WO2024210068A1 - Article and method for manufacturing article - Google Patents

Abstract

The present invention provides an article and an application of the article. The article includes a base material, and a metal and a surface layer provided on the base material. The surface layer contains a (poly)oxyfluoralkylene chain and a compound having a primary amino group or a secondary amino group. The metal has an electronegativity of 0.8-2.54.

Description

Article and method for manufacturing article

This disclosure relates to articles and methods for manufacturing articles.

In recent years, the performance required for a surface layer formed using a fluorinated ether compound has been increasing. For example, when the surface layer is applied to a member constituting a surface touched by fingers, the surface layer is required to have a performance (e.g., water repellency) that is not likely to decrease even when repeatedly worn, that is, a surface layer having excellent abrasion resistance.
For example, Patent Document 1 describes a surface treatment agent containing a fluorine-containing compound having a (poly)oxyfluoroalkylene chain.

International Publication No. 2022/209502

The surface treatment agent described in Patent Document 1 is capable of forming a surface layer having excellent durability because the fluorine-containing compound contained in the surface treatment agent adheres to various substrates through hydrogen bonds or chemical bonds.
However, depending on the substrate used, warping due to heat may occur, and there has been a demand for an article having a surface layer with excellent abrasion resistance and suppressed warping.

This disclosure has been made in light of these circumstances, and the problem that one embodiment of the present invention aims to solve is to provide an article and a method for manufacturing an article that has a surface layer with excellent abrasion resistance and is suppressed from warping.

The present disclosure includes the following aspects.
＜1＞
A substrate, a surface layer and a metal provided on the substrate,
the surface layer contains a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group,
The article, wherein the metal is a metal having an electronegativity of 0.8 to 2.54.
＜2＞
A substrate, a surface layer and a metal provided on the substrate,
the surface layer is formed using a surface treatment agent containing a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group,
The article, wherein the metal is a metal having an electronegativity of 0.8 to 2.54.
＜3＞
The article according to <1> or <2>, 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):
(G ¹ -) _a1 Q ¹ (-NHR ^A ) _b1 ... (A1)
(R ^B HN-) _b2 Q ² -G ² -Q ³ (-NHR ^C ) _b3 ... (A2)
however,
G ¹ is a (poly)oxyfluoroalkyl group, and when there are a plurality of G ¹ , the plurality of G ¹ may be the same or different;
^G2 is a (poly)oxyfluoroalkylene group;
^Q1 is a single bond or a linking group having a valence of a1+b1;
^Q2 is a single bond or a b2+1 valent linking group;
^Q3 is a single bond or a b3+1 valent linking group;
a1 is an integer of 1 or more,
b1 is an integer of 1 or more,
b2 is an integer of 1 or more,
b3 is an integer of 1 or more.
R ^A , R ^B , and R ^C each independently represent a hydrogen atom or an alkyl group;
^R may be linked with ^Q to form a ring;
R ^B may be linked with ^Q2 to form a ring;
R ³ may be linked to Q ³ to form a ring.
＜4＞
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.
＜5＞
The article according to any one of <1> to <4>, wherein the mass of the metal per unit area on the surface of the substrate on which the metal is provided is 0.0001 to 270 μg/ ^cm2 .
＜6＞
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.
＜７＞
The article according to any one of <1> to <6>, further comprising a structure that connects the substrate and the surface layer and has a structure derived from a compound.
＜8＞
The article according to any one of <1> to <7>, wherein the molar ratio of the metal to the (poly)oxyfluoroalkylene chain is 0.01 to 150,000 mol %.
＜9＞
A pretreatment is performed on a substrate by applying a solution containing a Brønsted acid, applying a solution containing a Lewis acid, or applying a solution containing a Brønsted acid and then applying a solution containing a Lewis acid;
A surface treatment agent containing a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group is applied to the pretreated substrate,
A surface treatment agent is applied to the substrate, and then a solution containing a Lewis acid is applied to the substrate, or
A method for producing an article, comprising applying a solution containing a surface treatment agent and a Lewis acid onto a substrate.
＜10＞
The method for producing an article according to <9>, wherein the Bronsted 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.
<11>
The method for producing an article according to <9> or <10>, wherein the metal constituting the Lewis acid is a metal having an electronegativity of 0.8 to 2.54.
＜12＞
The method for producing an article according to <11>, 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.
＜13＞
The method for producing an article according to any one of <9> to <12>, wherein the Lewis acid is at least one selected from the group consisting of La(OTf) ₃ , Nd(OTf) ₃ , and LiCl.
＜14＞
The method for producing 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% by mass.
＜15＞
The method for producing 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):
(G ¹ -) _a1 Q ¹ (-NHR ^A ) _b1 ... (A1)
(R ^B HN-) _b2 Q ² -G ² -Q ³ (-NHR ^C ) _b3 ... (A2)
however,
G ¹ is a (poly)oxyfluoroalkyl group, and when there are a plurality of G ¹ , the plurality of G ¹ may be the same or different;
^G2 is a (poly)oxyfluoroalkylene group;
^Q1 is a single bond or a linking group having a valence of a1+b1;
^Q2 is a single bond or a b2+1 valent linking group;
^Q3 is a single bond or a b3+1 valent linking group;
a1 is an integer of 1 or more,
b1 is an integer of 1 or more,
b2 is an integer of 1 or more,
b3 is an integer of 1 or more.
R ^A , R ^B , and R ^C each independently represent a hydrogen atom or an alkyl group;
^R may be linked with ^Q to form a ring;
R ^B may be linked with ^Q2 to form a ring;
R ³ may be linked to Q ³ to form a ring.
＜16＞
The method for producing an article according to any one of <9> to <15>, wherein the substrate contains at least one selected from the group consisting of an acrylonitrile/butadiene/styrene copolymer, an acrylonitrile/styrene copolymer, polyacrylonitrile, polymethyl methacrylate, polycarbonate, and polyethylene terephthalate.

According to one embodiment of the present invention, an article having a surface layer with excellent abrasion resistance and suppressed warping, and a method for manufacturing the article are provided.

In the present disclosure, the numerical ranges indicated using "to" include the numerical values before and after "to" as the minimum and maximum values, respectively.
In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
In this disclosure, the following terms have the following meanings:
In the present disclosure, the compound represented by formula (A1) will be referred to as compound (A1). The same applies to compounds, groups, etc. represented by other formulae.
The perfluoroalkyl group means a group in which all hydrogen atoms of an alkyl group are replaced with fluorine atoms. The fluoroalkyl group is a collective term for partial fluoroalkyl groups and perfluoroalkyl groups. The partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are replaced with fluorine atoms and which has one or more hydrogen atoms. In other words, the fluoroalkyl group is an alkyl group having one or more fluorine atoms.
The (poly)oxyfluoroalkyl group is a fluoroalkyl group having one or more oxy groups in the chain, and the same applies to a (poly)oxyfluoroalkylene group.
The term "surface layer" refers to a layer formed on the surface of a substrate.

[Items]
A first aspect of the article of the present disclosure includes a substrate, and a surface layer and a metal provided on the substrate, wherein the surface layer includes a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group, and the metal has an electronegativity of 0.8 to 2.54.
A second aspect of the article of the present disclosure includes a substrate, and a surface layer and a metal provided on the substrate, the surface layer being formed using a surface treatment agent containing a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group, and the metal being a metal having an electronegativity of 0.8 to 2.54. Hereinafter, the first and second aspects of the article of the present disclosure are also referred to as "the article".

This article has a surface layer and a metal provided on a substrate, and the surface layer contains a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group, so that the surface layer has excellent abrasion resistance and is also suppressed from warping.

Each component of the present article will be described below.
<Substrate>

The material of the substrate may be appropriately selected depending on the application of the present article, and may be either a transparent substrate or an opaque substrate, and may have any shape. When the substrate is in the form of a film or plate, the substrate may be a rigid material that has no flexibility, or a flexible material that has flexibility.
Specific examples of materials for the substrate include glass; acetylcellulose-based resins such as triacetylcellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; olefin resins such as polyethylene and polymethylpentene; acrylic resins such as polymethylmethacrylate; urethane resins; resins such as polyethersulfone, polycarbonate, polysulfone, polyether, polyetherketone, polyimide, polyacrylonitrile, polymethacrylonitrile, cycloolefin polymer, and cycloolefin copolymer; metals such as gold, platinum, and copper; metal oxides such as silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), indium tin oxide (ITO), lead zirconate titanate (PLT), silver oxide, and copper oxide; sapphire, stone, paper, and cloth.
The transparent substrate means a substrate having a normal incidence visible light transmittance of 25% or more in accordance with JIS R3106:1998 (ISO 9050:1990).

The substrate may also be a substrate having a hard coat layer formed on its surface, i.e., a substrate with a hard coat layer. In this disclosure, a substrate with a hard coat layer is included in the concept of a substrate.

Examples of the hard coat layer include an acrylate-based hard coat layer, a urethane acrylate-based hard coat layer, and an epoxy-based hard coat layer. Of these, the hard coat layer is preferably an acrylate-based hard coat layer or a urethane acrylate-based hard coat layer.

The thickness of the hard coat layer is preferably 0.01 μm to 2,000 μm, and particularly preferably 0.02 μm to 500 μm. Methods for measuring the thickness of the hard coat layer include a method of observing the cross section of the hard coat layer using an electron microscope (SEM, TEM, etc.), and a method using an optical interference thickness meter, a spectroscopic ellipsometer, a step gauge, etc.

In particular, from the viewpoint of reactivity with the primary amino group or secondary amino group contained in the specific compound, the base material preferably contains a resin, and more preferably contains a resin containing at least one selected from the group consisting of an ester group, a cyano group, an amide group, an imide group, a carbonate group, and a carbamate group.

Specifically, examples of the substrate include a resin having a functional group capable of reacting with the amino group in a side chain, and a resin having a functional group capable of reacting with the amino group in a main chain.
Examples of the resin having a functional group capable of reacting with an amino group on a side chain include ABS resin (acrylonitrile/butadiene/styrene copolymer), AS resin (acrylonitrile/styrene copolymer), PAN (polyacrylonitrile), and PMMA (polymethyl methacrylate).
Examples of the resin having a functional group capable of reacting with an amino group in the main chain include polyester (such as PET (polyethylene terephthalate)), polycarbonate, polyurethane, polyamide (such as nylon 6), and urethane acrylate.

From the viewpoint of obtaining a stronger bond between the substrate and the amino group, the substrate is preferably a resin having a functional group capable of reacting with the amino group at a side chain, and more preferably contains at least one type selected from the group consisting of ABS resin, AS resin, PAN, PMMA, polycarbonate, and PET.
When the substrate is a substrate with a hard coat layer, the hard coat layer preferably contains at least one selected from the group consisting of ABS resin, AS resin, PAN, PMMA, polycarbonate, and PET.
<Surface layer>
The present article has a surface layer and a metal on a substrate. The metal may be included in the surface layer, may be provided on the surface layer without being included in the surface layer, or may be provided between the substrate and the surface layer. The surface layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface of the substrate. The surface layer may spread in the form of a film on the surface of the substrate, or may be scattered in the form of dots.

In a first embodiment of the article of the present disclosure, the surface layer contains a (poly)oxyfluoroalkylene chain and a compound having a primary amino group or a secondary amino group (hereinafter also referred to as a "specific compound").

In the specific compound, the number of (poly)oxyfluoroalkylene chains is not particularly limited, and may be only one, or may be two or more.
In the specific compound, the number of primary amino groups or secondary amino groups is not particularly limited, and may be only one, or may be two or more.
In the specific compound, the (poly)oxyfluoroalkylene chain and the primary amino group or the secondary amino group may be bonded directly or via a linking group.
The (poly)oxyfluoroalkylene chain may contain a hydrogen atom, but from the viewpoint of further improving abrasion resistance, it is preferably a (poly)oxyperfluoroalkylene chain.

From the viewpoint of obtaining a surface layer having superior abrasion resistance, the specific compound is preferably at least one selected from the group consisting of fluorine-containing compounds represented by the following formula (A1) and the following formula (A2).
(G ¹ -) _a1 Q ¹ (-NHR ^A ) _b1 ... (A1)
(R ^B HN-) _b2 Q ² -G ² -Q ³ (-NHR ^C ) _b3 ... (A2)
however,
G ¹ is a (poly)oxyfluoroalkyl group, and when there are a plurality of G ¹ , the plurality of G ¹ may be the same or different;
^G2 is a (poly)oxyfluoroalkylene group;
^Q1 is a single bond or a linking group having a valence of a1+b1;
^Q2 is a single bond or a b2+1 valent linking group;
^Q3 is a single bond or a b3+1 valent linking group;
a1 is an integer of 1 or more,
b1 is an integer of 1 or more,
b2 is an integer of 1 or more,
b3 is an integer of 1 or more.
R ^A , R ^B , and R ^C each independently represent a hydrogen atom or an alkyl group;
^R may be linked with ^Q to form a ring;
R ^B may be linked with ^Q2 to form a ring;
R ³ may be linked to Q ³ to form a ring.

[ ^G1 ]
^G1 is a (poly)oxyfluoroalkyl group.

The (poly)oxyfluoroalkyl group for G ¹ is a fluoroalkyl group having --O-- at the end bonded to Q ¹ , having --O-- between carbon atoms in a carbon chain having 2 or more carbon atoms, or having both.

From the viewpoint of ease of production, ^G1 is preferably a structure represented by the following formula (G1-1).
R ^f0 O-[(R ^f1 O) _m1 (R ^f2 O) _m2 (R ^f3 O) _m3 (R ^f4 O) _m4 (R ^f5 O) _m5 (R ^f6 O) _m6 ]-R ^f7 - Formula (G1-1)
however,
R ^f0 is a fluoroalkyl group having 1 to 20 carbon atoms,
R ^f1 is a fluoroalkylene group having 1 carbon atom;
R ^f2 is a fluoroalkylene group having 2 carbon atoms,
R ^f3 is a fluoroalkylene group having 3 carbon atoms,
R ^f4 is a fluoroalkylene group having 4 carbon atoms,
R ^f5 is a fluoroalkylene group having 5 carbon atoms,
R ^f6 is a fluoroalkylene group having 6 carbon atoms.
R ^f7 is a fluoroalkylene group having 1 to 6 carbon atoms;
m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more, and m1+m2+m3+m4+m5+m6 is an integer of 0 to 500.

From the viewpoint of forming a surface layer excellent in durability, water and oil repellency, and fingerprint stain removability, it is preferable that m1+m2+m3+m4+m5+m6 is an integer of 1 to 500, i.e., ^G1 is a polyoxyfluoroalkyl group. From the viewpoint of forming a surface layer excellent in durability, water and oil repellency, and fingerprint stain removability, it is more preferable that m1+m2+m3+m4+m5+m6 is an integer of 1 to 300, further preferably an integer of 5 to 200, and particularly preferably an integer of 10 to 150.
In addition, the bonding order of (R ^f1 O) to (R ^f6 O) in formula (G1-1) is arbitrary.
In formula (G1-1), m1 to m6 respectively represent the number of (R ^f1 O) to (R ^f6 O), and do not represent the arrangement. For example, (R ^f5 O) _m5 represents that the number of (R ^f5 O) is m5, and does not represent a block arrangement structure of (R ^f5 O) _m5 . Similarly, the order of (R ^f1 O) to (R ^f6 O) does not represent the bonding order of each unit.

In R ^f0 , the fluoroalkyl group may be a straight-chain fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.
In R ^f3 to R ^f6 , the fluoroalkylene group may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.

Specific examples of R ^f1 include --CF ₂ -- and --CHF--.
Specific examples of R ^f2 include -CF ₂ CF ₂ -, -CHFCF ₂ -, -CHFCHF-, -CH ₂ CF ₂ -, and -CH ₂ CHF-.
Specific examples of R ^f3 include -CF ₂ CF ₂ CF ₂ -, _{-CF 2 CH 2} CF ₂ -, -CHFCF ₂ CF ₂ - _, -CHFCHF ₂ - _{, -CHFCHFCHF- ,} -CHFCH _{2 CF 2} - _, -C H2CF2CF2-, -CH2CHFCF2-, _-CH2CH2CF2- , _-CH2CF2CHF- , -CH2CH2CHF-, -CH2CH2CHF-, _-CF ( _CF3 ) _-CF2- , _-CF2 )-CF ₂ -, _{-CF ( CH 2} F _{) -CF 2} -, -CF( _CH3 ) _-CF2- , -CF( _CF3 )-CHF-, -CF( _CHF2 )-CHF-, -CF(CH2F)-CHF-, -CF( _CH3 )-CHF-, -CF(CF3)-CH2-, -CF( _CHF2 ) _-CH2- , -CF(CH ₂ F)-CH ₂ -, -CF(CH ₃ )-CH ₂ -, -CH(CF ₃ )-CF ₂ -, -CH(CHF ₂ )-CF ₂ -, -CH(CH _{2 F} ) _{-CF 2} -, -CH(CH _{3 )} -CF ₂ -, -CH(CF ₃ )-C HF-, -CH(CHF ₂ )-CHF-, -CH(CH ₂ F)-CHF-, -CH(CH ₃ )-CHF-, -CH(CF ₃ )-CH ₂ -, -CH(CHF ₂ )-CH ₂ -, and -CH(CH ₂ F)-CH ₂ -.
Specific examples of R ^f4 include -CF ₂ CF ₂ CF ₂ CF ₂ -, -CHFCF ₂ CF ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ CF ₂ -, -CF ₂ CHFCF ₂ CF ₂ -, -CHFCHF ₂ CF ₂ -, _{-CH 2 CHFCF} 2 CF ₂ -, -CF ₂ CH ₂ CF ₂ CF ₂ -, -CHFCH ₂ CF ₂ CF ₂ -, -CH ₂ CH ₂ CF ₂ CF ₂ -, -CHFCF ₂ CHFCF ₂ -, -CH ₂ CF ₂ CHFCF ₂ -, - CF ₂ CHFCHFCF ₂ -, -CHFCHFCF ₂ -, _{-CH 2} CHFCF ₂ -, -CF 2 CH ₂ CHFCF ₂ -, -CHFCH ₂ CHFCF ₂ -, -CH ₂ CH ₂ CHFCF ₂ -, -CF ₂ CH ₂ CH ₂ CF ₂ -, -CHFCH ₂ CH ₂ CF ₂ -, -CH ₂ CH ₂ CH ₂ CF ₂ -, -CHFCH ₂ CH ₂ CHF-, -CH ₂ CH ₂ CH ₂ CHF-, and -cycloC ₄ F ₆ -.
Specific examples of R ^f5 include -CF ₂ CF ₂ CF ₂ CF _{2 CF 2} -, -CHFCF ₂ CF _{2 CF 2 CF 2 -} , -CH ₂ CHFCF ₂ CF _{2 CF 2} - _, -CF ₂ CHFCF _{2 CF 2 CF 2} -, _{-CHFCH FCF2CF2CF2- , -CF2CH2CF2CF2CF2- , -CHFCH2CF2CF2CF2- , -CH2CH2CF2CF2CF2- , -CF2CF2CHFCF2CF2 - , -CHFCF 2 Examples include -CHFCF2CF2- , -CH2CF2CHFCF2CF2- , -CH2CF2CF2CF2CF2CH2- , and -cycloC5F8- . ​ ​}
Specific examples of R ^f6 include -CF ₂ CF ₂ CF ₂ CF _{2 CF 2} -, -CF ₂ CF ₂ CHFCHFCF ₂ CF ₂ -, -CHFCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -, -CHFCHFCHFCHFCHFCHF- _, -CHFCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ -, -CH ₂ CF ₂ CF ₂ CF ₂ CH ₂ -, and -cycloC ₆ F ₁₀ -.
Specific examples of R ^f0 include the same as those listed above for R ^f1 to R ^f6 .
Here, -cycloC ₄ F ₆ - means a perfluorocyclobutanediyl group, a specific example of which is a perfluorocyclobutane-1,2-diyl group, -cycloC ₅ F ₈ - means a perfluorocyclopentanediyl group, a specific example of which is a perfluorocyclopentane-1,3-diyl group, -cycloC ₆ F ₁₀ - means a perfluorocyclohexanediyl group, a specific example of which is a perfluorocyclohexane-1,4-diyl group.

Among these, from the viewpoint of improving abrasion resistance, R ^f0 is preferably a perfluoroalkyl group, and R ^f1 to R ^f6 are preferably perfluoroalkylene groups.

From the viewpoint of forming a surface layer having superior durability, ^G1 preferably contains at least one selected from the group consisting of structures represented by the following formulae (F1) to (F3):
(R ^f1 O) _m1 - (R ^f2 O) _m2 formula (F1)
(R ^f2 O) _m2 - (R ^f4 O) _m4 formula (F2)
(R ^f3 O) _m3 formula (F3)
However, the symbols in formulae (F1) to (F3) are the same as those in formula (G1-1).

In formula (F1) and formula (F2), the bonding order of (R ^f1 O) and (R ^f2 O), and (R ^f2 O) and (R ^f4 O) are each arbitrary. For example, (R ^f1 O) and (R ^f2 O) may be arranged alternately, (R ^f1 O) and (R ^f2 O) may be arranged in blocks, or may be arranged randomly. The same applies to formula (F3).
In formula (F1), m1 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (F2), m2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, m4 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (F3), m3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

From the viewpoint of ease of synthesis, G ¹ is preferably a group represented by the following formula (B1).
R ^f11 O-(R ^f12 O) _c1 -R ^f13 - Formula (B1)
however,
R ^f0 is a fluoroalkyl group having 1 to 20 carbon atoms;
R ^f12 and R ^f13 each independently represent a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of R ^f12 , the plurality of R ^f12 may be the same or different, and c1 represents an integer of 0 to 500.

Specific examples of R ^f11 are the same as those of R ^f0 described above. Specific examples of R ^f12 are the same as those of R ^f1 to R ^f6 described above. Specific examples of R ^f13 are the same as those of R ^f7 described above.

[ ^G2 ]
^G2 is a (poly)oxyfluoroalkylene group.

The (poly)oxyfluoroalkylene group in ^G2 is a fluoroalkylene group in which, in formula (A2), two ends bonded to ^Q2 or ^Q3 each independently have -O-, or have -O- between carbon atoms in a carbon chain having 2 or more carbon atoms, or a combination thereof.

From the viewpoint of ease of production, ^G2 is preferably a structure represented by the following formula (G2-1).
-(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 - Formula (G2-1)
However, m10 is 0 or 1, m11, m12, m13, m14, m15, and m16 are each independently an integer of 0 or 1 or more, and m11+m12+m13+m14+m15+m16 is preferably an integer of 1 to 500, more preferably an integer of 1 to 300, even more preferably an integer of 5 to 200, and particularly preferably an integer of 10 to 150. ^{R f1} , R ^f2 , R ^f3 , R ^f4 , R ^f5 , R ^f6 , and R ^f7 are the same as those in G ¹ above. The bonding order of (R ^f1 O) to (R ^f6 O) in formula (G2-1) is arbitrary, and is as described in formula (G1-1) above.

From the standpoint of water/oil repellency and fingerprint removability, it is preferred that m10 is 1 and m11+m12+m13+m14+m15+m16 is an integer of 1 to 500, that is, ^G2 is a polyoxyfluoroalkylene group.

From the viewpoint of forming a surface layer having superior durability, ^G2 preferably contains at least one selected from the group consisting of structures represented by the following formulae (F4) to (F6):
-O-(R ^f1 O) _m11 -(R ^f2 O) _m12 formula (F4)
-O-(R ^f2 O) _m12 -(R ^f4 O) _m14 formula (F5)
-O-(R ^f3 O) _m13 formula (F6)
However, the symbols in formulas (F4) to (F6) are the same as those in formula (G2-1) above.

In formula (F4) and formula (F5), the bonding order of (R ^f1 O) and (R ^f2 O), and (R ^f2 O) and (R ^f4 O) are each arbitrary. For example, (R ^f1 O) and (R ^f2 O) may be arranged alternately, (R ^f1 O) and (R ^f2 O) may be arranged in blocks, or may be arranged randomly. The same applies to formula (F6).
In formula (F4), m11 is more preferably an integer of 1 to 150, even more preferably an integer of 2 to 100, and particularly preferably an integer of 5 to 75. Furthermore, m12 is more preferably an integer of 1 to 150, even more preferably an integer of 2 to 100, and particularly preferably an integer of 5 to 75.
In formula (F5), m12 is more preferably an integer of 1 to 150, even more preferably an integer of 2 to 100, and particularly preferably an integer of 5 to 75. Furthermore, m14 is more preferably an integer of 1 to 150, even more preferably an integer of 2 to 100, and particularly preferably an integer of 5 to 75.
In formula (F6), m13 is more preferably an integer of 1 to 300, even more preferably an integer of 5 to 200, and particularly preferably an integer of 10 to 150.

From the viewpoint of ease of synthesis, G ² is preferably a polyfluoropolyether chain in which m10 in formula (G2-1) is 1, that is, G ² is preferably a group represented by the following formula (B1).
-O-(R ^f21 O) _c2 -R ^f22 - Formula (B2)
however,
R ^f21 and R ^f22 each independently represent a fluoroalkylene group having 1 to 6 carbon atoms, and when there are a plurality of R ^f21 , the plurality of R ^f21 may be the same or different,
c2 is an integer from 1 to 500.
Specific examples of R ^f21 are the same as those given above for R ^f1 to R ^f6 . Specific examples of R ^f22 are the same as those given above for R ^f7 .

The ratio of fluorine atoms in the (poly)oxyfluoroalkyl group in ^G1 and the (poly)oxyfluoroalkylene group in ^G2 [{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, in view of excellent water and oil repellency and fingerprint removability.
The molecular weight of the (poly)oxyfluoroalkyl group and the (poly)oxyfluoroalkylene group is preferably from 200 to 30,000, more preferably from 600 to 25,000, and even more preferably from 1,000 to 20,000, from the viewpoint of abrasion resistance.

[Q ¹ , Q ² , Q ³ ]
^Q1 is a single bond or a linking group having a valence of a1+b1.
^Q2 is a single bond or a b2+1 valent linking group.
^Q3 is a single bond or a b3+1 valent linking group.
Q ¹ , Q ² and Q ³ in the compound (A1) and the ^compound ( ^{A2 )} may have the same structure or different structures. Since they have the same structure, ^Q1 will be described below as a representative, and ^Q2 and ^Q3 are equivalent to ^Q1 unless otherwise specified.

When ^Q1 is a trivalent or higher linking group, it preferably has at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and an (a1+b1)-valent organopolysiloxane residue.

The ring structure constituting the branch point P is preferably one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a condensed ring consisting of two or more of these rings, from the viewpoints of ease of production of compound (A1) or compound (A2) and further superior abrasion resistance of the surface layer, and the ring structure shown in the following formula is particularly preferable. The ring structure may have a halogen atom, an alkyl group (which may contain an etheric oxygen atom between the carbon-carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, an oxo group (=O), etc. as a substituent.

Examples of organopolysiloxane residues constituting branch point P include the following groups. In the following formula, R ²⁵ is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The number of carbon atoms in the alkyl group and alkoxy group of R ²⁵ is preferably 1 to 10, and more preferably 1.

Q ¹ which is divalent or more is -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 -, -SO ₂ NR ²⁶ -, -Si(R ²⁶ ) ₂ -, -OSi(R ²⁶ ) ₂ -, -Si(CH ₃ ) ₂ -Ph-Si(CH ₃ ) ₂ and divalent organopolysiloxane residues (hereinafter referred to as "bond B"). Here, R ²⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Ph is a phenylene group. From the viewpoint of ease of production of compound (A1) or compound (A2), the number of carbon atoms in the alkyl group of R ²⁶ is preferably 1 to 3, and more preferably 1 to 2.

Examples of the divalent organopolysiloxane residue include groups of the following formula: In the following formula, R ²⁷ is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. The number of carbon atoms in the alkyl group and alkoxy group of R ²⁷ is preferably 1 to 10, and more preferably 1.

As the bond B, from the viewpoint of ease of production of compound (A1) or compound (A2), -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, -C(O)NR ²⁶ -, -C(O)ONR ²⁶ -, -NR 26C(O)-, -NR ^26C (O)O-, -NR ^{26C(O)NR 26 -} , -O- or -SO ₂ NR ²⁶ - is preferred, ^{-C(O)NR 26 -, -C(O)-, -NR 26 - or} -O- is more preferred, and from the viewpoint of further excellent abrasion resistance of the surface layer, -C(O)NR ²⁶ - or -C(O)- is even more preferred.

Examples of trivalent or higher ^Q1 include a combination of two or more divalent hydrocarbon groups R ²⁸ and one or more branch points P (for example, {P-(R ²⁸ -) _n1 }), a combination of two or more hydrocarbon groups R ²⁸ , one or more branch points P, and one or more bonds B (for example, {P-(B-R ²⁸ -) _n1 }), where n1 is an integer of 3 or more.

Furthermore, examples of the divalent ^Q1 include a divalent hydrocarbon group R ²⁸ and a combination of one or two divalent hydrocarbon groups R ²⁸ and a bond B (for example, -R ²⁸ -B-, -BR ²⁸ -B-).
Examples of the divalent hydrocarbon group in R ²⁸ include divalent aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups, etc.) and divalent aromatic hydrocarbon groups (phenylene groups, 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. R ²⁸ may be substituted with a fluorine atom.

When ^Q1 is divalent, the compound (A1) is represented by the following formula (A1a).
G ¹ -Q ¹ -NHR Formula ^A (A1a)
Here, ^G1 and ^Q1 are the same as those in compound (A1).

^Q1 is preferably a group represented by any one of the following formulae (g2-1) to (g2-7) from the viewpoint of ease of production of compound (A1) or compound (A2).

(-A-Q ¹² -) _e1 C(R ² ) _4-e1-e2 (-Q ²² -) _e2 formula g2-2
-A-Q ¹³ -N(-Q ²³ -) ₂ formula g2-3
(-A-Q ¹⁴ -) _h1 Z (-Q ²⁴ -) _h2 formula g2-4
(-A-Q ¹⁵ -) _i1 Si(R ³ ) _4-i1-i2 (-Q ²⁵ -) _i2 formula g2-5
-A-Q ²⁶ - Formula g2-6
-A-Q ¹² -CH(-Q ²² -)-Si(R ³ ) _3-i3 (-Q ²⁵ -) _i3 formula g2-7

In the formulae g2-1 to g2-7, A is connected to ^G1 or ^G2 , and Q ²² , Q ²³ , Q ²⁴ , Q ^{25 or Q 26 is} connected to the nitrogen atom.
A is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -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 -SO ₂ NR ⁶ - between carbon atoms, and when there is a plurality of As, the plurality of As may be the same or different.
Q ¹¹ is a single bond, —C(O)O—, —OC(O)—, —C(O)—, —OC(O)O—, —C(O)NR ⁶ —, —C(O)ONR ⁶ —, —NR ^6C (O)—, —NR ^6C (O)O—, —NR 6C(O)NR ⁶ —, —O— or —SO ₂ ^{NR 6 —} , an alkylene group, or an alkylene group having 2 or more carbon atoms having —C(O)O—, —OC(O)—, —C(O)—, —OC(O)O—, —C(O)NR ⁶ —, ^—C (O)ONR ⁶ —, —NR 6C(O)—, —NR ^6C (O)O—, or —NR ^6C (O)NR ⁶ It is a group having --, --O-- or --SO ₂ NR ⁶ --.
Q ¹² is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -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 -SO ₂ NR ⁶ - between carbon atoms, and when there is a plurality of Q ¹² , the plurality of Q ¹² may be the same or different.
^Q13 is a single bond (with the proviso that A is -C(O)-), an alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, -C(O)NR ⁶ -, -C(O)ONR ⁶ -, -NR ^6C (O)-, -NR ^6C (O)O-, -NR ^6C (O)NR ⁶ -, -O- or -SO ₂ NR ⁶ - between carbon atoms, or a group having -C(O)- at the N-terminal of the alkylene group.
^Q14 is ^Q12 when the atom in Z to which ^Q14 is bonded is a carbon atom, and is ^Q13 when the atom in Z to which ^Q14 is bonded is a nitrogen atom. When there are multiple ^Q14s , the multiple ^Q14s may be the same or different.
Q ¹⁵ is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -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 -SO ₂ NR ⁶ - between carbon atoms, and when there is a plurality of Q ¹⁵ , the plurality of Q ¹⁵ may be the same or different.
Q ²² is a single bond, an alkylene group, a group having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, -C(O)NR ⁶ -, -C(O)ONR ⁶ -, -NR 6C(O)-, -NR ^6C (O)O-, -NR ^6C (O)NR ⁶ -, -O- or -SO ₂ NR ⁶ - between carbon atoms in an alkylene group having ₂ or more carbon atoms, a group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or -O- at the end of the alkylene group not connected to NH 2, ^or an alkylene group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or -O- between carbon atoms and NH Q 22 is a group having —C(O)NR ⁶ —, —C(O)—, —NR ⁶ — or —O— at the end not connected to Q _22. When there are a plurality of Q ²² , the plurality of Q ²² may be the same or different.
Q ²³ is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -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 -SO ₂ NR ⁶ - between carbon atoms, and two Q ²³ 's may be the same or different.
^Q24 is ^Q22 when the atom in Z to which ^Q24 is bonded is a carbon atom, and is ^Q23 when the atom in Z to which ^Q24 is bonded is a nitrogen atom. When there are multiple ^Q24s , the multiple ^Q24s may be the same or different.
Q ²⁵ is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -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 -SO ₂ NR ⁶ - between carbon atoms, and when there is a plurality of Q ²⁵ , the plurality of Q ²⁵ may be the same or different.
Q ²⁶ is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -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 -SO ₂ NR ⁶ - between carbon atoms.
Z is a group having an h1+h2 valent ring structure having a carbon atom or nitrogen atom to which Q ¹⁴ is directly bonded and a carbon atom or nitrogen atom to which Q ²⁴ is directly bonded.
R ¹ is a hydrogen atom or an alkyl group, and when there are a plurality of R ¹ 's, the plurality of R ^1's may be the same or different.
R ² is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group, and when there are a plurality of R ^2's , the plurality of R ^2's may be the same or different.
^R3 is an alkyl group, and when there are a plurality of R3 ^'s , the plurality of ^R3's may be the same or different.
R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and when there are a plurality of R ^{6 s} , the plurality of R ^{6 s} may be the same or different.
d1 is an integer of 0 to 3, and is preferably 1 or 2.
d2 is an integer of 0 to 3, and preferably 1 or 2.
d1+d2 is an integer from 1 to 3.
d3 is an integer of 0 to 3, and is preferably 0 or 1.
d4 is an integer of 0 to 3, and preferably 2 or 3.
d3+d4 is an integer from 1 to 3.
d1+d3 is an integer of 1 to 5, and is preferably 1 or 2.
d2+d4 is an integer of 1 to 5, and is preferably 4 or 5.
e1 is an integer of 1 to 3, and preferably 1 or 2.
e2 is an integer of 1 to 3, preferably 2 or 3.
e1+e2 is an integer of 2 to 4, and preferably 1 or 2.
h1 is an integer of 1 or more, and is preferably 1 or 2.
h2 is an integer of 1 or more, preferably 2 or 3.
i1 is an integer of 1 to 3, and preferably 1 or 2.
i2 is an integer of 1 to 3, and is preferably 2 or 3.
i1+i2 is an integer of 2 to 4, and is preferably 3 or 4.
i3 is an integer of 1 to 3, and preferably 2 or 3.

^{From the viewpoints of ease of production of compound (A1) or compound (A2) and of forming a surface layer having superior durability, the number of carbon atoms in the alkylene group of Q 11 , Q 12 , Q 13 , Q 14 , Q 15 , Q 22} , Q 23 , Q 24 , Q ²⁵ or Q ²⁶ is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, in the case where an alkylene group has a specific bond between a carbon and a carbon atom, the lower limit of the number of carbon atoms in the alkylene group is 2.

Examples of the ring structure in Z include the ring structures described above, and the preferred embodiments are also the same. Since ^Q14 and ^Q24 are directly bonded to the ring structure in Z, for example, an alkylene group is not bonded to the ring structure and ^Q14 and ^Q24 are not bonded to the alkylene group.

The number of carbon atoms in the alkyl group of R ¹ , R ² or R ³ is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compound (A1) or compound (A2).
The number of carbon atoms in the alkyl group portion of the acyloxy group of ^R2 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of compound (A1) or compound (A2).
h1 is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1, from the viewpoint of ease of production of compound (A1) or compound (A2) and of forming a surface layer having superior durability.
h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3, from the viewpoint of ease of production of compound (A1) or compound (A2) and of forming a surface layer with improved durability.

^Q2 and ^Q3 in formula (A2) are the same as ^Q1 , and the preferred embodiments are also the same. However, in the above description of ^Q1 , a1 is replaced with 1, and b1 is replaced with b2 in ^Q2 and b3 in ^Q3 .

When ^Q2 and ^Q3 are divalent, the compound (A2) is represented by the following formula (A2a).
R ^B HN-Q ² -G ² -Q ³ -NHR ^C formula (A2a)
However, Q ² , G ² and Q ³ are the same as in compound (A2).

In the compound (A1) or compound (A2) contained in the present surface treatment agent, from the viewpoint of forming a surface layer having superior durability, at least one of Q ¹ , Q ² and Q ³ is preferably a group represented by the following formula (C1).
(-A ¹¹ -) _a2 Q ²¹ (-R ¹¹ -R ¹² -) _b4 formula (C1)
however,
In formula (C1), A ¹¹ is connected to G ¹ or G ² , and R ¹² is connected to a nitrogen atom;
A ¹¹ represents a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having -C(O)O-, -OC(O)-, -C(O)-, -OC(O)O-, -C(O)NR ¹³ -, -C(O)ONR ¹³ -, -NR ¹³ C(O)-, -NR ¹³ C(O)O-, -NR ¹³ C(O)NR ¹³ -, -O- or -SO ₂ NR ¹³ - between carbon atoms, and when there is a plurality of A ¹¹ , the plurality of A ¹¹ may be the same or different;
R ¹¹ is a group having a single bond, -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 -SO ₂ NR ¹³ -, and when there is a plurality of R ¹¹ , the plurality of R ¹¹ may be the same or different;
R ¹² is an alkylene group having 1 to 10 carbon atoms which may have a substituent, and in the alkylene group having 2 or more carbon atoms, -O- or -NR ^D - may be contained between carbon atoms, and R ^D is a hydrogen atom or an alkyl group;
When there are a plurality of R ¹² , the plurality of R ¹² may be the same or different.
R ¹³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and when there are a plurality of R ¹³ 's, the plurality of R ¹³ 's may be the same or different;
R ¹⁴ is an alkylene group having 1 to 10 carbon atoms;
The alkyl group or alkylene group for R ¹¹ , R ¹³ and R ¹⁴ may be substituted with a fluorine atom;
Q ²¹ is a2+b4 valent group,
a2 is an integer of 1 or more,
b4 is an integer of 1 or more.

In the compound (A1) or compound (A2), from the viewpoint of forming a surface layer having superior abrasion resistance, at least one of Q ¹ , Q ² and Q ³ is preferably a group represented by the following formula (C2).
-Q ²¹ -R ¹² - Formula (C2)
however,
^Q21 is a group represented by any one of the following formulas (1) to (15):
In formulae (1) to (15), *1 is connected to G ¹ or G ² , *2 is connected to R ¹² ,
Each T ^N independently represents a hydrogen atom or an alkyl group, and may be linked to R ¹² to form a ring;
T ^C represents a hydrogen atom or a substituent;
R ¹² is an alkylene group having 1 to 10 carbon atoms which may have a substituent, and in the alkylene group having 2 or more carbon atoms, -O- or -NR ^D - may be contained between carbon atoms, and R ^D is a hydrogen atom or an alkyl group.

^Q21 is any one of the following formulae (1) to (15), and is preferably formula (1), (2), (8), (12), or (15).

Each T ^N independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom.
When T ^N is an alkyl group, the alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Of these, the alkyl group is preferably a linear alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 or 2.

T ^C is a hydrogen atom or a substituent.
When T ^C is a substituent, examples of the substituent include a hydroxyl group, an optionally substituted alkyl group, an alkoxy group, a tertiary amino group, a halogen atom, and an imide group. When the alkyl group has a substituent, examples of the substituent include a tertiary amino group, a quaternary ammonium group, a hydroxyl group, an alkoxy group, a polyalkylene oxide group, a halogen atom, an imide group, and an aminocarbonyl group which may be substituted with an alkyl group.

R ¹² is an alkylene group having 1 to 10 carbon atoms which may have a substituent, and in the alkylene group having 2 or more carbon atoms, -O- or -NR ^D - may be contained between the carbon-carbon atom, and R ^D is a hydrogen atom or an alkyl group. The alkylene group may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group. Among them, the alkylene group is preferably a linear alkylene group. The number of carbon atoms of the alkylene group is preferably 2 to 10, and more preferably 2 to 6. Examples of the substituent that the alkylene group may have include a carboxy group, a hydroxyl group, a tertiary amino group, a quaternary ammonium group, an alkoxy group, a polyalkylene oxide group, a halogen atom, an imide group, and an aminocarbonyl group which may be substituted with an alkyl group.

[R ^A , R ^B , R ^C ]
R ^A , R ^B , and R ^C each independently represent a hydrogen atom or an alkyl group.
R ^A may be linked with Q ¹ to form a ring.
R 2 ^B may be linked with Q ² to form a ring.
R ³ may be linked to Q ³ to form a ring.

The alkyl groups represented by R ^A , R ^B , and R ^C may be linear alkyl groups, branched alkyl groups, or cyclic alkyl groups. Of these, the alkyl groups are preferably linear alkyl groups. The number of carbon atoms in the alkyl groups is preferably 1 to 6, and more preferably 1 or 2.

The molecular weight of compound (A1) and compound (A2) is preferably 3,000 or more, and more preferably 5,000 to 20,000. The molecular weight of compound (A1) and compound (A2) can be measured by gel permeation chromatography or nuclear magnetic resonance spectroscopy (NMR). Specifically, the molecular weight measurement using nuclear magnetic resonance spectroscopy (NMR) is performed by ¹ H-NMR and ¹⁹ F-NMR, and is calculated based on the number (average value) of oxyfluoroalkylene units using an internal standard substance (e.g., 1,4-bis(trifluoromethyl)benzene) or a terminal group as a standard. In other words, the above molecular weight means a "number average molecular weight".

Compound (A1) and compound (A2) preferably contain a ring structure. In compound (A1), G ¹ may contain a ring structure, Q ¹ may contain a ring structure, and R ^A may be linked to Q ¹ to form a ring. In compound (A2), G ² may contain a ring structure, Q ² and Q ³ may contain a ring structure, R ^B may be linked to Q ² to form a ring, and R ^C may be linked to Q ³ to form a ring.

In particular, in the compound (A1), it is preferable that ^Q1 contains a ring structure or ^R1 is linked to ^Q1 to form a ring. When ^Q1 contains a ring structure or R1 is linked to ^Q1 to form a ring, an intramolecular cyclization reaction is unlikely to occur. Therefore, it is considered that the reactivity with the substrate surface is excellent. ^A surface layer with excellent durability can be formed by the reaction between the amino group and the substrate surface.

For the same reason, in compound (A2), it is preferred that ^Q2 and ^Q3 contain a ring structure, or that ^R3 is linked to ^Q2 to form a ring, and ^R3 is linked to ^Q3 to form a ring.

The compound (A1) is preferably represented by any one of the following formulas (A11) to (A14).
however,
Ring A represents a heterocycle containing at least one nitrogen atom;
Ring B represents a heterocycle containing two nitrogen atoms;
Ring C represents a hydrocarbon ring or a heterocycle;
Ring D represents a heterocycle containing at least one nitrogen atom;
R ²¹ to R ²⁴ each independently represent a single bond or a linking group;
R ³¹ , R ³² , R ^A1 , and R ^A2 each independently represent a hydrogen atom or an alkyl group;
n1 and n2 each independently represent 1 or 2.

Examples of ring A include a pyrrole ring, a pyrrolidine ring, a pyridine ring, a piperidine ring, a pyrazolidine ring, an imidazolidine ring, and a piperazine ring. Of these, ring A is preferably a pyrrolidine ring, a piperidine ring, or a piperazine ring.
Examples of ring B include a pyrazolidine ring, an imidazolidine ring, and a piperazine ring. Of these, ring B is preferably a piperazine ring.
Examples of the hydrocarbon ring represented by ring C include aliphatic hydrocarbon rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, norbornene ring, and adamantane ring; and aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring. Examples of the heterocycle represented by ring C include pyrrole ring, furan ring, thiophene ring, pyrrolidine ring, imidazole ring, pyrazole ring, oxazole ring, imidazolidine ring, pyrazolidine ring, oxazolidine ring, pyridine ring, piperazine ring, pyran ring, piperazine ring, and morpholine ring. Among them, ring C is preferably a hydrocarbon ring, more preferably an aliphatic hydrocarbon ring, and even more preferably a cyclohexane ring.
Examples of ring D include a pyrrole ring, a pyrrolidine ring, a pyridine ring, a piperidine ring, a pyrazolidine ring, an imidazolidine ring, and a piperazine ring. Of these, ring D is preferably a pyrrolidine ring or a piperidine ring.

Each of R ²¹ to R ²⁴ is preferably independently a single bond or an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 6. The alkylene group may contain -O- or -NH-.

It is preferable that R ³¹ , R ³² , R ^A1 , and R ^A2 each independently represent a hydrogen atom or a methyl group.

In the above compound (A1), b1 is preferably an integer of 2 or more from the viewpoints of abrasion resistance, fingerprint removability, and water and oil repellency of the surface layer. By having two or more amino groups, adhesion to the substrate is further improved. On the other hand, b1 is preferably 10 or less, more preferably 6 or less, from the viewpoints of ease of production, etc.
In the above compound (A1), a1 is preferably an integer of 1 to 10, and more preferably an integer of 1 to 6, from the viewpoints of fingerprint removability of the surface layer, water and oil repellency, and ease of production of the compound.
In addition, in the above compound (A2), b2 and b3 are each preferably an integer of 2 or more from the viewpoint of the abrasion resistance, fingerprint removability, and water and oil repellency of the surface layer.By having two or more amino groups at one end of the polyfluoropolyether chain, the adhesion to the substrate is further improved.On the other hand, b2 and b3 are each preferably 10 or less, more preferably 6 or less, from the viewpoint of ease of production, etc.

Specific examples of specific compounds include the following compounds:

Here, ^G1 and ^G2 are as defined above, and ^Rf is a polyfluoropolyether chain.

The following describes an example of a method for producing compound (A1) or compound (A2). Although the production method is not limited to the following method, the following method can produce compound (A1) or compound (A2) in high yield.

The compound (A1) or the compound (A2) can be synthesized using a compound represented by the following formula (D1) or a compound represented by the following formula (D2).
(G ¹ -) _a1 Q ¹ (-C(=O)OCH ₃ ) _b1 formula (D1)
(H ₃ COC(=O)-) _b2 Q ² -G ² -Q ³ (-C(=O)OCH ₃ ) _b3
Formula (D2)
However, each symbol is as described above, and the preferred embodiments are also the same.
The compound (D1) and the compound (D2) can be synthesized by referring to the method described in, for example, WO 2013/121984.

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

The surface layer may contain components other than the specific compound as long as the effects of the present disclosure are achieved. Examples of other components include fluorine-containing compounds other than the specific compound.

Examples of the other fluorine-containing compounds include fluorine-containing compounds produced as a by-product in the production process of a specific compound (hereinafter also referred to as by-product fluorine-containing compounds) and known fluorine-containing compounds.
As the other fluorine-containing compound, a compound that is unlikely to reduce the effects of the present disclosure is preferable.

By-product fluorine-containing compounds include unreacted fluorine-containing compounds during the synthesis of a specific compound. When the surface layer contains by-product fluorine-containing compounds, the purification process for removing the by-product fluorine-containing compounds or reducing the amount of the by-product fluorine-containing compounds can be simplified.

Examples of known fluorine-containing compounds include those described in the following documents:
Perfluoropolyether-modified aminosilanes described in Japanese Patent Laid-Open No. 11-029585;
Silicon-containing organic fluorine-containing polymers as described in Japanese Patent No. 2874715;
Organosilicon compounds described in JP-A-2000-144097,
Perfluoropolyether-modified aminosilanes described in JP 2000-327772 A;
Fluorinated siloxanes described in Japanese Patent Publication No. 2002-506887;
Organosilicon compounds described in Japanese Patent Publication No. 2008-534696,
Fluorinated modified hydrogen-containing polymers as described in Japanese Patent No. 4138936;
Compounds described in U.S. Patent Application Publication No. 2010/0129672, WO 2014/126064, and JP 2014-070163 A,
Organosilicon compounds described in WO 2011/060047 and WO 2011/059430;
Fluorine-containing organosilane compounds described in WO 2012/064649;
Fluorooxyalkylene group-containing polymers described in JP 2012-72272 A;
Fluorine-containing ether compounds described in WO 2013/042732, WO 2013/121984, WO 2013/121985, WO 2013/121986, WO 2014/163004, JP 2014-080473 A, WO 2015/087902, WO 2017/038830, WO 2017/038832, and WO 2017/187775;
perfluoro(poly)ether-containing silane compounds described in JP 2014-218639 A, WO 2017/022437 A, WO 2018/079743 A, and WO 2018/143433 A;
Fluoropolyether group-containing polymer-modified silanes described in JP 2015-199906 A, JP 2016-204656 A, JP 2016-210854 A, and JP 2016-222859 A;
Fluorine-containing ether compounds described in WO 2018/216630, WO 2019/039226, WO 2019/039341, WO 2019/039186, WO 2019/044479, JP 2019-44158 A, WO 2019/044479, and WO 2019/163282.
In addition, examples of commercially available fluorine-containing compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC, and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, and OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd.

In order to fully exert the effects of the present disclosure, the content of other fluorine-containing compounds is preferably less than 50% by mass, more preferably less than 30% by mass, and even more preferably less than 10% by mass, relative to the total mass of the surface layer.

When the surface layer contains other fluorine-containing compounds, the content of the other fluorine-containing compounds relative to the total content of the specific compound and the other fluorine-containing compounds is preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less.
When the surface layer contains other fluorine-containing compounds, the total content of the specific compound and the other fluorine-containing compounds is preferably 80 mass % or more, more preferably 85 mass % or more, based on the total mass of the surface layer.

In a second embodiment of the article of the present disclosure, the surface layer is formed using a surface treatment agent containing a specific compound. Details of the specific compound are as described above.

The surface treatment agent may contain other components in addition to the specific compound. Examples of other components include the other fluorine-containing compounds listed above.

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

The surface treatment agent may contain a liquid medium. The surface treatment agent is preferably in liquid form, and may 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 the liquid properties can be controlled to suit the application method.

As the liquid medium, an organic solvent is preferred. The organic solvent may be a fluorine-containing solvent, a non-fluorine-containing solvent, or may contain both a fluorine-containing solvent and a non-fluorine-containing solvent.

Examples of the fluorine-containing solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound having a carbon number of 4 to 8. Commercially available products include, for example, C ₆ F ₁₃ H (product name "Asahiclean (registered trademark) AC-2000", manufactured by AGC), C ₆ F ₁₃ C ₂ H ₅ (product name "Asahiclean (registered trademark) AC-6000", manufactured by AGC), and C ₂ F ₅ CHFCHFCF ₃ (product name "Vertrel (registered trademark) XF", manufactured by Chemours).
Examples of the fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Examples of commercially available products include CF ₃ CH ₂ OCF ₂ CF ₂ H (product name "Asahiklin (registered trademark) AE-3000", manufactured by AGC), C ₄ F ₉ OCH ₃ (product name "Novec (registered trademark) 7100", manufactured by 3M), C ₄ F ₉ OC ₂ H ₅ (product name "Novec (registered trademark) 7200", manufactured by 3M), and C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ (product name "Novec (registered trademark) 7300", manufactured by 3M).
Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.
Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

Preferred non-fluorine solvents are compounds consisting of only hydrogen atoms and carbon atoms, and compounds consisting of only hydrogen atoms, carbon atoms, and oxygen atoms, and more preferable are hydrocarbons, alcohols, ketones, ethers, or esters.

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

Examples of alcohols include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, 1-pentanol, 2-pentanol, and tert-amyl alcohol.

Ketones include, for example, acetone, methyl ethyl ketone, and cyclohexanone.

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

Esters include, for example, ethyl acetate and butyl acetate.

The solvent may also be a nitrogen-containing compound, such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylene phosphoramide, N-methylcaprolactam, N-acetyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and tetramethylurea.

The content of the liquid medium 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, based on the total mass of the surface treatment agent.

The solid content of the surface treatment agent is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.01 to 10% by mass, and particularly preferably 0.01 to 1% by mass. The solid content includes the specific compound and, in some cases, other fluorine-containing compounds and other components. The solid content of the surface treatment agent is a value calculated from the mass of the surface treatment agent before heating and the mass after heating for 4 hours in a convection dryer at 120°C.

In the second embodiment of the article of the present disclosure, the method of forming the surface layer using the surface treatment agent is not particularly limited.

<Metal>
The article has a metal on a substrate. The metal is thought to have the effect of promoting the reaction between the substrate and the surface treatment agent. The article has higher adhesion to the substrate than conventional articles because it contains a metal in addition to the specific compound. During the manufacturing stage of the article, heat treatment can be performed at a lower temperature or in a shorter time than conventional articles, which reduces the load on the substrate and, as a result, suppresses warping.

The metal contained in the article is a metal with an electronegativity of 0.8 to 2.54.
In this disclosure, metals are also intended to include metalloids.
When the metal is in the form of a metal ion, the hydrolysis constant (pKh) of the metal ion is preferably 4.0 to 15.0, and more preferably 4.0 to 14.0.

The hydrolysis constant (pKh) is calculated from the following formula (Baes, Jr. CF: Mesmer, R. The Hydrolysis of Cations, Willy: New York, 1976.).
pKh= _-logKky
From the relationship of xMz ⁺ _{+ yH2O⇔Mx} (OH) _y ^(xzy)+ +yH ⁺ , _Kxy can be calculated by the following formula.

In addition, when the metal is in the form of a metal ion, the water exchange rate constant (WERC) of the metal ion is preferably 3.2×10 ⁶ M ⁻¹ sec ⁻¹ or more.

Water exchange constants are measured by nuclear magnetic resonance absorption, acoustic absorption, and multidentate ligand methods (Martell, A.B. Ed. Coordination Chemistry, Vol. 2, ACS Monograph 168, ACS: Washington, DC, 1978.).

When the metal is a metal ion, the hydrolysis constant of the metal ion is preferably 4.0 to 15.0 and the water exchange constant is 3.2×10 ⁶ M ⁻¹ sec ⁻¹ or more. More preferably, the hydrolysis constant of the metal ion is 5.0 to 15.0 and the water exchange constant is 1.0×10 ⁷ M ⁻¹ sec ⁻¹ or more. Still more preferably, the hydrolysis constant of the metal ion is 6.0 to 15.0 and the water exchange constant is 1.0×10 ⁷ M ⁻¹ sec ⁻¹ or more.

Specifically, the metal is preferably 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;
At least one selected from the group consisting of 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 is more preferred, and at least one selected from the group consisting of 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 is even more preferred,
It is particularly preferable that the element 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.
The metals contained in this article can be detected by TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) or LA-ICP-MS (Laser Ablation-Inductively Coupled Plasma) using ion sputtering.

From the viewpoint of further suppressing warping of the article, the mass of the metal per unit area on the surface of the substrate on which the metal is provided is preferably 0.0001 to 270 μg/cm ² , and more preferably 0.0001 to 100 μg/cm ² .

From the viewpoint of further suppressing warping of the article, the molar ratio of the metal to the (poly)oxyfluoroalkylene chain contained in the specific compound is preferably 0.01 to 150,000 mol %, and more preferably 0.1 to 100,000 mol %.

From the viewpoint of achieving superior abrasion resistance, it is preferable that the article further includes a structure that connects the substrate and the surface layer and has a structure derived from a specific compound.

Since the specific compound contains a primary amino group or a secondary amino group, when the base material has a functional group such as an ester group, a cyano group, an amide group, an imide group, a carbonate group, or a carbamate group, the amino group reacts with the functional group to bond during the manufacturing stage of the article, thereby connecting the base material and the surface layer. Having a structure derived from a specific compound means that the structure of the specific compound other than the primary amino group or secondary amino group is the same as that of the specific compound.

[Production method of the article]
The method for producing the article includes pretreating a substrate by applying a solution containing a Brønsted acid, applying a solution containing a Lewis acid, or applying a solution containing a Brønsted acid and then applying a solution containing a Lewis acid;
A surface treatment agent containing a specific compound is applied to the pretreated substrate, or
The surface treatment agent is applied onto the substrate, and then the solution containing the Lewis acid is applied thereto, or the solution containing the surface treatment agent and the Lewis acid is applied onto the substrate.

<Method of applying a surface treatment agent onto a pretreated substrate>
One aspect of the method for producing the present article is a method in which a substrate is pretreated by applying a solution containing a Brønsted acid, applying a solution containing a Lewis acid, or applying a solution containing a Brønsted acid and then applying a solution containing a Lewis acid, and then applying a surface treatment agent containing a specific compound to the pretreated substrate. The Lewis acid is believed to have the effect of promoting the reaction between the substrate and the surface treatment agent.

(Pretreatment)
The details of the substrate used in the pretreatment are as described above.

Examples of Bronsted acids include organic acids such as ascorbic acid, acetic acid, and citric acid, and inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and phosphoric acid. The Bronsted 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, and 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.

The solvent contained in the solution containing a Bronsted acid is not particularly limited, and may be water or an organic solvent. The organic solvent may be a non-fluorine solvent such as a hydrocarbon, alcohol, ketone, ether, or ester, or may be a fluorine-containing solvent. Specific examples of non-fluorine solvents and fluorine-containing solvents are as described above. The solvent can be appropriately selected based on the solubility, stability, etc. of the Bronsted acid.

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

The method for applying the solution containing a Bronsted acid is not particularly limited, and may be any of spin coating, roll coating, casting, wipe coating, squeegee coating, die coating, flow coating, spray coating, gravure coating, curtain coating, dip coating, and inkjet coating. From the viewpoint of improving durability, however, dip coating is preferred. Ultrasonic treatment may also be performed while dip coating is being performed.

The metal that constitutes the Lewis acid is preferably a metal with an electronegativity of 0.8 to 2.54, and specifically, the metals listed above are preferred.

Examples of anions constituting a Lewis acid include halide ions such as F ^- , Cl ^- and Br ^{- ,} alkoxide anions, CF ₃ SO ₃ ^- (OTf ^- ), CH ₃ SO ₃ ^- , a tosylate anion, a carboxylate anion, and C _n F _2n+1 SO ₃ ^- . Of these, the anion constituting a Lewis acid is preferably a halide or OTf ^- .

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

Examples of Lewis acids include TiCl ₄ , SnCl ₄ , 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 , AlCl ₃ , BF _3, LiCl, NaOTf, and Ce(OTf) _3. Among these, from the viewpoint of low environmental load, the Lewis acid is preferably at least one selected from the group consisting of La(OTf) ₃ , Nd(OTf) ₃ , and LiCl.

The solvent contained in the solution containing a Lewis acid is not particularly limited, and may be water or an organic solvent. The organic solvent may be a non-fluorine solvent such as a hydrocarbon, alcohol, ketone, ether, or ester, or may be a fluorine-containing solvent. Specific examples of non-fluorine solvents and fluorine-containing solvents are as described above. The solvent can be appropriately selected based on the solubility, stability, etc. of the Lewis acid.

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

The method for applying the solution containing a Lewis acid is not particularly limited, and may be any of spin coating, roll coating, casting, wipe coating, squeegee coating, die coating, flow coating, spray coating, gravure coating, curtain coating, dip coating, and inkjet coating. From the viewpoint of improving durability, however, dip coating is preferred.

In the pretreatment, when a solution containing a Brønsted acid is applied to a substrate and then a solution containing a Lewis acid is applied, it is preferable to dry the substrate to which the solution containing a Brønsted acid has been applied before applying the solution containing a Lewis acid in order to fix the Brønsted acid to the substrate. There are no particular limitations on the drying method, but from the viewpoint of suppressing warping of the article, a method of blowing air is preferable.

In order to strengthen the bond between the specific compound contained in the surface treatment agent and the substrate, it is preferable to carry out the pretreatment by applying a solution containing a Brønsted acid and then a solution containing a Lewis acid.

(Application of surface treatment agent)
Details of the surface treatment agent to be applied to the pretreated substrate and the specific compound contained in the surface treatment agent are as described above.

The method for applying the surface treatment agent containing a specific compound onto the pretreated substrate is not particularly limited, and may be any of the following: spin coating, roll coating, casting, wipe coating, squeegee coating, die coating, flow coating, spray coating, gravure coating, curtain coating, dip coating, and inkjet coating. From the viewpoint of coating processing time, however, spin coating is preferred.

It is preferable to dry the pretreated substrate before applying the surface treatment agent. There are no particular limitations on the drying method, but a method of blowing air is preferable from the viewpoint of suppressing warping of the article.

The pretreated substrate may be heated before applying the surface treatment agent. For example, the substrate may be heated using an electric furnace, an infrared (IR) furnace, etc.

<Method of applying a surface treatment agent onto a substrate and then applying a solution containing a Lewis acid>
Details of the substrate, the surface treatment agent applied to the substrate, and the specific compound contained in the surface treatment agent are as described above. Details of the solution containing a Lewis acid applied to the substrate to which the surface treatment agent has been applied are as described above.
Moreover, the preferred embodiments of the method for applying the surface treatment agent and the method for applying the solution containing a Lewis acid are as described above.
After the surface treatment agent is applied to the substrate, it is preferable to dry the substrate to which the surface treatment agent has been applied before applying the solution containing a Lewis acid. Although the drying method is not particularly limited, a method of blowing air is preferable from the viewpoint of suppressing warping of the article.

<Method of Coating a Solution Containing a Surface Treatment Agent and a Lewis Acid on a Substrate>
Details of the substrate, the surface treatment agent applied onto the substrate, and the Lewis acid are as described above.
The method for applying the solution containing the surface treatment agent and the Lewis acid onto the substrate is not particularly limited, and may be any of spin coating, roll coating, casting, wipe coating, squeegee coating, die coating, flow coating, spray coating, gravure coating, curtain coating, dip coating, and inkjet methods. From the viewpoint of the coating processing time, however, spin coating is preferred.

Among these, the preferred method for producing the present article is to apply a surface treatment agent containing a specific compound to a pretreated substrate. By applying at least one of a solution containing a Brönsted acid and a solution containing a Lewis acid to the substrate as a pretreatment, the substrate surface is activated and the reactivity with the specific compound contained in the surface treatment agent is improved, which is believed to result in a stronger bond between the substrate and the surface layer.

In the method for manufacturing the present article, it is preferable to apply a surface treatment agent containing a specific compound onto a pretreated substrate, or to apply a surface treatment agent onto the substrate and then apply a solution containing a Lewis acid, or to apply a solution containing a surface treatment agent and a Lewis acid onto the substrate and then perform firing. Note that after application, the substrate may be left as is without firing.

When firing, the firing temperature is preferably 30°C to 90°C and the firing time is preferably 1 to 60 minutes in order to prevent warping of the product.

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

[Synthesis of compound 1]

Compound 1a was synthesized with reference to the synthesis method of precursor (4a-2) described in WO 2013/121984. The average number of repeating units n is 13.
In a 30 mL eggplant flask, 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 the above compound 1a (number average molecular weight: about 4,500, 1.0 g, 0.22 mmol) were placed. The mixture was stirred at 25°C for 3 days using a magnetic stirrer. Thereafter, methanol (1 mL) was added to the obtained solution, stirred, allowed to stand, and the upper layer was removed with a pipette. This operation was repeated three times. AC-2000 (5 mL) was added to the obtained solution, and then the mixture was distilled off under reduced pressure. The resulting crude product was purified by column chromatography to obtain compound 1b (0.81 g).

The obtained compound 1b was dissolved in AC-2000 (6 mL) and cooled to 0°C. Then, 4N hydrogen chloride/ethyl acetate solution (2 mL) was added and stirred for 4 hours. After the solvent was distilled off under reduced pressure, AC-2000 (10 mL) and 5% by mass aqueous sodium carbonate solution (2 mL) were added. After stirring, the lower layer was dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain compound 1 (0.54 g).

[Synthesis of compound 2]

In a 50 mL recovery flask, 1,3-diamino-2-propanol (0.065 g, 0.72 mmol), AC-2000 (9 mL), 1,4-dioxane (5.5 mL), and the above compound 1a (number average molecular weight: about 4,500, 1.0 g, 0.22 mmol) were placed, and the mixture was stirred at 25° C. for 6 hours using a magnetic stirrer. After the solvent was distilled off under reduced pressure, the mixture was dissolved in Asahiklin AC-6000 (manufactured by AGC Corporation, hereinafter referred to as "AC-6000"), transferred to a separatory funnel, and washed with methanol, which was repeated three times. The AC-6000 was distilled off under reduced pressure, and a crude product of compound 2 (1.13 g) was obtained.
The obtained crude product of compound 2 was dissolved in AC-2000 (5 mL), 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. The solvent was distilled off under reduced pressure, and the obtained crude product was purified using a column to obtain compound 2a (0.48 g).

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 stirred for one day. The solvent was then removed by distillation under reduced pressure. The obtained crude product was added with AC-2000 (10 mL) and a 5% by mass aqueous solution of sodium hydrogen carbonate (2 mL), stirred, and allowed to stand. The lower layer was separated and then dried using sodium sulfate. After filtration, the solvent was removed by distillation under reduced pressure to obtain compound 2 (0.20 g).

Next, surface treatment agents 1 and 2 were prepared using compounds 1 and 2.

[Preparation of Surface Treatment Agents 1 and 2]
A mixed solution of AC-2000 and ethanol (ethanol concentration: 3 mass%) was added to Compound 1 (0.05 g) so that the content of Compound 1 was 0.1 mass%. The obtained solution was designated as Surface Treatment Agent 1. Surface Treatment Agent 2 was prepared from Compound 2 in the same manner.

[Production of goods]
(Examples 1 to 4, 7 to 9, 11, 13, 15, 16, 20 to 27)
As the substrate, a hard-coated PMMA substrate (acrylic plate (MR plate) manufactured by Acrisande Co., Ltd., surface hardness (pencil hardness) is 6H, 10 cm x 10 cm x 3 mm thick) was used. The substrate was immersed in 200 mL of a 20% by mass aqueous solution containing a Brønsted acid as described in Tables 1 to 5, and then treated with ultrasonic waves for 10 minutes. The substrate was removed and dried with air. The substrate was immersed in 200 mL of an aqueous solution containing a Lewis acid as described in Tables 1 to 5 and having a concentration as described in Tables 1 to 5, and then treated with ultrasonic waves for 10 minutes. The substrate was removed and dried with air. Using a spin coater (product name "Opticoat MS-B200", manufactured by Mikasa Co., Ltd.), 2 mL of a surface treatment agent containing a specific compound as described in Tables 1 to 5 was placed on the substrate, and rotated at a rotation speed of 500 rpm for 1 minute. Using an infrared furnace, baking was performed at the temperature and time as described in Tables 1 to 5 to obtain an article having a surface layer.

(Example 5)
An article having a surface layer was obtained in the same manner as in Example 1, except that the pretreatment with the solution containing a Bronsted acid and the solution containing a Lewis acid was not carried out.

(Examples 6, 10, 12, 14, and 17)
An article having a surface layer was obtained in the same manner as in Example 1, except that the pretreatment with the solution containing a Bronsted acid and the solution containing a Lewis acid was not performed and the baking was performed at the temperature and time shown in Tables 1 to 5.

(Example 18)
An article having a surface layer was obtained in the same manner as in Example 1, except that the pretreatment was carried out with a solution containing a Lewis acid, rather than using a solution containing a Bronsted acid.

(Example 19)
An article having a surface layer was obtained in the same manner as in Example 1, except that the pretreatment was carried out with a solution containing a Bronsted acid, rather than using a solution containing a Lewis acid.

The initial water contact angle was measured for the obtained article, and the abrasion resistance and warpage were evaluated.
In addition, the mass of the metal per unit area on the surface of the substrate was measured to be 1.39 μg/cm ² in Example 1, 1.44 μg/cm ² in Example 2, 0.069 μg/cm ² in Example 3, and 69.5 μg/cm ² in Example 4. In the article, the molar ratio of the metal to the (poly)oxyfluoroalkylene chain was 1250 mol% in Example 1.

<Initial water contact angle>
Approximately 2 μL of pure water was dropped onto the surface of the article on which the surface layer was formed (hereinafter also referred to as the "surface on which the surface layer was formed"). 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 performed at five different points on the surface on which the surface layer was formed, and the average value was calculated and used as the initial water contact angle. The 2θ method was used to calculate the contact angle. Note that an ionizer and air blowing treatment were performed for each measurement, and the water contact angle was measured.

<Wear resistance>
A triple flat surface abrasion tester (product name "PA-300A", manufactured by Daiei Scientific Instruments Manufacturing Co., Ltd.) equipped with an indenter (bottom area: 100 mm2) fitted with a Kanakin No. 3 was used to perform an abrasion test on the surface of the article on which the surface layer was formed, under the following abrasion conditions: 24°C, 40% RH atmosphere, load of 1,000 g, rotation speed of 60 rpm, and stroke length of 40 mm. After rubbing a specified number of times, the water contact angle was measured. The method for measuring the water contact angle was the same as that for measuring the initial water contact angle. Note that "-" in the table indicates that measurement was not possible.

＜Warping＞
The obtained article was placed on a flat and level surface plate. The height A2 of the central part of the article was measured with a vernier caliper. Similarly, the height A1 of the central part of the article before firing in the manufacturing process of the article was also measured. Warping was evaluated based on the value (ΔH) obtained by subtracting A1 from A2. It can be said that the smaller ΔH is, the more the warping is suppressed. In the table, the unit of ΔH indicating warping is mm. In the table, "-" in the column for the component means that the corresponding component was not added. "-" in the column for the number of rubs means that it was not performed.

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 include a substrate, a surface layer provided on the substrate, and a metal, the surface layer includes a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group, and the metal has an electronegativity of 0.8 to 2.54, and therefore it was found that the articles have excellent abrasion resistance and suppress warping.

The disclosure of Japanese Patent Application No. 2023-062399, filed on April 6, 2023, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims (16)

A substrate, and a surface layer and a metal provided on the substrate,
the surface layer contains a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group,
The article, wherein the metal has an electronegativity of 0.8 to 2.54. A substrate, and a surface layer and a metal provided on the substrate,
the surface layer is formed using a surface treatment agent containing a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group,
The article, wherein the metal has an electronegativity of 0.8 to 2.54. The article according to claim 1 or 2, 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):
(G ¹ -) _a1 Q ¹ (-NHR ^A ) _b1 ... (A1)
(R ^B HN-) _b2 Q ² -G ² -Q ³ (-NHR ^C ) _b3 ... (A2)
however,
G ¹ is a (poly)oxyfluoroalkyl group, and when there are a plurality of G ¹ , the plurality of G ¹ may be the same or different;
^G2 is a (poly)oxyfluoroalkylene group;
^Q1 is a single bond or a linking group having a valence of a1+b1;
^Q2 is a single bond or a b2+1 valent linking group;
^Q3 is a single bond or a b3+1 valent linking group;
a1 is an integer of 1 or more,
b1 is an integer of 1 or more,
b2 is an integer of 1 or more,
b3 is an integer of 1 or more.
R ^A , R ^B , and R ^C each independently represent a hydrogen atom or an alkyl group;
^R may be linked with ^Q to form a ring;
R ^B may be linked with ^Q2 to form a ring;
R ³ may be linked to Q ³ to form a ring. The article according to claim 1 or 2, 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. 3. The article according to claim 1, wherein the mass of the metal per unit area on the surface of the substrate on which the metal is provided is 0.0001 to 270 μg/cm ² . 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. The article according to claim 1 or 2, further comprising a structure that connects the substrate and the surface layer and has a structure derived from the compound. The article according to claim 1 or 2, wherein the molar ratio of the metal to the (poly)oxyfluoroalkylene chain is 0.01 to 150,000 mol %. A pretreatment is performed on a substrate by applying a solution containing a Brønsted acid, applying a solution containing a Lewis acid, or applying a solution containing a Brønsted acid and then applying a solution containing a Lewis acid;
applying a surface treatment agent containing a compound having a (poly)oxyfluoroalkylene chain and a primary amino group or a secondary amino group onto the substrate that has been pretreated;
Applying the surface treatment agent onto a substrate and then applying a solution containing a Lewis acid, or
A method for producing an article, comprising applying a solution containing the surface treatment agent and a Lewis acid onto a substrate. The method for producing an article according to claim 9, wherein the Bronsted 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. The method for manufacturing an article according to claim 9 or 10, wherein the metal constituting the Lewis acid has an electronegativity of 0.8 to 2.54. The method for manufacturing an article according to claim 11, 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. The method for producing an article according to claim 9 or 10, wherein the Lewis acid is at least one selected from the group consisting of La(OTf) ₃ , Nd(OTf) ₃ , and LiCl. The method for manufacturing an article according to claim 9 or 10, wherein the concentration of the Lewis acid in the solution containing the Lewis acid is 1 ppb by mass to 5% by mass. The method for producing an article according to claim 9 or 10, 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):
(G ¹ -) _a1 Q ¹ (-NHR ^A ) _b1 ... (A1)
(R ^B HN-) _b2 Q ² -G ² -Q ³ (-NHR ^C ) _b3 ... (A2)
however,
G ¹ is a (poly)oxyfluoroalkyl group, and when there are a plurality of G ¹ , the plurality of G ¹ may be the same or different;
^G2 is a (poly)oxyfluoroalkylene group;
^Q1 is a single bond or a linking group having a valence of a1+b1;
^Q2 is a single bond or a b2+1 valent linking group;
^Q3 is a single bond or a b3+1 valent linking group;
a1 is an integer of 1 or more,
b1 is an integer of 1 or more,
b2 is an integer of 1 or more,
b3 is an integer of 1 or more.
R ^A , R ^B , and R ^C each independently represent a hydrogen atom or an alkyl group;
^R may be linked with ^Q to form a ring;
R ^B may be linked with ^Q2 to form a ring;
R ³ may be linked to Q ³ to form a ring. The method for manufacturing an 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.