6.

[0332] Furthermore, in the aforementioned compound (A2), from the viewpoints of surface layer abrasion resistance, fingerprint removal, and water and oil repellency, b2 and b3 are each preferably integers of 2 or more. By having 2 or more amino groups at the ends of each side of the polyfluoropolyether chain, the adhesion to the substrate is further improved. On the other hand, from the viewpoints of ease of manufacture, b2 and b3 are each preferably 10 or less, more preferably 6 or less.

[0333] The following compounds can be listed as specific examples of particular compounds.

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343] It should be noted that G 1 and G 2 As mentioned above, R f It is a polyfluoropolyether chain.

[0344] An example of a method for producing compound (A1) or compound (A2) is given below. The method is not limited to the one described below, but compound (A1) or compound (A2) is obtained in high yield according to the method described below.

[0345] Compound (A1) or compound (A2) can be synthesized using the compound represented by formula (D1) or the compound represented by formula (D2).

[0346] (G 1 -) a1 Q 1 (-C(=O)OCH3) b1 Equation (D1)

[0347] (H3COC(=O)-) b2 Q 2 -G 2 -Q 3 (-C(=O)OCH3) b3 Formula (D2)

[0348] The symbols are as described above, and the preferred method is also the same.

[0349] It should be noted that compounds (D1) and (D2) can be synthesized, for example, by referring to the method described in International Publication No. 2013 / 121984.

[0350] In this article, the content of a specific compound is preferably 50 to 99.999% by mass, more preferably 30 to 99.9% by mass, relative to the total mass of the surface layer.

[0351] The surface layer may contain other components besides the specific compound to achieve the effects of this disclosure. Other fluorinated compounds besides the specific compound can be listed as such other components.

[0352] Other fluorinated compounds include those produced as a byproduct during the manufacture of a particular compound (hereinafter also referred to as byproduct fluorinated compounds) and known fluorinated compounds.

[0353] As for other fluorinated compounds, compounds that are less likely to reduce the effects of this disclosure are preferred.

[0354] Examples of byproduct fluorinated compounds include unreacted fluorinated compounds produced during the synthesis of specific compounds. When a surface layer contains byproduct fluorinated compounds, purification processes for removing or reducing the amount of these compounds can be simplified.

[0355] Fluorine-containing compounds are well-known examples, such as those described in the following documents.

[0356] The perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No. 11-029585

[0357] The silicon-containing organic fluoropolymer described in Japanese Patent No. 2874715

[0358] The organosilicon compounds described in Japanese Patent Application Publication No. 2000-144097

[0359] The perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No. 2000-327772

[0360] Fluorinated siloxanes as described in Japanese Patent Publication No. 2002-506887

[0361] The organosilicon compounds described in Japanese Patent Publication No. 2008-534696

[0362] The fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936

[0363] 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,

[0364] The organosilicon compounds described in International Publication No. 2011 / 060047 and International Publication No. 2011 / 059430,

[0365] Fluorinated organosilane compounds described in International Publication No. 2012 / 064649,

[0366] The polymers containing fluorinated alkylene oxides described in Japanese Patent Application Publication No. 2012-72272

[0367] 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.

[0368] The silane compounds containing perfluoro(poly)ethers 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

[0369] Fluorinated polyether-based polymer-modified silanes described in Japanese Patent Application Publication Nos. 2015-199906, 2016-204656, 2016-210854, and 2016-222859

[0370] 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.

[0371] In addition, commercially available fluorinated compounds include Shin-Etsu Chemical Co., Ltd.'s KY-100 series (KY-178, KY-185, KY-195, etc.), AGC Co., Ltd.'s Afluid (registered trademark) S550, and Daikin Industries Co., Ltd.'s Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, etc.

[0372] From the viewpoint of fully utilizing the effects of this disclosure, the content of other fluorinated compounds relative to the total mass of the surface layer is preferably less than 50% by mass, more preferably less than 30% by mass, and even more preferably less than 10% by mass.

[0373] When the surface layer contains other fluorinated compounds, the content of the other fluorinated compounds relative to the total content of the specific compound and other fluorinated compounds is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0374] When the surface layer contains other fluorinated compounds, the total content of the specific compound and other fluorinated compounds is preferably 80% by mass or more, more preferably 85% by mass or more, relative to the total mass of the surface layer.

[0375] In a second aspect of the disclosed article, the surface layer is formed using a surface treatment agent containing a specific compound. Details of the specific compound are as described above.

[0376] The surface treatment agent may optionally contain other components besides the specific compounds. Other fluorinated compounds mentioned above can be listed as such other components.

[0377] The content of the specific compound relative to the total mass of the surface treatment agent is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.05 to 10% by mass.

[0378] The surface treatment agent optionally includes a liquid medium. The surface treatment agent is preferably liquid, and can be a solution or a dispersion. By including a liquid medium, the form, viscosity, surface tension, etc., of the surface treatment agent can be adjusted, and its liquid properties can be controlled to be suitable for the coating method.

[0379] Organic solvents are preferred as liquid media. These organic solvents can be fluorinated, non-fluorinated, or a combination of both.

[0380] Examples of fluorinated solvents include fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, fluorinated alkylamines, and fluorinated alcohols.

[0381] As fluorinated alkanes, compounds with 4 to 8 carbon atoms are preferred. Examples of commercially available products include C6F. 13 H (Product name "ASAHIKLIN (registered trademark) AC-2000", manufactured by AGC Corporation), C6F 13 C2H5 (product name "ASAHIKLIN (registered trademark) AC-6000", manufactured by AGC Company) and C2F5CHFCHFCF3 (product name "Vertrel (registered trademark) XF", manufactured by Chemours Company).

[0382] Examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.

[0383] As fluoroalkyl ethers, compounds with 4 to 12 carbon atoms are preferred. Examples of commercially available products include CF3CH2OCF2CF2H (product name "ASAHIKLIN (registered trademark) AE-3000", manufactured by AGC), C4F9OCH3 (product name "Novec (registered trademark) 7100", manufactured by 3M), C4F9OC2H5 (product name "Novec (registered trademark) 7200", manufactured by 3M), and C2F5CF(OCH3)C3F7 (product name "Novec (registered trademark) 7300", manufactured by 3M).

[0384] Examples of fluoroalkylamines include perfluorotripropylamine and perfluorotributylamine.

[0385] Examples of fluoro alcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0386] As a non-fluorinated solvent, compounds consisting only of hydrogen and carbon atoms, and compounds consisting only of hydrogen, carbon and oxygen atoms are preferred, and hydrocarbons, alcohols, ketones, ethers or esters are more preferred.

[0387] Examples of hydrocarbons include aliphatic hydrocarbons such as pentane, octane, hexane, and decane, as well as aromatic hydrocarbons such as toluene, xylene, and benzene.

[0388] Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, and tert-pentanol.

[0389] Examples of ketones include acetone, methyl ethyl ketone, and cyclohexanone.

[0390] Examples of ethers include chain ethers such as diethyl ether, dipropyl ether, and methyl tert-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and 1,3-dioxane.

[0391] Examples of esters include ethyl acetate and butyl acetate.

[0392] In addition, the solvent can be a nitrogen-containing compound, such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylenephosphoramide, N-methylcaprolactam, N-acetyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, N,N'-dimethylpropenylurea and tetramethylurea.

[0393] The content of the liquid medium relative to the total mass of the surface treatment agent is preferably 75 to 99.999% by mass, more preferably 85 to 99.99% by mass, and even more preferably 90 to 99.9% by mass.

[0394] The solid content concentration of the surface treatment agent is preferably 0.001–40% by mass, more preferably 0.01–20% by mass, even more preferably 0.01–10% by mass, and particularly preferably 0.01–1% by mass. The solid content includes specific compounds and, depending on the circumstances, other fluorinated compounds and other components. The solid content concentration of the surface treatment agent is calculated from the mass of the surface treatment agent before heating and the mass after heating in a convection dryer at 120°C for 4 hours.

[0395] In the second aspect of the article disclosed herein, the method of forming a surface layer using a surface treatment agent is not particularly limited.

[0396] <Metal>

[0397] This article contains a metal on a substrate. It is believed that the metal promotes the reaction between the substrate and the surface treatment agent. In addition to a specific compound, this article contains a metal, resulting in higher adhesion to the substrate compared to previous methods. During the manufacturing process of this article, compared to previous methods, heat treatment can be performed at low temperatures or for a short time, reducing the load on the substrate and thus suppressing warping.

[0398] The metal contained in this product has an electronegativity of 0.8 to 2.54.

[0399] In this disclosure, metals also include half-metals.

[0400] Regarding the metal, when the metal is used to form metal ions, the hydrolysis constant (pKh) of the metal ions is preferably 4.0 to 15.0, more preferably 4.0 to 14.0.

[0401] The hydrolysis constant (pKh) is calculated using the following formula (Baes, Jr. CF: Mesmer, R. The Hydrolysis of Cations, Willy: New York, 1976).

[0402] pKh = -logK ky

[0403] According to The relationship K is obtained from the following formula. xy .

[0404]

[0405] Furthermore, regarding the metal, it is preferable that, when the metal forms metal ions, the water exchange rate constant (WERC) of the metal ions is 3.2 × 10⁻⁶. 6 M -1 sec -1 above.

[0406] The water exchange rate constant was determined by nuclear magnetic resonance absorption, acoustic absorption, and polydentate ligand method (Martell, ABEd. Coordination Chemistry, Vol. 2, ACS Monograph 168, ACS: Washington, DC, 1978).

[0407] Regarding the metal, when the metal is used to form metal ions, it is preferable that the hydrolysis constant of the metal ions is 4.0 to 15.0 and the water exchange rate constant is 3.2 × 10⁻⁶. 6 M -1 sec -1 The above. More preferably, the hydrolysis constant of the metal ion is 5.0–15.0, and the water exchange rate constant is 1.0 × 10⁻⁶. 7 M -1 sec -1 The above is further preferred. The hydrolysis constant of the metal ion is 6.0–15.0, and the water exchange rate constant is 1.0 × 10⁻⁶. 7 M -1 sec -1 above.

[0408] Specifically, the metal is preferably selected from at least one element chosen from the group consisting of Li, Na, K, Mg, Ca, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Cr, Mn, Fe, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Sn, Pb, Bi, Te, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0409] More preferably, it is selected from at least one of the following: Li, Na, K, Mg, Ca, Ba, Sc, Y, Ln, Ti, V, Cr, Mn, Fe, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Hg, Al, Ga, In, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; even more preferably, it is selected from at least one of the following: Li, Na, K, Ca, Ba, Sc, Y, Ln, Mn, Fe, Cu, Ag, Zn, Cd, Hg, Pb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0410] Particularly preferred is at least one selected from the group consisting of Li, Na, K, Ca, Ba, Sc, Y, Ln, Mn, Fe, Cu, Ag, Zn, Cd, Pb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

[0411] The metals contained in this article can be detected using TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) and / or LA-ICP-MS (Laser Ablation-Inductively Coupled Plasma).

[0412] From the viewpoint of further suppressing article warping, the mass of metal per unit area on the surface of the substrate with the metal disposed thereon is preferably 0.0001 to 270 μg / cm². 2 More preferably, it is 0.0001–100 μg / cm³. 2 .

[0413] From the viewpoint of further suppressing warping of articles, the molar ratio of metal to the (poly)oxyfluoroalkyl chain contained in a particular compound is preferably 0.01 to 150,000 mol%, more preferably 0.1 to 100,000 mol%.

[0414] From the viewpoint of superior wear resistance, this article preferably further includes a structure that connects the substrate to the surface layer and has a structure derived from a specific compound.

[0415] A particular compound contains a primary or secondary amino group. Therefore, when the substrate has functional groups such as ester, cyano, amide, imide, carbonate, or urethane groups, the amino group reacts with these functional groups to form a bond during the article manufacturing stage, thereby connecting the substrate to the surface layer. Having a structure derived from a particular compound means that the structure of the particular compound, except for the primary or secondary amino group, is identical to that of the particular compound.

[0416] [How to make the item]

[0417] In the manufacturing method of this article, any pretreatment is performed on the substrate, including coating with a solution containing Brønsted acid, coating with a solution containing Lewis acid, or coating with a solution containing Brønsted acid followed by coating with a solution containing Lewis acid.

[0418] Applying a surface treatment agent containing a specific compound onto a pretreated substrate; or

[0419] After applying a surface treatment agent to the substrate, a solution containing Lewis acid is applied; or

[0420] A solution containing a surface treatment agent and Lewis acid is applied to a substrate.

[0421] <Method for applying a surface treatment agent to a pretreated substrate>

[0422] One method of manufacturing this article is as follows: a substrate is pretreated by coating it with a solution containing Brønsted acid, coating it with a solution containing Lewis acid, or coating it with a solution containing Brønsted acid followed by coating it with a solution containing Lewis acid; a surface treatment agent containing a specific compound is then coated onto the pretreated substrate. It is believed that the Lewis acid promotes the reaction between the substrate and the surface treatment agent.

[0423] (Preprocessing)

[0424] The details of the substrate used during pretreatment are as described above.

[0425] Examples of Brønsted acids include organic acids such as ascorbic acid, acetic acid, and citric acid, as well as inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and phosphoric acid. The Brønsted acid is preferably at least one selected from the group consisting of ascorbic acid, acetic acid, citric acid, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and phosphoric acid. From the viewpoint of reducing the load on the substrate, it is more preferably at least one selected from the group consisting of citric acid, acetic acid, hydrochloric acid, and nitric acid.

[0426] The solvent in a solution containing Brønsted acid is not particularly limited and can be water or an organic solvent. Organic solvents can be non-fluorinated solvents such as hydrocarbons, alcohols, ketones, ethers, and esters, or fluorinated solvents. Specific examples of non-fluorinated and fluorinated solvents are described above. The solvent can be appropriately selected based on the solubility and stability of Brønsted acid.

[0427] In the solution containing Brønsted acid, the concentration of Brønsted acid is preferably 0.5 to 50% by mass, more preferably 1 to 20% by mass.

[0428] The method for coating the solution containing Brønsted acid is not particularly limited, and can be any of the following: spin coating, roller coating, casting, wiping coating, doctor blade coating, mold coating, flow coating, spray coating, gravure coating, curtain coating, dip coating, and inkjet coating. However, from the viewpoint of improving durability, dip coating is preferred. Alternatively, ultrasonic treatment can be performed simultaneously with dip coating.

[0429] The metal constituting the Lewis acid is preferably a metal with an electronegativity of 0.8 to 2.54, and more specifically, the aforementioned metals are preferred.

[0430] As anions that constitute Lewis acids, examples include F - Cl - ,Br - Isohalide ions; alkoxide anions; CF3SO3 - (OTf - CH3SO3 - p-Toluenesulfonate anion, carboxylate anion, C n F 2n+1 SO3 - The anion constituting the Lewis acid is preferably a halide or OTf. - .

[0431] Examples of ligands that constitute Lewis acids include acetylacetone, ethyl acetoacetate, and octanediol.

[0432] Examples of Lewis acids include TiCl4, SnCl4, Ti(OMe)4, Co(acac)2, La(OTf)3, Nd(OTf)3, Yb(OTf)3, Zn(OTf)2, Cu(OTf)2, AgOTf, Ba(OTf)2, Mn(OTf)2, AlCl3, BF3, LiCl, NaOTf, and Ce(OTf)3. From the viewpoint of low environmental impact, the Lewis acid is preferably selected from at least one of the groups consisting of La(OTf)3, Nd(OTf)3, and LiCl.

[0433] The solvent in a solution containing a Lewis acid is not particularly limited and can be water or an organic solvent. Organic solvents can be non-fluorinated solvents such as hydrocarbons, alcohols, ketones, ethers, and esters, or fluorinated solvents. Specific examples of non-fluorinated and fluorinated solvents are described above. The solvent can be appropriately selected based on the solubility and stability of the Lewis acid.

[0434] In a solution containing Lewis acid, the concentration of Lewis acid is preferably 1 ppb to 5% by mass, more preferably 100 ppb to 1% by mass.

[0435] There are no particular limitations on the method of coating a solution containing Lewis acid. It can be any of the following: spin coating, roller coating, casting, wiping coating, scraping coating, mold coating, flow coating, spraying, gravure coating, curtain coating, dip coating, and inkjet coating. From the point of view of improving durability, dip coating is preferred.

[0436] In the pretreatment process, if a solution containing Brønsted acid is applied to the substrate followed by a solution containing Lewis acid, in order to fix the Brønsted acid to the substrate, it is preferable to dry the substrate coated with the solution containing Brønsted acid before applying the solution containing Lewis acid. The drying method is not particularly limited, but from the viewpoint of suppressing warping of the article, blowing air is preferred.

[0437] From the viewpoint of making the specific compounds contained in the surface treatment agent bond more firmly to the substrate, the pretreatment is preferably: coating a solution containing Lewis acid after coating a solution containing Brønsted acid.

[0438] (Coating of surface treatment agent)

[0439] Details of the surface treatment agent applied to the pretreated substrate and the specific compounds contained in the surface treatment agent are as described above.

[0440] There is no particular limitation on the method of coating a surface treatment agent containing a specific compound onto a pretreated substrate. It can be any of the following methods: spin coating, roller coating, casting, wiping coating, scraping coating, mold coating, flow coating, spray coating, gravure coating, curtain coating, dip coating, and inkjet coating. From the viewpoint of coating processing time, spin coating is preferred.

[0441] It is preferable to dry the pretreated substrate before applying the surface treatment agent. The drying method is not particularly limited, but from the viewpoint of suppressing warping of the article, blowing air is preferred.

[0442] It should be noted that the pretreated substrate can be preheated before applying the surface treatment agent. For example, the substrate can be heated using an electric furnace or an infrared (IR) furnace.

[0443] <Method for coating a substrate with a surface treatment agent followed by coating with a solution containing Lewis acid>

[0444] Details of the substrate, the surface treatment agent applied to the substrate, and the specific compounds contained in the surface treatment agent are as described above. Details of the Lewis acid-containing solution applied to the substrate coated with the surface treatment agent are as described above.

[0445] Furthermore, preferred methods for applying the surface treatment agent and for applying the solution containing Lewis acid are as described above.

[0446] After applying the surface treatment agent to the substrate, it is preferable to dry the substrate coated with the surface treatment agent before applying the solution containing Lewis acid. The drying method is not particularly limited, but from the viewpoint of suppressing warping of the article, blowing air is preferred.

[0447] <Method for coating a substrate with a solution containing a surface treatment agent and a Lewis acid>

[0448] Details of the substrate, the surface treatment agent coated on the substrate, and the Lewis acid are as described above.

[0449] There is no particular limitation on the method of coating a solution containing a surface treatment agent and Lewis acid onto a substrate. It can be any of the following methods: spin coating, roller coating, casting, wiping coating, scraping coating, mold coating, flow coating, spraying, gravure coating, curtain coating, dip coating, and inkjet coating. From the viewpoint of coating processing time, spin coating is preferred.

[0450] The preferred method for manufacturing this article is to coat a pretreated substrate with a surface treatment agent containing a specific compound. It is believed that by pretreating the substrate with at least one of a solution containing Brønsted acid and a solution containing Lewis acid, the substrate surface is activated, its reactivity with the specific compound contained in the surface treatment agent is improved, resulting in a stronger bond between the substrate and the surface layer.

[0451] In the manufacturing method of this article, it is preferable to coat a pretreated substrate with a surface treatment agent containing a specific compound, or to coat the substrate with a surface treatment agent followed by a solution containing a Lewis acid, or to coat the substrate with a solution containing both a surface treatment agent and a Lewis acid followed by baking. It should be noted that it is also possible to leave the substrate unbaked after coating.

[0452] When firing, from the viewpoint of suppressing warping of the article, the firing temperature is preferably 30℃~90℃ and the firing time is preferably 1~60 minutes.

[0453] Example

[0454] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0455] [Synthesis of Compound 1]

[0456]

[0457] Compound 1a was synthesized following the synthetic method for precursor (4a-2) described in International Publication No. 2013 / 121984. The average number of repeating units n was 13.

[0458] Add 4-(aminomethyl)-1-tert-butoxycarbonylpiperidine (0.071 g, 1.33 mmol), 4-(N,N-dimethylamino)pyridine (0.081 g, 0.66 mmol), ASAHIKLIN AC-2000 (manufactured by AGC Corporation, 0.838 g, 0.5 mL, hereinafter referred to as "AC-2000"), 1,4-dioxane (0.517 g, 0.5 mL), and compound 1a (number average molecular weight: approximately 4500, 1.0 g, 0.22 mmol) to a 30 mL flask. Stir at 25 °C for 3 days using a magnetic stirrer. Then, add methanol (1 mL) to the resulting solution, stir, and allow to stand. Repeat the process three times to remove the supernatant using a pipette. Add AC-2000 (5 mL) to the resulting solution and remove the supernatant by vacuum distillation. The crude product was purified by column chromatography to obtain compound 1b (0.81 g).

[0459]

[0460] The obtained compound 1b was dissolved in AC-2000 (6 mL) and cooled to 0 °C. Then, a 4N hydrogen chloride / ethyl acetate solution (2 mL) was added, and the mixture was stirred for 4 hours. After removing the solvent by vacuum distillation, AC-2000 (10 mL) and a 5% (w / w) sodium carbonate aqueous solution (2 mL) were added. After stirring, the lower layer was dried using sodium sulfate. The solvent was removed by vacuum distillation, thus giving compound 1 (0.54 g).

[0461] [Synthesis of Compound 2]

[0462]

[0463] In a 50 mL round-bottom flask, 1,3-diamino-2-propanol (0.065 g, 0.72 mmol), AC-2000 (9 mL), 1,4-dioxane (5.5 mL), and compound 1a (number average molecular weight: approximately 4500, 1.0 g, 0.22 mmol) were added. The mixture was stirred at 25 °C for 6 hours using a magnetic stirrer. After removing the solvent by vacuum distillation, the solution was dissolved in ASAHIKLIN AC-6000 (manufactured by AGC Corporation, hereinafter referred to as "AC-6000"), transferred to a separatory funnel, and the washing process with methanol was repeated three times. After removing AC-6000 by vacuum distillation, the crude product of compound 2 (1.13 g) was obtained.

[0464] The crude product of compound 2 was dissolved in an AC-2000 (5 mL) container, and triethylamine (0.1 mL, 0.72 mmol), 1,4-dioxane (1 mL), and di-tert-butyl dicarbonate (0.12 mL, 0.54 mmol) were added. The mixture was then stirred at 25 °C for 2 weeks using a magnetic stirrer. After removing the solvent by vacuum distillation, the crude product was purified by column chromatography to obtain compound 2a (0.48 g).

[0465]

[0466] The obtained compound 2a (0.2 g) was dissolved in AC-2000 (1.5 mL) and cooled to 0 °C. Then, a 4N hydrogen chloride / ethyl acetate solution (1.1 mL) was added, and the mixture was stirred for 1 day. Next, the solvent was removed by vacuum distillation. The crude product was then added to AC-2000 (10 mL) and a 5% (w / w) sodium bicarbonate aqueous solution (2 mL), stirred, and allowed to stand. The lower layer was separated and dried using sodium sulfate. After filtration, the solvent was removed by vacuum distillation to obtain compound 2 (0.20 g).

[0467] Next, surface treatment agent 1 and surface treatment agent 2 were prepared using compound 1 and compound 2.

[0468] [Preparation of Surface Treatment Agent 1 and Surface Treatment Agent 2]

[0469] A mixed solution of AC-2000 and ethanol (ethanol concentration: 3% by mass) was added relative to compound 1 (0.05 g) to bring the content of compound 1 to 0.1% by mass. The resulting solution was used as surface treatment agent 1. Surface treatment agent 2 was prepared from compound 2 using the same method.

[0470] [Item crafting]

[0471] (Examples 1 to 4, 7 to 9, 11, 13, 15, 16, 20 to 27)

[0472] As the substrate, a PMMA substrate (acrylic sheet (MR sheet) manufactured by Acrysunday Co., Ltd., with a surface hardness (pencil hardness) of 6H and a thickness of 10cm × 10cm × 3mm) that has undergone hard coating was used. The substrate was immersed in 200mL of an aqueous solution containing Brønsted acid as described in Tables 1-5, and then treated with ultrasound for 10 minutes. The substrate was then removed and dried in air. The substrate was then immersed in 200mL of an aqueous solution containing Lewis acids as described in Tables 1-5 at the concentrations described in Tables 1-5, and then treated with ultrasound for 10 minutes. The substrate was then removed and dried in air. Using a spin coater (product name "Opticoat MS-B200", manufactured by MIKASA Co., Ltd.), 2mL of a surface treatment agent containing the specific compounds described in Tables 1-5 was placed on the substrate and rotated at 500rpm for 1 minute. The substrate was then fired in an infrared furnace at the temperatures and times described in Tables 1-5 to obtain an article with a surface layer.

[0473] (Example 5)

[0474] Articles with a surface layer were obtained using the same method as in Example 1, without pretreatment with solutions containing Brønsted acid and Lewis acid.

[0475] (Examples 6, 10, 12, 14, 17)

[0476] Without pretreatment with solutions containing Brønsted acid and Lewis acid, the article with a surface layer was obtained by calcination at the temperatures and times recorded in Tables 1 to 5, except that the same method as in Example 1 was used.

[0477] (Example 18)

[0478] Instead of using a solution containing Brønsted acid, a solution containing Lewis acid was used for pretreatment, and otherwise an article with a surface layer was obtained by the same method as in Example 1.

[0479] (Example 19)

[0480] Instead of using a solution containing Lewis acid, a solution containing Brønsted acid was used for pretreatment, and otherwise an article with a surface layer was obtained by the same method as in Example 1.

[0481] The initial water contact angle of the obtained items was measured to evaluate abrasion resistance and warpage.

[0482] In addition, the mass of metal per unit area relative to the surface of the substrate was measured, and the result in Example 1 was 1.39 μg / cm³. 2 In Example 2, it was 1.44 μg / cm³. 2In Example 3, it was 0.069 μg / cm³. 2 In Example 4, it was 69.5 μg / cm³. 2 In the article, the molar ratio of the metal to the (poly)oxyfluoroalkyl chain is 1250 mol% in Example 1.

[0483] <Initial water contact angle>

[0484] Approximately 2 μL of pure water was added to the surface of the article where the surface layer was formed (hereinafter referred to as the "surface layer forming surface"). The water contact angle was measured using a contact angle measuring device (product name "DM-500", manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different points on the surface layer forming surface, and the average value was calculated as the initial water contact angle. The contact angle was calculated using the 2θ method. It should be noted that an ionizer and a forced-air treatment were performed for each measurement before determining the water contact angle.

[0485] <Abrasion Resistance>

[0486] For the surface layer forming of the item, use a pressure head equipped with KANAKIN No. 3 (bottom area: 100mm²). 2 The wear test was conducted using a 3-stage surface wear testing machine (product name "PA-300A", manufactured by Daiei Scientific Instruments Co., Ltd.) under the following conditions: 24℃, 40% RH atmosphere, 1000g load, 60rpm rotation speed, and 40mm stroke length. After a specified number of friction cycles, the water contact angle was measured. The method for measuring the water contact angle is the same as that for measuring the initial water contact angle. It should be noted that "-" in the table indicates that the water contact angle cannot be measured.

[0487] <Warp>

[0488] The resulting article was placed on a flat and level platform. The height A2 of the central portion of the article was measured using vernier calipers. Similarly, the height A1 of the central portion was measured for articles before firing during the manufacturing process. Warpage was evaluated based on the value (ΔH) obtained by subtracting A1 from A2. It can be said that the smaller the ΔH, the more suppressed the warpage. It should be noted that the unit of ΔH representing warpage in the table is mm. In the table, "-" in the component column indicates that the component was not added. "-" in the number of friction cycles column indicates that it was not performed.

[0489] [Table 1]

[0490]

[0491] [Table 2]

[0492]

[0493] [Table 3]

[0494]

[0495] [Table 4]

[0496]

[0497] [Table 5]

[0498]

[0499] [Table 6]

[0500]

[0501] As shown in Tables 1 to 6, the articles of Examples 1 to 4, 7 to 9, 11, 13, 15, 16, 18, and 20 to 27 contain a substrate, a surface layer disposed on the substrate, and a metal. The surface layer contains a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amino group. The metal has an electronegativity of 0.8 to 2.54. Therefore, the articles exhibit excellent wear resistance and warpage is suppressed.

[0502] It should be noted that the publication of Japanese Patent Application No. 2023-062399, filed on April 6, 2023, is incorporated herein by reference in its entirety. Furthermore, all documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if they were specifically and separately described.

Claims

1. An article comprising a substrate, a surface layer disposed on the substrate, and a metal. The surface layer comprises a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amino group. The metal is a metal with an electronegativity of 0.8 to 2.

54.

2. An article comprising a substrate, a surface layer disposed on the substrate, and a metal. The surface layer is formed using a surface treatment agent comprising a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amino group. The metal is a metal with an electronegativity of 0.8 to 2.

54.

3. The article according to claim 1 or 2, wherein, The compound is selected from at least one of the groups consisting of fluorine-containing compounds represented by the following formulas (A1) and (A2). (G 1 -) a1 Q 1 (-NHR A ) b1 …(A1) (R B HN-) b2 Q 2 -G 2 -Q 3 (-NHR C ) b3 …(A2) in, G 1 It is a (poly)fluoroalkyl group, in the presence of multiple G 1 In the case of multiple Gs 1 Choose either the same or different from each other. G 2 It is a (poly)oxyfluorine alkyl group. Q 1 It is a linking group with a single bond or an a1+b1 valence. Q 2 It is a single bond or a linker group with a b2+1 valence. Q 3 It is a linker group with a single bond or a b3+1 valence. a1 is an integer greater than or equal to 1. b1 is an integer greater than or equal to 1. b2 is an integer greater than or equal to 1. b3 is an integer greater than or equal to 1. R A R B and R C Each is independently a hydrogen atom or an alkyl group. R A Optional and Q 1 Connect to form a ring, R B Optional and Q 2 Connect to form a ring, R C Optional and Q 3 They connect to form a ring.

4. The article according to claim 1 or 2, wherein, The metal is selected from at least one of the following groups: Li, Na, K, Mg, Ca, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Cr, Mn, Fe, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Sn, Pb, Bi, Te, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

5. The article according to claim 1 or 2, wherein, The mass of the metal per unit area is 0.0001–270 μg / cm² relative to the surface of the substrate on which the metal is disposed. 2 .

6. The article according to claim 1 or 2, wherein, The substrate comprises at least one selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, acrylonitrile / styrene copolymer, polyacrylonitrile, polymethyl methacrylate, polycarbonate and polyethylene terephthalate.

7. The article of claim 1 or 2, further comprising a structure connecting the substrate and the surface layer and having a structure derived from the compound.

8. The article according to claim 1 or 2, wherein, The molar ratio of the metal to the (poly)oxyfluorine alkyl chain is 0.01 to 150,000 mol%.

9. A method for manufacturing an article, wherein, Any pretreatment of the substrate, including coating with a solution containing Brønsted acid, coating with a solution containing Lewis acid, or coating with a solution containing Brønsted acid followed by coating with a solution containing Lewis acid. A surface treatment agent comprising a compound having a (poly)oxyfluoroalkyl chain and having a primary or secondary amino group is coated onto the pretreated substrate; or After applying the surface treatment agent to the substrate, a solution containing Lewis acid is applied; or A solution containing the surface treatment agent and Lewis acid is coated onto the substrate.

10. The method of manufacturing the article according to claim 9, wherein, The Brønsted acid is selected from at least one of the following groups: ascorbic acid, acetic acid, citric acid, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and phosphoric acid.

11. The method of manufacturing the article according to claim 9 or 10, wherein, The metal constituting the Lewis acid is a metal with an electronegativity of 0.8 to 2.

54.

12. The method of manufacturing the article according to claim 11, wherein, The metal is selected from at least one of the following groups: Li, Na, K, Mg, Ca, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Cr, Mn, Fe, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Sn, Pb, Bi, Te, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

13. The method of manufacturing the article according to claim 9 or 10, wherein, The Lewis acid is selected from at least one of the groups consisting of La(OTf)3, Nd(OTf)3 and LiCl.

14. The method of manufacturing the article according to claim 9 or 10, wherein, In the solution containing the Lewis acid, the concentration of the Lewis acid is 1 ppb to 5 ppm by mass.

15. The method of manufacturing the article according to claim 9 or 10, wherein, The compound is selected from at least one of the groups consisting of fluorine-containing compounds represented by the following formulas (A1) and (A2). (G 1 -) a1 Q 1 (-NHR A ) b1 …(A1) (R B HN-) b2 Q 2 -G 2 -Q 3 (-NHR C ) b3 …(A2) in, G 1 It is a (poly)fluoroalkyl group, in the presence of multiple G 1 In the case of multiple Gs 1 Choose either the same or different from each other. G 2 It is a (poly)oxyfluorine alkyl group. Q 1 It is a linking group with a single bond or an a1+b1 valence. Q 2 It is a single bond or a linker group with a b2+1 valence. Q 3 It is a linker group with a single bond or a b3+1 valence. a1 is an integer greater than or equal to 1. b1 is an integer greater than or equal to 1. b2 is an integer greater than or equal to 1. b3 is an integer greater than or equal to 1. R A R B and R C Each is independently a hydrogen atom or an alkyl group. R A Optional and Q 1 Connect to form a ring, R B Optional and Q 2 Connect to form a ring, R C Optional and Q 3 They connect to form a ring.

16. The method of manufacturing the article according to claim 9 or 10, wherein, The substrate comprises at least one selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, acrylonitrile / styrene copolymer, polyacrylonitrile, polymethyl methacrylate, polycarbonate and polyethylene terephthalate.

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