Fluoroether compound, fluoroether composition, coating liquid, article, and method for manufacturing article

Abstract

The object of this invention is to provide a fluorinated ether compound, a fluorinated ether composition, a coating liquid, and an article having a surface layer with excellent fingerprint removal and finger slipperiness, and a method for manufacturing the same. A fluorinated ether compound is represented by formula (1) or formula (2). {(R f1 -A 1 -) p1 Si(-R) 1 ) 3‑p1} q1 -Q 1 (-T) n1 (-R) f2 ) r1 Equation (1). {(R) f1 -A 1 -) p2 Si(-R) 1 ) 3‑p2} q2 -Q 2 (-T) n2 -R f3 -Q 3 (-T) n3 {-Si(-R) 2 ) 3‑p3 (-A) 2 -R f1 ) p3} q3 Equation (2). The symbols in the equation are as described in the instruction manual.

Description

Technical Field

[0001] This invention relates to fluorinated ether compounds, fluorinated ether compositions, coating liquids, articles, and methods for manufacturing articles. Background Technology

[0002] Fluorinated ether compounds with fluorinated polyether chains and hydrolyzable silyl groups have attracted much attention because they can impart excellent water and oil repellency, abrasion resistance, low fingerprint adhesion, fingerprint stain removal and finger slippage to the surface of substrates.

[0003] For example, in Patent Document 1, a fluorinated ether compound having a perfluoropolyether chain and a hydrolyzable silyl group was proposed as a fluorinated ether compound capable of forming a surface layer on the surface of a substrate with excellent fingerprint stain removal and durability.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2017 / 038832 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] The purpose of this invention is to provide a fluorinated ether compound, a fluorinated ether composition, a coating liquid, and an article having a surface layer with excellent fingerprint removal and finger slipperiness, as well as a method for manufacturing the same.

[0009] Solution for solving the problem

[0010] The present invention provides fluorinated compounds having the following [1] to [9] structures, methods for manufacturing the same, compositions containing fluorinated compounds, coating liquids, articles, and methods for manufacturing the same.

[0011] [1] A fluorinated ether compound, represented by formula (1) or formula (2).

[0012] {(R f1 -A 1 -) p1 Si(-R 1 ) 3-p1} q1 -Q 1 (-T) n1 (-R f2 ) r1 Equation (1)

[0013] {(R f1 -A 1 -) p2 Si(-R1 ) 3-p2} q2 -Q 2 (-T) n2 -R f3 -Q 3 (-T) n3 {-Si(-R 2 ) 3-p3 (-A 2 -R f1 ) p3} q3 Equation (2)

[0014] in,

[0015] R f1 For a monovalent polyfluorinated polyether chain with optional substituents, there exist multiple R... f1 They can choose to be the same or different from each other.

[0016] R f2 It is a monovalent polyfluorinated polyether chain, with multiple R... f2 They can choose to be the same or different from each other.

[0017] R f3 It is a divalent polyfluorinated polyether chain.

[0018] A 1 and A 2 Each is independently -O- or C(=O)-O-, and there are multiple A's. 1 and A 2 Each can independently choose to be the same as or different from the others.

[0019] R 1 and R 2 The R group is an alkyl group, a hydrolyzable group, or a hydroxyl group, and there are multiple R groups present. 1 and R 2 They can choose to be the same or different from each other.

[0020] Q 1 It is a linker group with a valence of q1+n1+r1.

[0021] Q 2 It is a linker group with a valence of q2+n2+1.

[0022] Q 3 It is a linker group with a valence of q3+n3+1.

[0023] T is -Si(-R) 3-a (-L) a When there are two or more T's, the two or more T's can be chosen to be the same or different.

[0024] R is an alkyl group.

[0025] L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T can be chosen to be the same or different.

[0026] a is 2 or 3.

[0027] q1 is an integer greater than or equal to 1.

[0028] When q1 is 1, p1 is either 1 or 2.

[0029] When q1 is 2 or higher, p1 is an integer from 0 to 3, at least one of the multiple p1s is 1 or 2, and the multiple p1s can be chosen to be the same or different from each other.

[0030] n1 is an integer greater than or equal to 0, and r1 is an integer greater than or equal to 1.

[0031] q2 is an integer greater than or equal to 1.

[0032] When q2 is 1, p2 is either 1 or 2.

[0033] When q2 is 2 or higher, p2 is an integer from 0 to 3. At least one of the multiple p2s is 1 or 2, and the multiple p2s can be chosen to be the same or different from each other.

[0034] n2 is an integer greater than or equal to 0.

[0035] q3 is an integer greater than or equal to 0.

[0036] When q3 is 1 or higher, p3 is an integer from 0 to 3. If there are multiple p3s, they can be chosen to be the same or different from each other.

[0037] n3 is an integer greater than or equal to 0, and q3+n3 is an integer greater than or equal to 1.

[0038] [2] According to the fluorinated ether compound of [1], wherein the aforementioned R f1 It is represented by the following formula (3A).

[0039] L 1 -R f11a -(OR f12 ) m1 -(CH2) s1 - Equation (3A)

[0040] L 1 For hydrogen atoms, fluorine atoms, hydroxyl groups, -C(O)X, -C(O)OR 10 -C(O)N(R) 10 )2,

[0041] X is a hydrogen atom or a halogen atom.

[0042] R 10Each of the R atoms is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (optionally having fluorine atoms), or a phenyl group having fluorine atoms, and multiple R atoms exist. 10 At that time, there are multiple R 10 They can choose to be the same or different from each other.

[0043] R f11a It is a fluoroalkylene group with 1 to 20 carbon atoms.

[0044] R f12 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0045] When m1 is an integer from 0 to 500, and m1 is greater than 2, there are multiple R... f12 Choose either the same or different, where s1 is an integer from 0 to 20.

[0046] [3] According to [1] or [2], the fluorinated ether compound, wherein the aforementioned R f2 It is represented by the following formula (3).

[0047] R f11 -(OR f12 ) m1 - Equation (3)

[0048] in,

[0049] R f11 It is a fluoroalkyl group with 1 to 20 carbon atoms.

[0050] R f12 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0051] When m1 is an integer from 0 to 500, and m1 is greater than 2, there are multiple R... f12 Choose either the same or different.

[0052] [4] According to the fluorinated ether compounds of [1] to [3], wherein the aforementioned R f3 It is represented by the following formula (4).

[0053] -R f13 -(OR f13 ) m2 - Equation (4)

[0054] in,

[0055] R f13 It is a fluoroalkylene group with 1 to 6 carbon atoms, and contains multiple R... f13 Choose either the same or different.

[0056] m2 is an integer from 0 to 500.

[0057] [5] According to the fluorinated ether compounds of [1] to [4], wherein the aforementioned Q1 Q 2 and Q 3 Each can be represented independently by any of the following equations (5-1) to (5-7).

[0058]

[0059] (-A 11 -Q 12 -)C(-R e2 ) 2-d3 (-Q 32 -)(-Q 22 -) d3 Equation (5-2)

[0060] (-A 11 -Q 13 -)N(-Q 33 -)(-Q 23 -) Equation (5-3)

[0061] (-A 11 -Q 14 -)Z(-Q 34 -)(-Q 24 -) d4 Equation (5-4)

[0062] (-A 11 -Q 15 -)Si(-R e3 ) 2-d5 (-Q 35 -)(-Q 25 -) d5 Equation (5-5)

[0063] -A 11 -Q 12 -CH(-Q 32 -)-Si(R e3 ) 3-d6 (-Q 25 -) d6 Equation (5-6)

[0064] -A 11 -Q 12 -CH(-Q 22 -)-Si(R e3 ) 2-d7 (-Q 35 -)(-Q 25 -) d7 Equation (5-7)

[0065] In equations (5-1) to (5-7), A 11 Side and Rf2 Or R f3 Connection, Q 22 Q 23 Q 24 、 or Q 25 The side is connected to T, Q 32 Q 33 Q 34 Or Q 35 With the help of Si and R f1 connect,

[0066] A 11 For single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2-,

[0067] Q 11 For single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2-, alkylene groups, or alkylene groups having a -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups,

[0068] Q 12 It is a single bond, an alkylene group, or an alkylene group having a -C(O)NR bond between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups,

[0069] Q 13 It is a single bond (where A is a single bond). 11 Alkyl groups are -C(O)-; alkylene groups having -C(O)NR between carbon atoms in carbon-carbon pairs. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR6 -、-O-、-SO2NR 6 -or-NR 6 A group containing SO2-; or a group having a -C(O)- terminal on the N-side of the alkylene group.

[0070] In Q 14 When the atom in the bonded Z is a carbon atom, Q 14 For Q 12 In Q 14 When the atom in the bonded Z is a nitrogen atom, Q 14 For Q 13 ,

[0071] Q 15 It is an alkylene group; or an alkylene group having a -C(O)NR bond between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups,

[0072] Q 22 and Q 32 Each is independently an alkylene group; in alkylene groups having two or more carbon atoms, there is a -C(O)NR between the carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups; having a -C(O)NR terminal on the side of the alkylene group not connected to Si. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 A group consisting of SO2-; or a -C(O)NR group between carbon atoms in an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- and has -C(O)NR at the end on the side not connected to Si. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6-、-O-、-SO2NR 6 -or-NR 6 The SO2- group contains multiple Q groups. 22 At that time, there are multiple Qs. 22 Choose either the same or different.

[0073] Q 23 and Q 33 Each is independently an alkylene group; or has a -C(O)NR between carbon atoms in alkylene groups having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups,

[0074] In Q 24 Or Q 34 When the atom in the bonded Z is a carbon atom, Q 24 and Q 34 Each independently for Q 22 Or Q 32 In Q 24 Or Q 34 When the atom in the bonded Z is a nitrogen atom, Q 24 and Q 34 Each independently for Q 23 Or Q 33 There are multiple Qs 24 At that time, there are multiple Qs. 24 Choose either the same or different.

[0075] Q 25 and Q 35 Each is independently an alkylene group; or has a -C(O)NR between carbon atoms in alkylene groups having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 The SO2- group contains multiple Q groups. 25 At that time, there are multiple Qs. 25 Choose either the same or different.

[0076] Z is a group with a d4+2 valence ring structure, and the d4+2 valence ring structure has the same characteristics as Q. 14 Q 24 and Q 34 Directly bonded carbon or nitrogen atoms,

[0077] Re1 It consists of hydrogen atoms or alkyl groups, and contains multiple R atoms. 1 At that time, there are multiple R 1 Choose either the same or different.

[0078] R e2 It can be a hydrogen atom, hydroxyl group, alkyl group or acyloxy group.

[0079] R e3 It is an alkyl group.

[0080] R 6 It is an alkyl or phenyl group with 1 to 6 carbon atoms and hydrogen atoms.

[0081] d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1+d2 is an integer from 1 to 6.

[0082] d3 is 1 or 2.

[0083] d4 is an integer greater than or equal to 1.

[0084] d5 is 1 or 2.

[0085] d6 is an integer from 1 to 3.

[0086] d7 is 1 or 2.

[0087] [6] A fluorinated ether composition comprising the fluorinated ether compounds of [1] to [5] and other fluorinated ether compounds.

[0088] [7] A coating liquid containing a fluorinated ether compound of [1] to [5] or a fluorinated ether composition of [6], and containing a liquid medium.

[0089] [8] An article having a surface layer formed of a fluorinated ether compound of [1] to [5] or a fluorinated ether composition of [6] on the surface of a substrate.

[0090] [9] A method for manufacturing an article, wherein a surface layer is formed by dry coating or wet coating using a fluorinated ether compound of [1] to [5], a fluorinated ether composition of [6] or a coating liquid of [7].

[0091] The effects of the invention

[0092] The present invention provides a fluorinated ether compound, a fluorinated ether composition, a coating liquid, and an article having a surface layer with excellent fingerprint removal and finger slipperiness, as well as a method for manufacturing the same. Attached Figure Description

[0093] Figure 1 This is a schematic cross-sectional view illustrating an example of the article of the present invention. Detailed Implementation

[0094] In this specification, the compound represented by formula (1) is referred to as compound (1). Compounds represented by other formulas are also based on this designation.

[0095] The following terms in this specification have the following meanings.

[0096] "Reactive silyl groups" refers to the collective term for hydrolyzable silyl groups and silanol groups (Si-OH). Reactive silyl groups are defined as -Si(-R) in, for example, formula (1) or formula (2). 3-a (-L) a and -Si(-R 1 ) or Si(-R 2 In ), R 1 Or R 2 In the case of hydrolyzable groups or hydroxyl groups.

[0097] "Hydrolyzable silane" refers to a group that can undergo a hydrolysis reaction to form a silanol group.

[0098] "Surface layer" refers to a layer formed on the surface of a substrate.

[0099] When the fluorinated ether compound is a mixture of multiple fluorinated ether compounds with different chain lengths of polyfluorinated polyether chains, the "molecular weight" of the polyfluorinated polyether chain is determined by... 1 H-NMR and 19 The number-average molecular weight is calculated by determining the number (average value) of oxyfluoroalkyl units using F-NMR.

[0100] When the fluorinated ether compound is a polyfluorinated polyether chain with a single chain length, the "molecular weight" of the polyfluorinated polyether chain is determined by... 1 H-NMR and 19 F-NMR determined R f The molecular weight is calculated based on the structure.

[0101] The "~" sign indicating a range of values ​​means that the values ​​recorded before and after it are included as the lower and upper limits.

[0102] [Fluoroether compounds]

[0103] The fluorinated ether compound of the present invention (hereinafter also referred to as "the compound") is a compound represented by formula (1) or formula (2).

[0104] {(R f1 -A 1 -) p1 Si(-R 1 ) 3-p1} q1 -Q 1 (-T) n1 (-Rf2 ) r1 Equation (1)

[0105] {(R f1 -A 1 -) p2 Si(-R 1 ) 3-p2} q2 -Q 2 (-T) n2 -R f3 -Q 3 (-T) n3 {-Si(-R 2 ) 3-p3 (-A 2 -R f1 ) p3} q3 Equation (2)

[0106] in,

[0107] R f1 For a monovalent polyfluorinated polyether chain with optional substituents, there exist multiple R... f1 They can choose to be the same or different from each other.

[0108] R f2 It is a monovalent polyfluorinated polyether chain, with multiple R... f2 They can choose to be the same or different from each other.

[0109] R f3 It is a divalent polyfluorinated polyether chain.

[0110] A 1 and A 2 Each is independently -O- or C(=O)-O-, and there are multiple A's. 1 and A 2 Each can independently choose to be the same as or different from the others.

[0111] R 1 and R 2 The R group is an alkyl group, a hydrolyzable group, or a hydroxyl group, and there are multiple R groups present. 1 and R 2 They can choose to be the same or different from each other.

[0112] Q 1 It is a linker group with a valence of q1+n1+r1.

[0113] Q 2 It is a linker group with a valence of q2+n2+1.

[0114] Q 3 It is a linker group with a valence of q3+n3+1.

[0115] T is -Si(-R) 3-a (-L) a When there are two or more T's, the two or more T's can be chosen to be the same or different.

[0116] R is an alkyl group.

[0117] L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T can be chosen to be the same or different.

[0118] a is 2 or 3.

[0119] q1 is an integer greater than or equal to 1.

[0120] When q1 is 1, p1 is either 1 or 2.

[0121] When q1 is 2 or higher, p1 is an integer from 0 to 3, at least one of the multiple p1s is 1 or 2, and the multiple p1s can be chosen to be the same or different from each other.

[0122] n1 is an integer greater than or equal to 0, and r1 is an integer greater than or equal to 1.

[0123] q2 is an integer greater than or equal to 1.

[0124] When q2 is 1, p2 is either 1 or 2.

[0125] When q2 is 2 or higher, p2 is an integer from 0 to 3. At least one of the multiple p2s is 1 or 2, and the multiple p2s can be chosen to be the same or different from each other.

[0126] n2 is an integer greater than or equal to 0.

[0127] q3 is an integer greater than or equal to 0.

[0128] When q3 is 1 or higher, p3 is an integer from 0 to 3. If there are multiple p3s, they can be chosen to be the same or different from each other.

[0129] n3 is an integer greater than or equal to 0, and q3+n3 is an integer greater than or equal to 1.

[0130] The above compound (1) has two polyfluoropolyether chains, a reactive silyl group, and a specific linking group [A] connecting the aforementioned polyfluoropolyether chains to the aforementioned reactive silyl group. 1 -Si(R 1 )-Q 1 ].

[0131] In addition, the above compound (2) has three polyfluoropolyether chains, a reactive silyl group, and a specific linking group [A] that connects the aforementioned polyfluoropolyether chains to the aforementioned reactive silyl group. 1 -Si(R 1 )-Q 2 ] and [Q3 -Si(R 2 )-A 2 ].

[0132] This compound possesses a polyfluoropolyether chain. The surface layer of this compound with a polyfluoropolyether chain exhibits excellent fingerprint stain removal properties. Furthermore, this compound, while possessing at least one reactive silyl group [T], also has [Si(R] attached to the [Si(R]] group. 1 )] and [Si(R 2 [T] also functions as a reactive silyl group. In this compound, the reactive silyl group [T] and [Si(R] are disposed at positions slightly separated from [T]. 1 )] and [Si(R 2 The two polyfluoropolyether chains [R] are firmly chemically bonded to the substrate. At this point, in compound (1), the two polyfluoropolyether chains [R] are... f1 ] and [R f2 In compound (2), the two polyfluoropolyether chains [R] are located at relatively far apart positions. f1 ] and [R f1 The components are positioned at relatively large intervals. As a result, a surface layer with excellent abrasion resistance, fingerprint and smudge removal properties, and finger slippage is formed.

[0133] Furthermore, regarding this compound, two polyfluoropolyether chains [R] can be readily introduced into compound (1) by the manufacturing method described later. f1 ] and [R f2 In compound (2), two polyfluoropolyether chains [R] are readily introduced. f1 ] and [R f3 This compound allows for the easy introduction of different polyfluoroethylene (PFE) chains, increasing the design freedom of the molecule. Therefore, it also has the advantage of easily designing molecular structures that match the physical properties required for the surface layer of an item. It should be noted that different PFE chains can include those with different numbers of carbon atoms in the oxyfluoroalkyl groups constituting the chain, and those with different molecular weights.

[0134] R f1 and R f2 It is a monovalent polyfluorinated polyether chain.

[0135] As R f1 From the viewpoint of superior surface layer abrasion resistance and fingerprint removal properties, the fluorination rate of the polyfluoropolyether chain, expressed by the following mathematical formula (1), is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%. If the fluorination rate is above the above lower limit, the fluorine content of the polyfluoropolyether chain increases, and the sliding properties and fingerprint removal properties are improved.

[0136] Mathematical formula (1): Fluorination rate (%) = (Number of fluorine atoms) / {(Number of fluorine atoms) + (Number of hydrogen atoms)} × 100

[0137] From the perspective of balancing fingerprint and dirt removal and slip resistance on the surface layer, each polyfluoropolyether chain (R... f1 Or R f2 The molecular weight of the polyfluoropolyether chain is preferably 1,000 to 20,000, more preferably 2,500 to 15,000, and even more preferably 3,000 to 10,000. If the molecular weight of the polyfluoropolyether chain is above the lower limit mentioned above, the flexibility of the polyfluoropolyether chain is improved and the amount of fluorine in the molecule is increased, resulting in improved finger slippage and fingerprint removal. On the other hand, if the molecular weight of the polyfluoropolyether chain is below the upper limit mentioned above, the surface layer exhibits excellent abrasion resistance.

[0138] Among them, any one of R f1 and A 1 Or A 2 A fluorine atom is bonded to the terminal carbon atom of the link. Additionally, in R... f2 The and Q 1 At least one fluorine atom is bonded to the terminal carbon atom of the connection.

[0139] R f1 The polyfluoroether chain in the compound may optionally have substituents. These substituents can impart a tight bond to the polyfluoroether chain, or, starting with these substituents, further introduce other compounds such as polyfluoroether chains. Preferably, the substituent is located at the end of the polyfluoroether chain. That is, R f1 The preferred structure is the one shown in formula (3A).

[0140] L 1 -R f11a -(OR f12 ) m1 -(CH2) s1 - Equation (3A)

[0141] in,

[0142] L 1 For hydrogen atoms, fluorine atoms, hydroxyl groups, -C(O)X, -C(O)OR 10 -C(O)N(R) 10 )2,

[0143] X is a hydrogen atom or a halogen atom.

[0144] R 10 Each of the R atoms is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms optionally containing a fluorine atom, or a phenyl group optionally containing a fluorine atom, and there exist multiple R atoms. 10 At that time, there are multiple R 10 They can choose to be the same or different from each other.

[0145] R f11a It is a fluoroalkylene group with 1 to 20 carbon atoms.

[0146] R f12 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0147] When m1 is an integer from 0 to 500, and m1 is greater than 2, there are multiple R... f12 Choose either the same or different.

[0148] s1 is an integer from 0 to 20.

[0149] It should be noted that L 1 When L is a hydrogen atom or a fluorine atom 1 -R f11a R in equation (3) as described later f11 The methods are the same, and the preferred methods are also the same.

[0150] Halogen atoms in X above can be listed as fluorine, chlorine, bromine, and iodine atoms.

[0151] As R 10 Preferably, it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, optionally containing fluorine atoms.

[0152] Furthermore, from the viewpoint of ease of synthesis of this compound, s1 is preferably an integer from 1 to 6.

[0153] From the perspective of fingerprint removal and finger swiping, R f2 The polyfluoropolyether chain in the preferred form is the structure shown in formula (3).

[0154] R f11 -(OR f12 ) m1 - Equation (3)

[0155] in,

[0156] R f11 It is a fluoroalkyl group with 1 to 20 carbon atoms.

[0157] R f12 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0158] When m1 is an integer from 0 to 500, and m1 is greater than 2, there are multiple R... f12 Choose either the same or different.

[0159] R f11 The fluoroalkyl group that forms the end of the polyfluoropolyether chain has a carbon number of 1 to 20, which is good for the surface layer’s abrasion resistance and fingerprint removal.

[0160] As Rf11 From the viewpoint that the fluoroalkyl group has better surface layer abrasion resistance and fingerprint stain removal, the fluorination rate shown in the aforementioned mathematical formula (1) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, i.e., perfluoroalkyl.

[0161] R f11 The fluoroalkyl group can be straight-chain, branched, or cyclic.

[0162] As long as the carbon number of the fluoroalkyl group with straight or branched chain is 1 to 20, it is preferable to have 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms, from the viewpoint of excellent abrasion resistance and fingerprint stain removal of the surface layer.

[0163] Examples of fluoroalkyl groups having straight or branched chains include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF(CF3)-, etc.

[0164] R f11 The fluoroalkyl group (also known as fluorocycloalkyl group) with a cyclic structure preferably has 3 to 20 carbon atoms, more preferably 4 to 8, and particularly preferably 4 to 6. If it is within the above range, the surface layer has excellent abrasion resistance and fingerprint stain removal properties.

[0165] As fluoroalkyl groups with cyclic structures, examples include groups of the following formula. In the formula, * denotes a linking bond.

[0166]

[0167] In this formula, some of the fluorine atoms may be substituted with hydrogen atoms.

[0168] R f12 It is a fluoroalkyl group, and from the viewpoint of excellent surface layer abrasion resistance and fingerprint stain removal, the number of carbon atoms is 1 to 6.

[0169] As R f12 From the viewpoint of superior surface layer abrasion resistance and fingerprint removal properties, the fluorination rate expressed by the aforementioned mathematical formula (1) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, i.e., perfluoroalkylene. If the fluorination rate is above the aforementioned lower limit, the fluorine content of the polyfluoropolyether chain increases, and the sliding properties and fingerprint removal properties are improved.

[0170] R f12 The fluorinated alkyl group can be straight-chain, branched, or cyclic.

[0171] Examples of fluoroalkyl groups having straight or branched chains include -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF2CF2CF2-, -CF2CF2CF2CF2CF2-, -CF2CF2CF2CF2CF2-, -CF2CF(CF3)-, etc.

[0172] In addition, fluoroalkyl groups with cyclic structures can be listed as examples of groups with the following formula. In the formula, * denotes a linking bond.

[0173]

[0174] In this formula, some of the fluorine atoms may be substituted with hydrogen atoms.

[0175] m1 represents oxyfluoride alkyl group OR f12 The number of repetitions. m1 can be any integer from 0 to 500. From the viewpoint of superior water and oil repellency, abrasion resistance, and fingerprint and dirt removal, it is preferably 1 to 500, and more preferably 2 to 300.

[0176] The (OR) of equations (3) and (3A) f12 ) m1 The preferred structure is the one shown in formula (3B).

[0177] [(OR 11 ) m11 (OR 12 ) m12 (OR 13 ) m13 (OR 14 ) m14 (OR 15 ) m15 (OR 16 ) m16 Equation (3B)

[0178] in,

[0179] R 11 It is a fluorinated alkylene group with 1 carbon atom.

[0180] R 12 It is a fluorinated alkylene group with 2 carbon atoms.

[0181] R 13 It is a fluorinated alkylene group with 3 carbon atoms.

[0182] R 14 It is a fluoroalkylene group with 4 carbon atoms.

[0183] R 15 It is a fluoroalkylene group with 5 carbon atoms.

[0184] R 16 It is a fluorinated alkylene group with 6 carbon atoms.

[0185] m11, m12, m13, m14, m15, and m16 represent integers greater than or equal to 0 or 1, and m11+m12+m13+m14+m15+m16 are integers from 1 to 500.

[0186] It should be noted that in equation (3B), (OR) 11 )~(OR 16 The bonding order of (OR) is arbitrary. In equation (3B), m11 to m16 represent (OR) respectively. 11 )~(OR 16 The number of ) does not indicate configuration. For example, (OR 15 ) m5 (OR) 15 The quantity is m5, which does not represent (OR) 15 ) m5 The block configuration structure. Similarly, (OR 11 )~(OR 16 The order in which these are recorded does not indicate the bonding order of the individual units.

[0187] R 11 ~R 16 For specific examples, please refer to the aforementioned R f12 specific example.

[0188] From the perspective of excellent water and oil repellency, abrasion resistance, and fingerprint and dirt removal properties, in formula (3B), (OR) f12 ) m1 Preferably, it is a structure represented by any one of the following formulas (3C) to (3F).

[0189] (OR 11 ) m11 -(OR 12 ) m12 (3C)

[0190] (OR 12 ) m12 -(OR 14 ) m14 (3D)

[0191] (OR 13 ) m13 (3F)

[0192] The symbols in equations (3C) to (3F) are the same as those in equation (3A) mentioned above.

[0193] In equations (3C) and (3D) above, (OR) 11 ) and (OR12 (OR) 12 ) and (OR 14 The bonding order of ) is arbitrary. In equation (3C), for example (OR) 11 ) and (OR 12 (OR) can be configured alternately. f1 ) and (OR f2 ) can be configured as blocks, and can also be random. The same applies in equation (3D).

[0194] In formula (3C), m11 is preferably 1 to 30, more preferably 1 to 20. Additionally, m12 is preferably 1 to 30, more preferably 1 to 20.

[0195] In formula (3D), m12 is preferably 1 to 30, more preferably 1 to 20. Additionally, m14 is preferably 1 to 30, more preferably 1 to 20.

[0196] In formula (3F), m13 is preferably 1 to 30, and more preferably 1 to 20.

[0197] Furthermore, from the viewpoint of improving sliding properties, in the polyfluorinated polyether chain of formula (3B), (OR) is preferred. 11 The ratio of ) is high. Specifically, the ratio expressed by the following mathematical formula (2) is preferably 0.2 or more, preferably 0.5 or more, preferably 1.0 or more, and more preferably 2.0 or more.

[0198] Mathematical expression (2): m11 / (m12+m13+m14+m15+m16)

[0199] R f3 It consists of divalent polyfluorinated polyether chains. This compound exhibits excellent fingerprint removal and finger-slippery properties on its surface layer due to the presence of polyfluorinated polyether chains.

[0200] As R f3 From the viewpoint of superior surface layer abrasion resistance and fingerprint removal properties, the fluorination rate expressed by the aforementioned mathematical formula (1) is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%. If the fluorination rate is above the aforementioned lower limit, the fluorine content of the polyfluorinated polyether chain increases, and the sliding properties and fingerprint removal properties are improved.

[0201] From the perspective of balancing fingerprint removal and slip resistance on the surface layer, R f3 The molecular weight is preferably 1000-20000, more preferably 2500-15000, and even more preferably 3000-10000. If R f3If the molecular weight is above the lower limit mentioned above, the flexibility of the polyfluorinated polyether chain increases and the fluorine content in the molecule increases, thus improving finger slippage and fingerprint removal. On the other hand, if R f3 If the molecular weight is below the upper limit mentioned above, the surface layer will have excellent abrasion resistance.

[0202] Among them, in R f3 The and Q 2 and Q 3 A fluorine atom is bonded to the terminal carbon atom of the connection.

[0203] From the perspective of fingerprint removal and finger swiping, R f3 The preferred structure is the one shown in formula (4).

[0204] -R f13 -(OR f13 ) m2 - Equation (4)

[0205] in,

[0206] R f13 It is a fluoroalkylene group having 1 to 6 carbon atoms.

[0207] When m2 is an integer from 0 to 500, and m2 is greater than or equal to 1, there are multiple R... f13 Choose either the same or different.

[0208] R f13 The fluoroalkyl groups having 1 to 6 carbon atoms can be referred to the aforementioned R f12 The preferred method is also the same.

[0209] m2 represents oxyfluoride alkyl group OR f13 The number of repetitions. m2 can be any integer from 0 to 500. From the viewpoint of superior water and oil repellency, abrasion resistance, and fingerprint and dirt removal, it is preferred to be 1 to 500, and more preferably 2 to 300.

[0210] Equation (4) (OR) f13 ) m2 The preferred structure is the one shown in formula (4A).

[0211] [(OR 11 ) m11 (OR 12 ) m12 (OR 13 ) m13 (OR 14 ) m14 (OR 15 ) m15 (OR 16 ) m16 Equation (4A)

[0212] In formula (4A), the symbols are the same as those in formula (3B) above, and the preferred method is also the same as that in formula (3B) above.

[0213] In equations (1) and (2), T represents -Si(R). 3-a (L) a The reactive silyl group is shown. Wherein, R is an alkyl group, L is a hydrolyzable group or hydroxyl group, and two or more Ls in each T can be the same or different, and a is 2 or 3.

[0214] Reactive silyl groups are groups obtained by bonding either or both of hydrolyzable groups and hydroxyl groups to silicon atoms.

[0215] Hydrolyzable groups are groups that form hydroxyl groups through hydrolysis. Specifically, hydrolyzable silane groups form silanol groups (Si-OH) through hydrolysis. These silanol groups further undergo intermolecular dehydration condensation to form Si-O-Si bonds. Additionally, the silanol groups react with hydroxyl groups (substrate-OH) on the substrate surface through dehydration condensation to form chemical bonds (substrate-O-Si).

[0216] Examples of hydrolyzable groups include alkoxy groups, halogen atoms, acyl groups, and isocyanate groups. As an alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. As a halogen atom, a chlorine atom is preferred.

[0217] From the viewpoint of facilitating the manufacture of this compound, alkoxy or halogen atoms are preferred as hydrolyzable groups. From the viewpoint of minimizing degassing during coating and ensuring excellent storage stability of this compound, alkoxy groups with 1 to 4 carbon atoms are preferred. When long-term storage stability of this compound is required, ethoxy groups are particularly preferred. When the reaction time after coating is set to a short time, methoxy groups are particularly preferred.

[0218] In addition, alkyl groups having 1 to 6 carbon atoms can be listed as examples.

[0219] Si(-R) in equations (1) and (2) 1 ) 3-p1 Si(-R) 1 ) 3-p2 and -Si(-R 2 ) 3-p3 This makes it part of the linking group that connects the polyfluoropolyether chain to the reactive silyl group.

[0220] R 1 and R 2 Each R is independently an alkyl, hydrolyzable, or hydroxyl group, and multiple R groups exist. 1 and R 2 They can be either the same or different from each other. R1 and R 2 The alkyl and hydrolyzable groups can be the same as those in the aforementioned reactive silyl groups, and the preferred method is also the same.

[0221] Among them, the preferred option is: multiple R exist. 1 At least one of them is a hydrolyzable group or a hydroxyl group. Additionally, it is preferred that the plurality of R groups are present. 2 At least one of them is a hydrolyzable group or a hydroxyl group. In this case, similar to the aforementioned T, SiR 1 and SiR 2 It undergoes a dehydration condensation reaction with the hydroxyl groups (substrate-OH) on the substrate surface, further improving the adhesion.

[0222] Q in equation (1) 1 It is a linker group with a valence of q1+n1+r1. Q 1 Preferably, it has at least one branch point (P1) selected from the group consisting of organopolysiloxane residues with C, N, Si, ring structures and q1+n1+r1 valence.

[0223] From the viewpoint of ease of manufacturing this compound and excellent surface layer resistance to abrasion, light, and chemicals, the aforementioned ring structure is preferably selected from one of the following groups: aliphatic rings of 3- to 8-membered rings, aromatic rings of 3- to 8-membered rings, heterocyclic rings of 3- to 8-membered rings, and fused rings formed from two or more of these rings. The ring structure listed below is particularly preferred. The ring structure may optionally have substituents such as halogen atoms, alkyl groups (optionally including an ether-like oxygen atom between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, or oxygen groups (=O).

[0224]

[0225] Organopolysiloxane residues with a valence of q1+n1+r1 can be listed as, for example, the following groups. Wherein, R in the following formula... 5 It can be a hydrogen atom, alkyl group, alkoxy group, or phenyl group. R 5 The alkyl and alkoxy groups preferably have 1 to 10 carbon atoms, and more preferably 1.

[0226]

[0227] In this compound (1), Si, T or R in formula (1) f2 Alternatively, it can be directly bonded to the aforementioned branch point (P1), or by selecting -C(O)NR. 6 -, -C(O)O-, -C(O)-, -O-, -NR 6 -, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR6 -、-SO2NR 6 -、-Si(R 6 )2-、-OSi(R 6 The bond is formed by at least one bond (P2) in the group consisting of )2-, -Si(CH3)2-Ph-Si(CH3)2- and divalent organopolysiloxane residues. Wherein, R 6 R is an alkyl or phenyl group with 1 to 6 carbon atoms and hydrogen atoms, and Ph is a phenylene group. From the viewpoint of easy preparation of this compound, R 6 The alkyl group preferably has 1 to 3 carbon atoms, and more preferably 1 to 2.

[0228] Examples of divalent organopolysiloxane residues include groups of the following formula. In the following formula, R... 7 It can be a hydrogen atom, alkyl group, alkoxy group, or phenyl group. R 7 The alkyl and alkoxy groups preferably have 1 to 10 carbon atoms, and more preferably 1.

[0229]

[0230] From the viewpoint of ease of preparation of this compound, the bond (P2) is preferably selected from -C(O)NR. 6 -、-C(O)-、-NR 6 At least one bond in the group consisting of - and -O-, particularly preferably -C(O)NR 6 -or -C(O)-, -O-.

[0231] As Q 1 Combinations of two or more divalent hydrocarbon groups with one or more branch points (P1) or combinations of two or more hydrocarbon groups with one or more branch points (P1) and one or more bonds (P2) can be listed.

[0232] Examples of divalent hydrocarbon groups include 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 particularly preferably 1 to 4.

[0233] From the perspective of the ease of manufacturing this compound, Q 1 Preferably, it has a structure represented by any of the following formulas (5-1) to (5-7).

[0234]

[0235] (-A 11 -Q 12 -)C(-R e2 ) 2-d3 (-Q 32-)(-Q 22 -) d3 Equation (5-2)

[0236] (-A 11 -Q 13 -)N(-Q 33 -)(-Q 23 -) Equation (5-3)

[0237] (-A 11 -Q 14 -)Z(-Q 34 -)(-Q 24 -) d4 Equation (5-4)

[0238] (-A 11 -Q 15 -)Si(-R e3 ) 2-d5 (-Q 35 -)(-Q 25 -) d5 Equation (5-5)

[0239] -A 11 -Q 12 -CH(-Q 32 -)-Si(R e3 ) 3-d6 (-Q 25 -) d6 Equation (5-6)

[0240] -A 11 -Q 12 -CH(-Q 22 -)-Si(R e3 ) 2-d7 (-Q 35 -)(-Q 25 -) d7 Equation (5-7)

[0241] In equations (5-1) to (5-7), A 11 Side and R f2 Or R f3 Connection, Q 22 Q 23 Q 24 Or Q 25 The side is connected to T, Q 32 Q 33 Q 34 Or Q 35 With the help of Si and R f1 connect,

[0242] A 11For single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2-,

[0243] Q 11 For single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2-, alkylene groups; or, alkylene groups having a -C(O)NR bond between carbon atoms in carbon-carbon atoms of the carbon-carbon pair. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups,

[0244] Q 12 It is a single bond, an alkylene group; or, in an alkylene group having two or more carbon atoms, a -C(O)NR bond between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups,

[0245] Q 13 It is a single bond (where A is a single bond). 11 Alkyl groups are -C(O)-; alkylene groups having -C(O)NR between carbon atoms in carbon-carbon pairs. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 A group containing SO2-; or a group having a -C(O)- terminal on the N-side of the alkylene group.

[0246] In Q 14 When the atom in the bonded Z is a carbon atom, Q 14 For Q 12 In Q 14 When the atom in the bonded Z is a nitrogen atom, Q 14For Q 13 ,

[0247] Q 15 It is an alkylene group; or, in an alkylene group having two or more carbon atoms, it has a -C(O)NR bond between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups,

[0248] Q 22 and Q 32 Each is independently an alkylene group; in alkylene groups having two or more carbon atoms, there is a -C(O)NR between the carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups; having a -C(O)NR terminal on the side of the alkylene group not connected to Si. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 A group consisting of SO2-; or, having a -C(O)NR group between carbon atoms in an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- and has -C(O)NR at the end on the side not connected to Si. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 The SO2- group contains multiple Q groups. 22 At that time, there are multiple Qs. 22 Choose either the same or different.

[0249] Q 23 and Q 33 Each is independently an alkylene group; or, in alkylene groups having two or more carbon atoms, a -C(O)NR group is formed between carbon atoms. 6-, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups,

[0250] In Q 24 Or Q 34 When the atom in the bonded Z is a carbon atom, Q 24 and Q 34 Each independently for Q 22 Or Q 32 In Q 24 Or Q 34 When the atom in the bonded Z is a nitrogen atom, Q 24 and Q 34 Each independently for Q 23 Or Q 33 There are multiple Qs 24 At that time, there are multiple Qs. 24 Choose either the same or different.

[0251] Q 25 and Q 35 Each is independently an alkylene group; or, in alkylene groups having two or more carbon atoms, a -C(O)NR group is formed between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 The SO2- group contains multiple Q groups. 25 At that time, there are multiple Qs. 25 Choose either the same or different.

[0252] Z is a group with a d4+2 valence ring structure, and the d4+2 valence ring structure has the same characteristics as Q. 14 Q 24 and Q 34 Directly bonded carbon or nitrogen atoms,

[0253] R e1 It consists of hydrogen atoms or alkyl groups, and contains multiple R atoms. 1 At that time, there are multiple R 1 Choose either the same or different.

[0254] R e2 It can be a hydrogen atom, hydroxyl group, alkyl group or acyloxy group.

[0255] R e3 It is an alkyl group.

[0256] R 6It is an alkyl or phenyl group with 1 to 6 carbon atoms and hydrogen atoms.

[0257] d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1+d2 is an integer from 1 to 6.

[0258] d3 is 1 or 2.

[0259] d4 is an integer greater than or equal to 1.

[0260] d5 is 1 or 2.

[0261] d6 is an integer from 1 to 3.

[0262] d7 is 1 or 2.

[0263] From the perspective of ease of manufacturing this compound and superior surface layer properties of abrasion resistance, light resistance, and chemical resistance, Q 11 Q 12 Q 13 Q 14 Q 15 Q 22 Q 23 Q 24 Q 25 Q 32 Q 33 Q 34 and Q 35 The alkylene group is preferably a straight-chain alkylene group with 1 to 10 carbon atoms, more preferably with 1 to 6 carbon atoms, and even more preferably with 1 to 4 carbon atoms. The lower limit for the number of carbon atoms in the alkylene group having a specific bond between carbon atoms is 2.

[0264] As a loop structure in Z, the loop structures at the aforementioned branch point (P1) can be listed, and their preferred forms are also the same. It should be noted that Q... 14 Q 24 and Q 34 A ring structure directly bonded to Z.

[0265] From the perspective of ease of manufacturing this compound, R e1 R e2 and R e3 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0266] From the perspective of ease of manufacturing this compound, R e2 The alkyl moiety of the acyloxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2.

[0267] From the viewpoint of ease of manufacturing this compound and excellent abrasion resistance and fingerprint stain removal properties of the surface layer, d4 is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

[0268] As Q 1 Other forms can be listed as Q having the structure shown in any of the following equations (6-1) to (6-7). 1 .

[0269]

[0270] (-A 11 -Q 12 -)C(-R e2 ) 2-d3 (-Q 32 -)(-Q 22 -G) d3 Equation (6-2)

[0271] (-A 11 -Q 13 -)N(-Q 33 -)(-Q 23 -G) Equation (6-3)

[0272] (-A 11 -Q 14 -)Z(-Q 34 -)(-Q 24 -G) d4 Equation (6-4)

[0273] (-A 11 -Q 15 -)Si(-R e3 ) 2-d5 (-Q 35 -)(-Q 25 -G) d5 Equation (6-5)

[0274] -A 11 -Q 12 -CH(-Q 32 -)-Si(R e3 ) 3-d6 (-Q 25 -G) d6 Equation (6-6)

[0275] -A 11 -Q 12 -CH(-Q 22 -G)-Si(R e3 ) 2-d7 (-Q 35 -)(-Q25 -G) d7 Equation (6-7)

[0276] In equations (6-1) to (6-7), A 11 With R f2 Connection, G and T connection, Q 32 Q 33 Q 34 Or Q 35 With the help of Si and R f1 connect.

[0277] G is the group shown in the following formulas (6-8), and the symbols other than G are the same as those in formulas (5-1) to (5-7).

[0278] -Si(R 8 ) 3-k (-Q 41 -) k Equation (6-8)

[0279] In equation (6-8), Si and Q 22 Q 23 Q 24 Or Q 25 Or Q 26 Connection, Q 41 Connect to T. R 8 It is an alkyl group. Q 41 It is an alkylene group; in alkylene groups having two or more carbon atoms, there is a -C(O)NR between the carbon atoms. 6 -、-C(O)-、-NR 6 - or -O- groups; or -(OSi(R 9 )2) p -O-, 2 or more Qs 41 Choose either the same or different. k is 2 or 3. R 8 It is an alkyl or phenyl group with 1 to 6 carbon atoms and hydrogen atoms. R 9 It is an alkyl, phenyl, or alkoxy group, with two Rs. 9 Choose either the same or different. p is an integer from 0 to 5. When p is 2 or higher, there are 2 or more (OSi(R)). 9 2) Choose either the same or different.

[0280] From the perspective of ease of manufacturing this compound and superior surface layer properties of abrasion resistance, light resistance, and chemical resistance, Q 41 The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4. Wherein, the lower limit for the number of carbon atoms in the alkylene group when a specific bond exists between carbon atoms is 2.

[0281] From the perspective of ease of manufacturing this compound, R 8 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and particularly preferably 1 to 2.

[0282] From the perspective of ease of manufacturing this compound, R 9 The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and particularly preferably 1 to 2.

[0283] From the perspective of the excellent storage stability of this compound, R 9 The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

[0284] p is preferably 0 or 1.

[0285] Q 2 Q is a linking group with a valence of q² + n² + 1. 3 It is a linker group with a valence of q³+n³+1. Q 2 and Q 3 With the aforementioned Q 1 The same applies, and the preferred method is also the same. Specifically, in the aforementioned Q... 1 In the description, respectively, compound (1) is replaced by compound (2), R f2 Replaced with R f3 n1 is replaced with n2 or n3, q1 is replaced with q2 or q3, and r1 is replaced with 1.

[0286] It should be noted that q1 and q2 are each independently an integer of 1 or more, preferably 1 to 6, and more preferably 1 to 3. q3 can be 0 or an integer of 1 or more. q3 is preferably 0 to 6, and more preferably 0 to 3. In addition, n1, n2, and n3 can each independently be 0 or an integer of 1 or more. n1 to n3 are each preferably 0 to 6, more preferably 0 to 3, and even more preferably 1 to 3.

[0287] The following compounds can be listed as specific examples of this compound.

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295] In this equation, m21 to m121 each independently represent the number of repetitions, and the bonding order of OCF2 and OCF2CF2 is arbitrary. R f This indicates a fluoroalkyl or polyfluoropolyether chain. m21 to m121 are each an independent integer from 1 to 500, and the aforementioned m1 is appropriately adjusted within the range of 1 to 500.

[0296] <Method for manufacturing this compound>

[0297] Regarding the synthesis of compound (1), as an example, a method (A) can be listed that causes the following compound (1A) to react with the following compound (1B) or the following compound (2B).

[0298] R f2 -Q 1 (-T) n1+1 Equation (1A)

[0299] R f1 -OH Formula (1B)

[0300] R f1 -COOH Formula (2B)

[0301] The symbols are the same as those in equation (1), and the preferred method is also the same.

[0302] In addition, regarding the synthesis method of compound (2), as an example, a method (B) can be listed that causes the following compound (2A) to react with the following compound (1B) or the following compound (2B).

[0303] (T-) n2+1 Q 2 -R f3 -Q 3 (-T) n3+1 Equation (2A)

[0304] R f1 -OH Formula (1B)

[0305] R f1 -COOH Formula (2B)

[0306] The symbols are the same as those in equation (2), and the preferred method is also the same.

[0307] The above synthetic methods all involve reacting the L in T with compound (1B) or compound (2B). According to this method, it is easy to prepare compound (1) by reacting the L in T with compound (2B). f1 With R f2 R in compound (2) f1 With Rf3 Different polyfluoropolyether chains increase the degree of freedom in molecular design.

[0308] It should be noted that when multiple Ls are present in compounds (1A) and (2A), these multiple Ls may sometimes react with compounds (1B) or (2B) to introduce multiple Rs. f1 (For example, the following compound (1C) or the following compound (2C)).

[0309] {R f1 -A 1 -Si(R 1 )2}2-Q 1 (-T) n1-1 -R f2 Equation (1C)

[0310] {R f1 -A 1 -Si(R 1 )2}2-Q 2 (-T) n2-1 -R f3 -Q 3 (-T) n3-1 {-Si(R 2 )2-A 2 -R f1 Equation 2 (2C)

[0311] The symbols are the same as those in equation (1) or equation (2), and the preferred methods are also the same.

[0312] However, it can be confirmed that the aforementioned compound (1) is preferentially generated according to the aforementioned method (A), and the aforementioned compound (2) is preferentially generated according to the aforementioned method (B). In addition, compounds (1C) and (2C), which exist as byproducts, can also function as coating agents exhibiting fingerprint removal and finger sliding properties, and can also be used as coating agents mixed with this compound, as described later.

[0313] Compounds (1A) and (2A) can be synthesized with reference to, for example, International Publication Nos. 2017 / 038832, 2017 / 038830, and 2018 / 216630. Compound (1B) can be synthesized with reference to International Publication No. 2017 / 038832. Compound (2B) can be synthesized with reference to International Publication No. 2017 / 038832. Alternatively, commercially available products can be used.

[0314] [Compositions containing fluorine compounds]

[0315] The fluorinated compound composition of the present invention (hereinafter also referred to as the "composition") comprises the aforementioned fluorinated compound as the "composition," and comprises fluorinated compounds other than the "composition" and at least one of the following impurities. Examples of impurities include compounds unavoidable in the manufacture of the "composition" and other fluorinated compounds. It should be noted that the composition does not contain the liquid medium described later.

[0316] Other fluorinated compounds include byproducts of the manufacture of this compound (hereinafter also referred to as byproduct fluorinated compounds) and known fluorinated compounds used for the same purpose as this compound. It should be noted that compounds (1A) and (2A) used as raw materials in the aforementioned synthesis method are known fluorinated compounds used for the same purpose as this compound.

[0317] As for other fluorinated compounds, those with a low risk of reducing the properties of this compound are preferred.

[0318] From the viewpoint of fully utilizing the properties of this compound, the content of other fluorinated compounds in the total composition is preferably less than 50% by mass, more preferably less than 30% by mass, and even more preferably less than 10% by mass.

[0319] Examples of byproduct fluorinated compounds include those synthesized in this compound. Examples include compounds (1C) and (2C), which are byproducts of the aforementioned synthesis method. These compounds (1C) and (2C) can also function as coating agents exhibiting fingerprint removal and finger-slip properties. Therefore, when this composition contains byproduct fluorinated compounds, the refining process for removing or reducing the amount of these byproduct fluorinated compounds can be simplified.

[0320] As well-known fluorine-containing compounds, examples include those described in the following documents.

[0321] Japanese Patent Application Publication No. 11-029585 discloses a perfluoropolyether-modified aminosilane.

[0322] The silicon-containing organic fluoropolymer disclosed in Japanese Patent No. 2874715

[0323] Organosilicon compounds as described in Japanese Patent Application Publication No. 2000-144097

[0324] Japanese Patent Application Publication No. 2000-327772 discloses a perfluoropolyether-modified aminosilane.

[0325] Fluorinated siloxanes as described in Japanese Patent Publication No. 2002-506887

[0326] Organosilicon compounds listed in Japanese Patent Publication No. 2008-534696

[0327] The fluorinated polymer containing modified hydrogen disclosed in Japanese Patent No. 4138936

[0328] Compounds described in U.S. Patent Application Publication No. 2010 / 0129672, International Publication No. 2014 / 126064, and Japanese Patent Application Publication No. 2014-070163.

[0329] Organosilicon compounds described in International Publication No. 2011 / 060047 and International Publication No. 2011 / 059430,

[0330] Fluorinated organosilane compounds described in International Publication No. 2012 / 064649

[0331] Polymers containing fluoroalkylene groups as described in Japanese Patent Application Publication No. 2012-72272

[0332] 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.

[0333] Silane compounds containing perfluoro(poly)ethers as described in Japanese Patent Application Publication No. 2014-218639, International Publication No. 2017 / 022437, International Publication No. 2018 / 079743, and International Publication No. 2018 / 143433.

[0334] Japanese Patent Application Publication Nos. 2015-199906, 2016-204656, 2016-210854, and 2016-222859 disclose polymer-modified silanes containing fluorinated polyether groups.

[0335] 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, and International Publication No. 2019 / 163282.

[0336] 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.

[0337] The proportion of this compound in the composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0338] When this composition contains other fluorinated compounds, the proportion of the other fluorinated compounds in this composition relative to the total of this compound and the 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.

[0339] The total proportion of this compound and other fluorinated compounds in this composition is preferably 80% by mass or more, more preferably 85% by mass or more.

[0340] If the content of this compound and other fluorinated compounds is within the aforementioned range, the surface layer will exhibit excellent water and oil repellency, abrasion resistance, fingerprint and dirt removal properties, finger slippage, and appearance.

[0341] [Coating liquid]

[0342] The coating liquid of the present invention (hereinafter also referred to as the coating liquid) contains the compound or the composition and includes a liquid medium. The coating liquid can be any liquid, including solutions and dispersions.

[0343] This coating liquid only needs to contain this compound or this composition, and may contain impurities such as byproducts generated during the manufacturing process of this compound.

[0344] The concentration of this compound or composition in the coating solution is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass.

[0345] As a liquid medium, an organic solvent is preferred. The organic solvent can be a fluorinated organic solvent, a non-fluorinated organic solvent, or may contain both.

[0346] Examples of fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluorinated alkyl ethers, fluorinated alkylamines, and fluorinated alcohols.

[0347] As a fluorinated alkane, compounds with 4 to 8 carbon atoms are preferred. Examples of commercially available products include C6F. 13 H (AGC Company, ASAHIKLIN (registered trademark) AC-2000), C6F 13 C2H5 (manufactured by AGC Corporation, ASAHIKLIN (registered trademark) AC-6000), C2F5CHFCHFCF3 (manufactured by Chemours Corporation, Vertrel (registered trademark) XF), etc.

[0348] Examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.

[0349] As fluoroalkyl ethers, compounds with 4 to 12 carbon atoms are preferred. Examples of commercially available products include CF3CH2OCF2CF2H (manufactured by AGC, ASAHIKLIN (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300).

[0350] Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.

[0351] Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

[0352] As a non-fluorinated organic solvent, compounds formed only of hydrogen atoms and carbon atoms, as well as compounds formed only of hydrogen atoms, carbon atoms and oxygen atoms, are preferred. Examples include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents and ester organic solvents.

[0353] The coating solution preferably contains 75 to 99.999% by mass of a liquid medium, more preferably 85 to 99.99% by mass, and particularly preferably 90 to 99.9% by mass.

[0354] In addition to containing the present compound or composition and a liquid medium, this coating liquid may also contain other components without impairing the effects of the present invention.

[0355] Other components include known additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reactions of hydrolyzable silanes.

[0356] The content of other components in this coating solution is preferably 10% by mass or less, more preferably 1% by mass or less.

[0357] The concentration of the compound in this coating solution, or the total concentration of this composition and other components (hereinafter also referred to as the solids concentration), is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.01 to 1% by mass. The solids concentration of the coating solution is calculated based on the mass of the coating solution before heating and the mass after heating in a convection dryer at 120°C for 4 hours.

[0358] [thing]

[0359] Figure 1 This is a cross-sectional schematic diagram illustrating an example of an article of the present invention. The first article of the present invention is an article 20 having a substrate 12, a base layer 14, and a surface layer 22 in sequence.

[0360] The aforementioned base layer contains an oxide containing silicon, and the aforementioned surface layer contains a condensate of the aforementioned compound.

[0361] The material and shape of the substrate in the first article described above can be appropriately selected according to the intended use of the article. Examples of substrate materials include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. Glass can be chemically strengthened. In particular, substrates requiring water and oil repellency include substrates for touch panels, substrates for displays, and substrates constituting the housing of electronic devices. Substrates for touch panels and substrates for displays are light-transmitting. "Light-transmitting" means that the transmittance of visible light under perpendicular incidence, according to JIS R3106:1998 (ISO 9050:1990), is 25% or more. Glass or transparent resin is preferred as the material for a touch panel substrate.

[0362] The substrate can undergo surface treatments such as corona discharge treatment, plasma treatment, and plasma graft polymerization treatment on the surface where the base layer is provided. The adhesion between the substrate and the base layer is further improved after surface treatment, resulting in further improvement in the wear resistance of the surface layer. From the perspective of further improving the wear resistance of the surface layer, corona discharge treatment or plasma treatment is preferred as the surface treatment.

[0363] The substrate layer is a layer containing at least an oxide containing silicon, and may further contain other elements. By containing silicon oxide, the substrate layer undergoes dehydration condensation of part of the structure (2) of the aforementioned compound, forming Si-O-Si bonds between itself and the substrate layer, thus forming a surface layer with excellent wear resistance.

[0364] The silica content in the substrate layer only needs to be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. If the silica content is at or above the lower limit of the aforementioned range, Si-O-Si bonds are sufficiently formed in the substrate layer, thus ensuring the mechanical properties of the substrate layer. The silica content is the balance after deducting the total content of other elements (in the case of oxides) from the mass of the substrate layer.

[0365] From the perspective of surface layer durability, the oxide in the base layer preferably also contains one or more elements selected from alkali metals, alkaline earth metals, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. By containing these elements, the bonding between the base layer and the aforementioned compound is strengthened, and wear resistance is improved.

[0366] When the substrate layer contains one or more of iron, nickel and chromium, their total content, in terms of the ratio to silicon oxide, is preferably 10 to 1100 ppm by mass, more preferably 50 to 1100 ppm by mass, further preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass.

[0367] When the base layer contains one or more of aluminum and zirconium, their total content is preferably 10 to 2500 ppm by mass, more preferably 15 to 2000 ppm by mass, and even more preferably 20 to 1000 ppm by mass.

[0368] When the base layer contains alkali metal elements, their total content is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and even more preferably 1.0 to 10% by mass. It should be noted that lithium, sodium, potassium, rubidium, and cesium can be cited as alkali metal elements.

[0369] When the base layer contains platinum group elements, their total content is preferably 0.02 ppm by mass or more and 800 ppm by mass or less, more preferably 0.04 ppm by mass or more and 600 ppm by mass or less, and even more preferably 0.7 ppm by mass or more and 200 ppm by mass or less. It should be noted that platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium.

[0370] When the base layer contains one or more selected from boron and phosphorus, the ratio of the total molar concentration of boron and phosphorus to the molar concentration of silicon is preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, from the perspective of the wear resistance of the surface layer.

[0371] When the base layer contains alkaline earth metal elements, from the perspective of the wear resistance of the surface layer, the ratio of the total molar concentration of the alkaline earth metal elements to the molar concentration of silicon is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2. It should be noted that examples of alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.

[0372] From the perspective of improving the adhesion of this compound, improving the water and oil repellency and abrasion resistance of the article, the substrate layer is preferably a silicon oxide layer containing alkali metal atoms. Specifically, the average concentration of alkali metal atoms in this silicon oxide layer in a region 0.1–0.3 nm deep from the surface in contact with the aforementioned surface layer is preferably 2.0 × 10⁻⁶. 19 atoms / cm 3 That's all. On the other hand, from the perspective of fully ensuring the mechanical properties of the silicon oxide layer, the average concentration of the aforementioned alkali metal atoms is preferably 4.0 × 10⁻⁶. 22 atoms / cm 3 the following.

[0373] The thickness of the substrate layer is preferably 1–200 nm, and particularly preferably 2–20 nm. If the thickness of the substrate layer is above the lower limit of the aforementioned range, the improved adhesion provided by the substrate layer can be easily and sufficiently obtained. If the thickness of the substrate layer is below the upper limit of the aforementioned range, the wear resistance of the substrate layer itself becomes higher. As a method for measuring the thickness of the substrate layer, methods based on cross-sectional observation of the substrate layer using an electron microscope (SEM, TEM, etc.) can be cited; methods using optical interferometer film thickness gauges, spectral ellipsometers, height difference gauges, etc. can also be cited.

[0374] Methods for forming the substrate layer include, for example, depositing a vapor-deposited material having the desired composition of the substrate layer onto the surface of a substrate.

[0375] As an example of vapor deposition, vacuum vapor deposition can be cited. Vacuum vapor deposition is a method in which the vapor deposition material evaporates and adheres to the surface of a substrate in a vacuum tank.

[0376] The temperature during vapor deposition (e.g., when using a vacuum vapor deposition apparatus, the temperature of the vessel for vapor deposition) is preferably 100–3000 °C, and particularly preferably 500–3000 °C.

[0377] The pressure during vapor deposition (e.g., when using a vacuum vapor deposition apparatus, setting the absolute pressure inside the tank for vapor deposition material) is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.

[0378] When using vapor deposition materials to form the base layer, one type of vapor deposition material can be used, or two or more vapor deposition materials containing different elements can be used.

[0379] Examples of evaporation methods for vapor deposition materials include resistance heating, where the vapor deposition material is melted and evaporated on a resistance-heated boat made of a high-melting-point metal; and electron gun methods, where the vapor deposition material is directly heated by irradiating it with an electron beam, causing the surface to melt and evaporate. Among these methods, the electron gun method is preferred because it allows for localized heating, enabling the evaporation of high-melting-point substances; the areas not irradiated by the electron beam are at low temperatures, thus eliminating concerns about reactions with the container; and it minimizes the risk of impurity contamination. For the vapor deposition material used in the electron gun method, molten granules or sintered bodies are preferred because they are less prone to dispersion even when airflow is generated.

[0380] The surface layer on the substrate layer contains condensates of the aforementioned compound. These condensates include: hydrolysis of the hydrolyzable silane group in the compound to form a silanol group (Si-OH); intermolecular condensation of the silanol group to form a Si-O-Si bond; and condensation of the silanol group in the compound with silanol groups or Si-OM groups (where M is an alkali metal element) on the surface of the substrate layer to form a Si-O-Si bond. Additionally, the surface layer may contain condensates of fluorinated compounds other than the compound itself. That is, the surface layer contains a fluorinated compound with reactive silane groups in a state where some or all of the reactive silane group of the fluorinated compound has undergone a condensation reaction.

[0381] The thickness of the surface layer is preferably 1–100 nm, and particularly preferably 1–50 nm. If the thickness of the surface layer is above the lower limit of the aforementioned range, the effects of the surface layer are fully realized. If the thickness of the surface layer is below the upper limit of the aforementioned range, the utilization efficiency is high.

[0382] The thickness of the surface layer is obtained using an X-ray diffractometer for thin film analysis. The thickness of the surface layer can be calculated as follows: using an X-ray diffractometer for thin film analysis, the interference pattern of reflected X-rays is obtained by the X-ray reflectance method, and the thickness can be calculated from the vibration period of the interference pattern.

[0383] The second article of the present invention is an article 20 having a substrate 12 and a surface layer 22.

[0384] The aforementioned substrate contains an oxide comprising silicon.

[0385] The aforementioned surface layer contains a condensate of the aforementioned compound.

[0386] The substrate of the second article has the same composition as the base layer in the first article. Therefore, even if the surface layer is formed directly on the substrate, the wear resistance of the surface layer is excellent.

[0387] The substrate material of the second article only needs to have the same composition as the aforementioned base layer, and can be, for example, a glass substrate. Since the material of the substrate is the same as that of the aforementioned base layer, this description is omitted. Furthermore, the composition of the surface layer is also the same as that of the first article, so this description is also omitted.

[0388] [Item crafting method]

[0389] The method for manufacturing the article of the present invention is as follows: using the aforementioned fluorinated compound, the aforementioned composition containing the fluorinated compound, or the aforementioned coating liquid, a surface layer is formed by a dry coating method or a wet coating method.

[0390] This compound and composition can be directly used in dry coating processes. They are suitable for forming surface layers with excellent adhesion via dry coating. Examples of dry coating methods include vacuum evaporation, CVD, and sputtering. From the perspectives of suppressing the decomposition of this compound and the simplicity of the apparatus, vacuum evaporation is a suitable method.

[0391] In vacuum evaporation, granular materials containing this compound can be used within porous metal bodies formed from metal materials such as iron and steel. These granular materials can be manufactured by impregnating a solution of this compound into the porous metal body and then drying it to remove the liquid medium. This coating solution can be used as the solution for this compound.

[0392] This coating solution is suitable for wet coating methods. Examples of wet coating methods include spin coating, line coating, spray coating, blade coating, dip coating, mold coating, inkjet coating, flow coating, roller coating, casting, Langmuir-Blodgett coating, and gravure coating.

[0393] To improve the abrasion resistance of the surface layer, operations can be performed as needed to promote the reaction between the compound and the substrate. Examples of such operations include heating, humidification, and light irradiation. For instance, heating the substrate on which the surface layer is formed in a humid atmosphere can promote the hydrolysis of hydrolyzable groups, the reaction of hydroxyl groups on the substrate surface with silanol groups, and the formation of siloxane bonds resulting from the condensation reaction of silanol groups.

[0394] After surface treatment, compounds that are not chemically bonded to the surface layer, i.e., other compounds or the substrate, can be removed as needed. Specific methods include, for example, allowing solvent to flow through the surface layer, or wiping with a cloth soaked in solvent.

[0395] Example

[0396] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. It should be noted that Examples 1 to 10 and Example 12 are examples, and Examples 11 and 13 are comparative examples. Furthermore, hereinafter, CCl2FCClF2 will be designated as R-113, CClF2CF2CCl2CF2CF3 as R-419, CF3CH2OCF2CF2H as AE-3000, and C6F... 13 H is denoted as AC-2000, CF3CF2CHCl2 as AK-225, and C4F9OC2H5 as HFE-7200.

[0397] [Example 1] Synthesis of Compound I

[0398] (Synthesis Example 1-1)

[0399] The following compound (1a) was synthesized according to the method described in Examples 3-4 of International Publication No. 2017 / 038832.

[0400] Equation (1a)

[0401]

[0402] The average value of x1 is 13.

[0403] (Synthesis Example 1-2)

[0404] The following compound (1b) was synthesized according to the method described in Examples 1-5 of International Publication No. 2017 / 038832.

[0405] Equation (1b)

[0406]

[0407] The average value of y1 is 21, and the average value of z1 is 20.

[0408] (Synthesis Example 1-3)

[0409] Under a nitrogen atmosphere, 0.0 g of HFE-72002, 5.0 g of the aforementioned compound (1a), and an equal molar amount of the aforementioned compound (1b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain compound (I). Si-NMR confirmed that the Si atoms of compound (1a) form bonds with the OH atoms of compound (1b). Furthermore, F-NMR confirmed the product.

[0410] Equation (1)

[0411]

[0412] The average value of x1 is 13, the average value of y1 is 21, and the average value of z1 is 20.

[0413] [Example 2] Synthesis of Compound II

[0414] (Synthesis example 2-1)

[0415] The following compound (2b) was synthesized according to the method described in Example 7 of International Publication No. 2013 / 121984.

[0416] Equation (2b)

[0417]

[0418] The average value of x2 is 13.

[0419] (Synthesis example 2-2)

[0420] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 2.0 g of the aforementioned compound (1a), and an equal molar amount of the aforementioned compound (2b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain compound (II). Si-NMR confirmed that the Si atoms of compound (1a) formed bonds with the OH atoms of compound (2b). Furthermore, F-NMR confirmed the product.

[0421] Equation (II)

[0422]

[0423] The average of x² is 13, and the average of y² is 13.

[0424] [Example 3] Synthesis of Compound III

[0425] (Synthesis example 3-1)

[0426] Prepare FLUOROL INK (registered trademark) D4000 (compound (3b) below) manufactured by Solvay Solexis.

[0427] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 1.0 g of the aforementioned compound (1a), and an equal molar amount of the aforementioned compound (3b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain compound (III). Si-NMR confirmed that the Si atoms of compound (1a) formed bonds with the OH atoms of compound (3b). Furthermore, F-NMR confirmed the product.

[0428] Equation (3b)

[0429]

[0430] Among them, the average value of y3 is 21 and the average value of z3 is 20.

[0431] Equation (III)

[0432]

[0433] The average value of x3 is 13, the average value of y3 is 21, and the average value of z3 is 20.

[0434] [Example 4] Synthesis of compound IV

[0435] (Synthesis Example 4-1)

[0436] The following compound (4a) was synthesized according to the method described in Example 11-3 of International Publication No. 2017 / 038830.

[0437] Equation (4a)

[0438]

[0439] The average value of x4 is 13.

[0440] (Synthesis Example 4-2)

[0441] The following compound (4b) was synthesized according to the method described in Example 1-1 of International Publication No. 2017 / 038832.

[0442] Equation (4b)

[0443]

[0444] Among them, the average value of y4 is 21 and the average value of z4 is 20.

[0445] (Synthesis Example 4-3)

[0446] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 2.0 g of the aforementioned compound (4a), and an equal molar amount of the aforementioned compound (4b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain the following compound (IV). Si-NMR confirmed that the Si atoms of compound (4a) form bonds with the OH atoms of compound (4b). Furthermore, F-NMR confirmed the product.

[0447] Formula (IV)

[0448]

[0449] The average value of x4 is 13, the average value of y4 is 21, and the average value of z4 is 20.

[0450] [Example 5] Synthesis of compound V

[0451] (Synthesis Example 5-1)

[0452] The following compound (5a) was synthesized according to the method described in Examples 5-8 of International Publication No. 2018 / 216630.

[0453] Equation (5a)

[0454]

[0455] The average value of x5 is 9.

[0456] (Synthesis example 5-2)

[0457] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 1.0 g of the aforementioned compound (5a), and an equal molar amount of the aforementioned compound (1b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain compound (V). The product was confirmed by NMR. Si-NMR confirmed that the Si atoms of compound (5a) form bonds with the OH atoms of compound (1b). Furthermore, F-NMR confirmed the product.

[0458] Formula (V)

[0459]

[0460] Among them, the average of x5 is 9, the average of y5 is 21, and the average of z5 is 20.

[0461] [Example 6] Synthesis of compound VI

[0462] (Synthesis Example 6-1)

[0463] The following compound (6-1) was synthesized according to the method of Example 1 in International Publication No. 2013 / 121984. The fraction with an average of 5 x 6 fractions of the following formula (6-1) was separated by silica gel chromatography.

[0464] Equation (6-1)

[0465]

[0466] The average value of x6 is 5.

[0467] (Synthesis Example 6-2)

[0468] Compound (6-1) 9.0 g, ASAHIKLIN AK-225 (product name, manufactured by AGC) 50 g, and 2.0 M ammonia-methanol solution 7.5 g were added to a 100 cc pressure reactor and stirred at room temperature for 6 hours. Subsequently, the solvent was distilled off to obtain compound (6-2) as described below.

[0469] Equation (6-2)

[0470]

[0471] (Synthesis Example 6-3)

[0472] 9.0 g of compound (6-2), 75 g of AK-225, and 30 g of diethyl ether were added to a 300 cc g-faced flask and stirred in an ice bath. Then, 0.31 g of lithium aluminum hydride was slowly added while stirring at room temperature. The solid precipitated by adding 0.3 cc of a saturated aqueous solution of sodium sulfate was removed by Celite filtration. The resulting filtrate was concentrated and purified by silica gel column chromatography to give compound (6-3).

[0473] Equation (6-3)

[0474]

[0475] (Synthesis Example 6-4)

[0476] Add 0.2 g of HO(C=O)C(CH2CH=CH2)3, 10 mL of dichloromethane, and 0.2 mL of oxalyl chloride to a 50 cc flask. Stir while chilled, then add 0.02 g of DMF (N,N-dimethylformamide). After stirring at room temperature, concentrate to obtain 0.18 g of Cl(C=O)C(CH2CH=CH2)3.

[0477] Separately, 1.8 g of compound (6-3) and 0.35 mL of triethylamine were added to a 50 cc flask, along with 2 mL of the above-mentioned Cl(C=O)C(CH2CH=CH2)3 and 1,3-bis(trifluoromethylbenzene). The mixture was stirred for 1 hour, and the solvent was distilled off. The crude product was purified by silica gel column chromatography to obtain compound (6-4).

[0478] Equation (6-4)

[0479]

[0480] (Synthesis Example 6-5)

[0481] Compound (6-4) 0.6 g, a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass) 0.003 g, aniline 0.0009 g, and AC-6000 (product name, manufactured by AGC) 1.0 g were added to a 50 cc flask purged with nitrogen. Then, 0.11 g of trimethoxysilane was added, and the mixture was stirred at 40 °C. Subsequently, equal amounts of the xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), aniline, and AC-6000 were added, and the mixture was stirred for 7 hours. The solvent was then distilled off to obtain compound (6a).

[0482] Equation (6a)

[0483]

[0484] (Synthesis Example 6-6)

[0485] Under a nitrogen atmosphere, 0.0 g of HFE-72001, 0.5 g of the aforementioned compound (6a), and an equal molar amount of the aforementioned compound (1b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain compound (VI). Si-NMR confirmed that the Si atoms of compound (6a) form bonds with the OH atoms of compound (1b). Furthermore, F-NMR confirmed the product.

[0486] Formula (VI)

[0487]

[0488] Among them, the average value of x6 is 5, the average value of y6 is 21, and the average value of z6 is 20.

[0489] [Example 7] Synthesis of compound VII

[0490] (Synthesis Example 7-1)

[0491] Add 3.0 g of compound (7-1), 0.55 g of HO-CH2C(CH2CH=CH2)3, 0.14 g of NaF, and 3.0 g of AC-2000 to a 50 ml flask and stir at 30 °C for 5 hours. Purify the crude compound using silica gel chromatography to obtain compound (7-2).

[0492] Equation (7-1)

[0493]

[0494] The average value of x7 is 13.

[0495] Equation (7-2)

[0496]

[0497] (Synthesis Example 7-2)

[0498] Compound (7-2) 1.0 g, a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass) 0.003 g, aniline 0.0009 g, and AC-6000 1.0 g were added to a nitrogen-purged 50 cc gai flask, followed by the addition of 0.11 g of trimethoxysilane. The mixture was stirred at 40 °C. Subsequently, equal amounts of the xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), aniline, and AC-6000 were added and stirred. The solvent was then distilled off to obtain compound (7a).

[0499] Equation (7a)

[0500]

[0501] (Synthesis Example 7-3)

[0502] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 1.5 g of the aforementioned compound (7a), and an equal molar amount of the aforementioned compound (1b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain compound (VII). Si-NMR confirmed that the Si atoms of compound (7a) form bonds with the OH atoms of compound (1b). Furthermore, F-NMR confirmed the product.

[0503] Equation (VII)

[0504]

[0505] Among them, the average value of x7 is 13, the average value of y7 is 21, and the average value of z7 is 20.

[0506] [Example 8] Synthesis of compound VIII

[0507] (Synthesis example 8-1)

[0508] Compound (8-1) was synthesized using the same synthetic method as described in Synthesis Examples 1-4 of Japanese Patent No. 6024816.

[0509] CH3OCOCF2-(OCF2) x8 -(OCF2CF2) y8 -OCF2CO2CH3 Equation (8-1)

[0510] The average value of x8 is 26, and the average value of y8 is 22.

[0511] (Synthesis example 8-2)

[0512] Compound (8-2) was synthesized according to the methods described in International Publication No. 2018 / 216630 (Examples 13-1) to (Examples 13-2).

[0513] CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2OTs Formula (8-2)

[0514] (Ots represents -O-SO2-Ph-CH3, Ph represents phenylene.)

[0515] (Synthesis Example 8-3)

[0516] 4 g of compound (8-2), 30 g of compound (8-1), and 160 g of 1,3-bis(trifluoromethyl)benzene were added to a 300 mL three-necked flask, along with 12 g of cesium carbonate. The mixture was stirred at 70 °C under a nitrogen atmosphere. After filtering the solids, the mixture was washed with water, and the organic phase was recovered. The mixture was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 12 g of compound (8-3).

[0517] CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2O-CH2-CF2-{(OCF2) x8 (OCF2CF2) y8 Equation (8-3) -OCF2-CH2-OH

[0518] (Synthesis Example 8-4)

[0519] 12 g of compound (8-3) and 2.3 g of sodium fluoride powder were added to a 100 mL flask, along with 11 g of CF3CF2CF2OCF(CF3)C(O)F. The mixture was stirred under a nitrogen atmosphere. After removing the sodium fluoride powder by filtration, excess CF3CF2CF2OCF(CF3)C(O)F was removed by vacuum distillation to obtain 12 g of compound (8-4).

[0520] CF3CF2CF2-O-CHF-CF2OCH2CH2CH2CH2CH2CH2O-CH2-CF2-{(OCF2) x8 (OCF2CF2) y8}-OCF2-CH2-OC(O)CF(CF3)OCF2CF2CF3 Formula (8-4)

[0521] (Synthesis Example 8-5)

[0522] A cooler maintaining a temperature of 20°C, a NaF granular filling layer, and a cooler maintaining a temperature of 0°C are connected in series at the gas outlet of a 1L nickel-made autoclave. A liquid return line is installed to return the liquid collected by the 0°C cooler back to the autoclave.

[0523] 750g of CFE-419 was added to the autoclave while stirring at 25°C. Nitrogen was purged into the autoclave for 1 hour at 25°C, followed by purging of 20% fluorine gas for 1 hour at a flow rate of 2.0 L / h at 25°C. While purging 20% ​​fluorine gas at the same flow rate, a solution obtained by dissolving 6.0g of compound (8-4) in 54g of CFE-419 was injected into the autoclave over 1 hour. While purging 20% ​​fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). 4mL of a benzene solution containing 0.05g / mL benzene in CFE-419 was heated from 25°C to 40°C and injected into the autoclave, with the benzene inlet closed. After stirring, another 4mL of benzene solution was injected while maintaining the temperature at 40°C, with the inlet closed. This process was repeated. The total amount of benzene injected was 0.17g. 20% fluorine gas was continuously stirred while being blown in at the same flow rate. The pressure inside the autoclave was set to atmospheric pressure, and nitrogen gas was blown in. The contents of the autoclave were concentrated using a rotary evaporator to obtain 6.1 g of compound (8-5).

[0524] CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x8 (OCF2CF2) y8}-OCF2-CF2-OC(O)CF(CF3)OCF2CF2CF3 Formula (8-5)

[0525] (Synthesis Example 8-6)

[0526] 6.1 g of compound (8-5) and 10 g of AK-225 were added to a round-bottom flask made of PFA. While cooling in an ice bath with stirring, 10 g of methanol was slowly added dropwise from a dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours. The reaction mixture was concentrated using a rotary evaporator to give 5.5 g of compound (8-6).

[0527] CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x8 (OCF2CF2) y8 Equation (8-6) -OCF2-C(O)OCH3

[0528] (Synthesis Example 8-7)

[0529] Add 2.4 g of sodium borohydride powder and 15 g of AC-2000 to a 300 cc three-necked round-bottom flask. While cooling in an ice bath and stirring, slowly add a solution containing 30 g of compound (8-6), 4 g of methanol, and 60 g of AC-2000 dropwise from a dropping funnel under a nitrogen atmosphere, keeping the internal temperature below 10°C. After the entire amount has been added, add another 4 g of methanol. Then, stir at 10°C. Cool again in an ice bath and add hydrochloric acid solution dropwise.

[0530] After the reaction was complete, the organic phase was recovered by washing with hydrochloric acid solution and water sequentially. The recovered organic phase was concentrated and removed by vacuum distillation to obtain compound (8-7).

[0531] CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x8 (OCF2CF2) y8 Equation (8-7) -OCF2-CH2-OH

[0532] (Synthesis example 8-8)

[0533] Add 0.67 g of HO(C=O)C(CH2CH=CH2)3, 33 mL of dichloromethane, and 0.67 mL of oxalyl chloride to a 200 cc flask. Stir while chilled, then add 0.0393 g of DMF (N,N-dimethylformamide). After stirring at room temperature, concentrate to obtain 0.6 g of Cl(C=O)C(CH2CH=CH2)3.

[0534] In a separate 50cc flask, 7g of compound (8-7), 7g of AC-6000, 0.4g of triethylamine, and 0.2g of N,N-dimethyl-4-aminopyridine were added, along with 0.6g of the aforementioned Cl(C=O)C(CH2CH=CH2)3. The mixture was stirred at 30°C. The resulting reaction solution was purified by silica gel chromatography to obtain compound (8-8).

[0535] CF3CF2CF2-O-CF2-CF2OCF2CF2CF2CF2CF2CF2O-CF2-CF2-{(OCF2) x8 (OCF2CF2) y8 Equation (8-8): -OCF2-CH2-O(C=O)C(CH2CH=CH2)3

[0536] (Synthesis Example 8-9)

[0537] 1.0 g of compound (8-8), 0.003 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), 0.0009 g of aniline, and 1.0 g of AC-6000 were added to a 50 cc flask purged with nitrogen. Then, 0.11 g of trimethoxysilane was added, and the mixture was stirred at 40 °C for 4 hours. Subsequently, 0.003 g of the xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass), aniline, and AC-6000 were added, and the mixture was stirred. The solvent was then distilled off to obtain 1.1 g of compound (8a).

[0538] Equation (8a)

[0539]

[0540] The average value of x8 is 26, and the average value of y8 is 22.

[0541] (Synthesis Example 8-10)

[0542] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 1.0 g of the aforementioned compound (8a), and an equal molar amount of the aforementioned compound (1b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain compound (VIII). Si-NMR confirmed that the Si atoms of compound (8a) formed bonds with the OH atoms of compound (1b). Furthermore, F-NMR confirmed the product.

[0543] Formula (VIII)

[0544]

[0545] Among them, the average value of x8 is 26, the average value of y8 is 22, the average value of z8 is 21, and the average value of w8 is 20.

[0546] [Example 9] Synthesis of compound IX

[0547] (Synthesis Example 9-1)

[0548] The following compound (9-1) was obtained by following the method described in Example 7 of International Publication No. 2013 / 121984.

[0549] CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x9 (CF2CF2O)-CF2CF2CF2-CH2OH… Equation (9-1)

[0550] The average value of x9 is 14.

[0551] (Synthesis Example 9-2)

[0552] Compound (9-1) (6.8 g, 1.5 mmol), 2,6-dimethylpyridine (0.76 g, 7.1 mmol), and AE-3000 (28.0 g) were added and stirred at 0 °C. Trifluoromethanesulfonic anhydride (0.99 g, 3.5 mol) was added, and the mixture was stirred at room temperature. After washing with water, the solvent was distilled off, and the mixture was subjected to flash chromatography using silica gel to obtain 6.8 g of compound (9-2).

[0553] CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x9 (CF2CF2O)-CF2CF2CF2-CH2OTf…Equation (9-2)

[0554] Wherein, OTf is trifluoromethanesulfonic acid group: -OS(=O)2(-CF3).

[0555] (Synthesis Example 9-3)

[0556] Diethyldiallyl malonate (60.0 g, 250 mmol), lithium chloride (23.7 g, 559 mmol), water (6.5 g, 360 mmol), and dimethyl sulfoxide (263 g) were added, and the mixture was stirred at 160 °C. After cooling to room temperature, water was added, and the mixture was extracted with ethyl acetate. Hexane was added to the organic layer, and the mixture was washed with saturated brine and dried with sodium sulfate. After filtration, the solvent was distilled off, yielding 39.5 g of the following compound (9-3).

[0557]

[0558] (Synthesis Example 9-4)

[0559] After adding THF (260 mL) and diisopropylamine (29.8 mL, 294 mmol), the solution was cooled to -78 °C. A solution of n-butyllithium hexane (2.76 M, 96.6 mL, 294 mmol) was added, and the temperature was raised to 0 °C. After stirring, the solution was cooled to -78 °C to prepare a THF solution of diisopropylaminolithium (LDA). Compound (9-3) (39.5 g, 235 mmol) was added to the THF solution, and after stirring, allyl bromide (24.1 mL, 278 mmol) was added. The temperature was raised to 0 °C, 1 M hydrochloric acid (100 mL) was added, and THF was removed by vacuum distillation. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was distilled off, and the solution was subjected to flash chromatography using silica gel to obtain 45.0 g of compound (9-4).

[0560]

[0561] (Synthesis Example 9-5)

[0562] The compound (9-4) (45.0 g, 216 mmol) was dissolved in THF (620 mL) and cooled to 0 °C. A THF solution of lithium aluminum hydride (104 mL, 260 mmol) was added and stirred. Water and a 15% sodium hydroxide aqueous solution were added, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and the mixture was subjected to flash chromatography using silica gel to obtain 31.3 g of the compound (9-5).

[0563]

[0564] (Synthesis Example 9-6)

[0565] Acetonitrile (380 mL), the aforementioned compound (9-5) (31.3 g, 188 mmol), triphenylphosphine (64.3 g, 245 mmol), and carbon tetrachloride (33.9 g, 221 mmol) were added, and the mixture was stirred at 90 °C. After concentration, ethyl acetate / hexane was added and the mixture was stirred. After filtration and concentration, the mixture was distilled (70 °C, 3 hPa) to give 28.2 g of the following compound (9-6).

[0566]

[0567] (Synthesis Example 9-7)

[0568] THF (35 mL) and iodine (0.180 g, 0.71 mmol) were added to magnesium (2.36 g, 97.2 mmol) and stirred at room temperature. A THF (35 mL) solution of the aforementioned compound (9-6) (14.0 g, 75.9 mmol) was added and the mixture was heated under reflux for 2 hours to prepare a solution (0.80 M) of the following compound (9-7).

[0569]

[0570] (Synthesis Example 9-8)

[0571] 1-Bromo-4-chlorobutane (2.9 g, 16.8 mmol), 1-phenyl-1-propyne (0.20 g, 1.7 mmol), and CuCl2 (0.05 g, 0.36 mmol) were added, and the mixture was stirred at 0 °C. Compound (9-7) (0.80 M, 24.0 mL, 19.3 mmol) was added and stirred. 1 M hydrochloric acid was added, and the mixture was extracted with dichloromethane, followed by the addition of sodium sulfate. After filtration and concentration, the mixture was distilled (120 °C, 3 hPa) to obtain 3.45 g of compound (9-8).

[0572]

[0573] (Synthesis Example 9-9)

[0574] THF (2.6 mL) and iodine (14.0 mg, 0.055 mmol) were added to magnesium (0.17 g, 6.9 mmol) and stirred at room temperature. A THF (2.6 mL) solution of the aforementioned compounds (9-8) (1.41 g, 5.9 mmol) was added and the mixture was heated under reflux for 2 hours to prepare a solution (0.74 M) of the following compounds (9-9).

[0575]

[0576] (Synthesis Example 9-10)

[0577] After adding CuCl2 (9.9 mg, 0.074 mmol), 1-phenyl-1-propyne (0.019 g, 0.16 mmol), 1,3-bis(trifluoromethyl)benzene (23 mL), and the aforementioned compound (9-2) (1.5 g, 0.32 mmol), compound (9-9) (4.5 mL, 1.0 M, 3.3 mmol) was added. The mixture was stirred at room temperature, washed with 1 M hydrochloric acid, and dried over sodium sulfate. After filtration, the solvent was distilled off, and AC-6000 was added. After washing with DMF and MeOH, the mixture was subjected to flash chromatography using silica gel to obtain 0.25 g of the following compound (9-10).

[0578] Equation (9-10)

[0579]

[0580] (Synthesis Example 9-11)

[0581] AC2000 (1.5 g), the above compounds (9-10) (0.25 g, 0.048 mmol), a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 2%, 8.9 mg), aniline (1.3 mg), and trimethoxysilane (26.9 mg, 0.221 mmol) were added. After stirring at 40 °C, the solvent was removed by vacuum distillation, thereby obtaining 0.25 g of the fluorinated ether compound (9a) shown below. The Mw / Mn ratio of compound (9a) determined by the aforementioned GPC method is 1.06.

[0582] Equation (9a)

[0583]

[0584] (Synthesis Example 9-12)

[0585] In a 100 mL PFA flask, 0.93 g of 20% KBr aqueous solution, 0.2 g of 2,2,6,6-tetramethylpiperidine-1-oxide (TEMPO), and 25 g of acetonitrile were added to 25 g of the following compounds (9-12) to obtain a mixture. The mixture was stirred, and a mixture of 18 g of 25% sodium hypochlorite aqueous solution and 2.5 g of sodium bicarbonate was slowly added. The mixture was heated at 40 °C for about 48 hours to obtain a reaction mixture. After cooling the reaction mixture, 30 g of 10% sulfuric acid aqueous solution and 30 g of AC-2000 were added to acidify the reaction mixture. The mixture was washed three times each with water and saturated brine to recover the organic phase. The organic phase was then mixed with 10.0 g of silica gel and filtered through a filter to recover the organic phase. The recovered organic phase was concentrated using a rotary evaporator to obtain the following compound (9b).

[0586] CF3-O-(CF2CF2OCF2CF2CF2CF2O) y9 Equation (9-12) is given by: CF2CF2OCF2CF2CF2-CH2OH

[0587] The average value of y9 is 13.

[0588] Equation (9b)

[0589]

[0590] (Synthesis Example 9-13)

[0591] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 1.0 g of the aforementioned compound (9a), and an equal molar amount of the aforementioned compound (9b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain the following compound (IX). Si-NMR confirmed that the Si atoms of compound (9a) form bonds with the OH atoms of compound (9b). Furthermore, F-NMR confirmed the product.

[0592] Formula (IX)

[0593]

[0594] Among them, the average value of x9 is 14 and the average value of y9 is 13.

[0595] [Example 10] Synthesis of compound X

[0596] (Synthesis Example 10-1)

[0597] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 2.0 g of the aforementioned compound (9a), and an equal molar amount of the aforementioned compound (1b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain the following compound (X). The product was confirmed by NMR.

[0598] Formula (X)

[0599]

[0600] The average value of x10 is 14, the average value of y10 is 21, and the average value of z10 is 20.

[0601] [Example 11] Synthesis of compound XI

[0602] (Synthesis Example 11-1)

[0603] According to Example 6 of International Publication No. 2013 / 121084, the following compound (XI) was obtained.

[0604] Formula (XI)

[0605]

[0606] The average value of x11 is 13.

[0607] [Example 12] Synthesis of compound XII

[0608] (Synthesis Example 12-1)

[0609] The following compound (12a) was obtained in Synthesis Example 1 and Synthesis Example 2 of International Publication No. 2019 / 151445.

[0610] Equation (12a)

[0611]

[0612] The average value of x12 is 22.

[0613] (Synthesis Example 12-2)

[0614] Under a nitrogen atmosphere, 10.0 g of HFE-7200, 1.0 g of the aforementioned compound (12a), and an equal molar amount of the aforementioned compound (1b) were added to a 50 mL flask. The mixture was heated and stirred at 60 °C to obtain compound (XII). Si-NMR confirmed that the Si atoms of compound (12a) form bonds with the OH atoms of compound (1b). Furthermore, F-NMR confirmed the presence of the product.

[0615] Formula (XII)

[0616]

[0617] Among them, the average value of x12 is 22, the average value of y12 is 21, and the average value of z12 is 20.

[0618] [Item creation and evaluation]

[0619] Using the compounds obtained in Examples 1 to 12, and a mixture XIII of the aforementioned compound (1a) and the aforementioned compound (1b), a surface treatment of the substrate was performed to obtain an article having a surface layer.

[0620] For each example, the surface treatment is performed using the dry coating method and the wet coating method described below, thereby forming a surface layer (hereafter referred to as process A).

[0621] Furthermore, under a state where sufficient load is applied to the article after process A in each example, preparation is carried out by wiping the surface layer with BEMCOT moistened with isopropyl alcohol (also known as process B).

[0622] Chemically strengthened glass was used as the substrate. The resulting articles were evaluated using the methods described below. The results are shown in Table 1.

[0623] (Dry coating method)

[0624] Dry coating was performed using a vacuum evaporation apparatus (ULVAC, VTR-350M) (vacuum evaporation method). 0.5 g of each compound or mixture obtained in Examples 1-13 was filled into a molybdenum boat within the vacuum evaporation apparatus, and the vacuum evaporation apparatus was evacuated to 1 × 10⁻⁶. -3 Below Pa. A boat containing the compound is heated at a rate of 10°C / min or less. When the evaporation rate, based on a crystal oscillating film thickness gauge, exceeds 1 nm / s, the baffle is opened to begin film deposition on the substrate surface. The baffle is closed when the film thickness reaches approximately 50 nm, ending film deposition on the substrate surface. The substrate with the deposited compound is then heated at 200°C for 30 minutes and cleaned with isopropanol, thereby obtaining an article with a surface layer on the substrate surface.

[0625] (Wet coating method)

[0626] The compounds or mixtures obtained in Examples 1-13 were mixed with C4F9OC2H5 (manufactured by 3M, Novec 7200, a registered trademark) as a liquid medium to prepare a coating solution with a solid content concentration of 0.05%. The substrate was immersed in the coating solution and left for 30 minutes, then the substrate was lifted (dipping method). The coating film was dried at 200°C for 30 minutes and cleaned with isopropanol, thereby obtaining an article having a surface layer on the substrate surface.

[0627] (Evaluation Method)

[0628] <Finger Sliding>

[0629] Using a load-varying tribological testing system (Shinto Science, HHS2000), the coefficient of dynamic friction of the surface layer relative to artificial skin (Idemitsu TECNOFINE, PBZ13001) was measured under the conditions of a contact area of ​​3 cm × 3 cm and a load of 0.98 N. A lower coefficient of dynamic friction indicates better finger slippage. The evaluation criteria are shown below.

[0630] ◎(Excellent): The coefficient of kinetic friction is less than 0.15.

[0631] ○(Good): The coefficient of kinetic friction is above 0.15 and less than 0.20.

[0632] △(Optional): The coefficient of kinetic friction is greater than 0.20 and less than 0.25.

[0633] × (Not allowed): The coefficient of kinetic friction is 0.25 or higher.

[0634] Fingerprint Removal

[0635] Artificial fingerprint liquid (a liquid containing oleic acid and squalene) was applied to the flat surface of a silicone rubber plug. Excess oil was wiped away with a non-woven fabric (BEMCOT M-3, manufactured by Asahi Kasei Corporation, registered trademark) to prepare the fingerprint impression. This fingerprint impression was placed on the surface layer and pressed for 10 seconds under a load of 9.8 N. The haze of the area with the fingerprint was measured using a haze meter as the initial value. The area with the fingerprint was then wiped using a reciprocating penetration tester (manufactured by KNT Corporation) equipped with a tissue paper, under a load of 4.9 N. The haze value was measured after each reciprocating wipe, and the number of wipes required for the haze to decrease to less than 10% from the initial value was determined. Fewer wipes indicate easier removal of fingerprint smudges and better fingerprint smudge removal properties. The evaluation criteria are as follows.

[0636] ◎(Excellent): Wipes less than 3 times.

[0637] ○(Good): Wipe 4 to 6 times.

[0638] △(Optional): Wipe 6 to 8 times.

[0639] × (Not allowed): Wipe more than 9 times.

[0640] [Table 1]

[0641] Table 1

[0642]

[0643] It has been clearly stated that compounds such as compounds I through X possess R... f1 -A 1 -Si(R 1The surface layer obtained by the compound with the )2- structure exhibits excellent finger slippage and fingerprint removal properties. A comparison with the results of Example 13, which was prepared by mixing compound (1a) and compound (1b) as raw materials of compound I, clearly demonstrates that the compound exhibits significantly superior finger slippage and fingerprint removal properties compared to the mixture of raw materials.

[0644] Industrial availability

[0645] Articles having a surface layer containing this compound are useful as a component used in the following articles: optical articles, touch panels, anti-reflective films, anti-reflective glass, SiO2-treated glass, tempered glass, sapphire glass, quartz substrates, mold metals, etc.

[0646] Products: Car navigation systems, mobile phones, digital cameras, digital camcorders, mobile information terminals (PDAs), portable audio players, car stereos, gaming devices, eyeglass lenses, lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), photocopiers, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprinted templates, molds, etc.

[0647] This application claims priority based on Japanese Special Application No. 2020-137440 filed on August 17, 2020, and all its disclosures are cited herein.

[0648] Explanation of reference numerals in the attached figures

[0649] 10: Substrate with a base layer; 12: Substrate; 14: Base layer;

[0650] 20: Item; 22: Surface layer

Claims

1. A fluorinated ether compound, represented by the following formula (1), {(R f1 -A 1 -) p1 Si(-R 1 )) 3-p1} q1 -Q 1 (-T) n1 (-R f2 )) r1 Formula (1) in, R f1 For a monovalent polyfluorinated polyether chain with optional substituents, there exist multiple R... f1 They can choose to be the same or different from each other. R f2 It is a monovalent polyfluorinated polyether chain, with multiple R... f2 They can choose to be the same or different from each other. R f1 Or R f2 The molecular weight is 1000~20000. A 1 Each is independently -O- or C(=O)-O-, and there are multiple A's. 1 Each can independently choose to be the same as or different from the others. R 1 It is an alkyl group, a hydrolyzable group, or a hydroxyl group having 1 to 6 carbon atoms, and multiple R groups exist. 1 The hydrolyzable groups may be the same or different from each other, and are alkoxy groups, halogen atoms, or isocyanate groups having 1 to 6 carbon atoms. Q 1 It is a linker group with a valence of q1+n1+r1. T is -Si (-R) 3-a (-L) a When there are two or more T's, the two or more T's can be chosen to be the same or different. R is an alkyl group having 1 to 6 carbon atoms. L is a hydrolyzable group or a hydroxyl group, and two or more Ls in each T may be the same or different. The hydrolyzable group is an alkoxy group, a halogen atom, or an isocyanate group with 1 to 6 carbon atoms. a is 2 or 3. q1 is an integer greater than or equal to 1. When q1 is 1, p1 is either 1 or 2. When q1 is 2 or higher, p1 is an integer from 0 to 3. At least one of the multiple p1 values ​​is 1 or 2, and the multiple p1 values ​​can be chosen to be the same or different from each other. n1 is an integer greater than or equal to 0, and r1 is an integer greater than or equal to 1. Wherein, the R f1 Expressed as follows (3A), L 1 -R f11a - (OR f12 ) m1 - (CH2) s1 - Formula (3A) L 1 For hydrogen atoms, fluorine atoms, hydroxyl groups, -C(O)OR 10 -C(O)N(R) 10 )2, R 10 Each of the R atoms is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (optionally containing fluorine atoms), or a phenyl group having fluorine atoms, and multiple R atoms exist. 10 At that time, there are multiple R 10 They can choose to be the same or different from each other. R f11a It is a fluoroalkylene group with 1 to 20 carbon atoms. R f12 It is a fluoroalkylene group having 1 to 6 carbon atoms. When m1 is an integer between 0 and 500, and m1 is greater than 2, there are multiple R... f12 Choose either the same or different. s1 is an integer between 0 and 20. Wherein, the R f2 It can be expressed by the following formula (3), R f11 -(OR f12 ) m1 - Formula (3) in, R f11 It is a fluoroalkyl group with 1 to 20 carbon atoms. R f12 It is a fluoroalkylene group having 1 to 6 carbon atoms. When m1 is an integer between 0 and 500, and m1 is greater than 2, there are multiple R... f12 Choose either the same or different. Wherein, Q 1 Each can be expressed independently by any one of the following equations (5-1) to (5-7). (-A 11 -Q 12 -)C(-R e2 ) 2-d3 (-Q 32 -) (-Q 22 -) d3 Formula (5-2) (-A 11 -Q 13 -)N(-Q 33 -) (-Q 23 -) Formula (5-3) (-A 11 -Q 14 -)Z(-Q 34 -)(-Q 24 -) d4 Formula (5-4) (-A 11 -Q 15 -)If(-R e3 ) 2-d5 (-Q 35 -)(-Q 25 -) d5 formula (5-5) -A 11 -Q 12 -CH(-Q 32 -)-If (R e3 ) 3-d6 (-Q 25 -) d6 formula (5-6) -A 11 -Q 12 -CH(-Q 22 -)-If (R e3 ) 2-d7 (-Q 35 -)(-Q 25 -) d7 formula (5-7) In equations (5-1) to (5-7), A 11 Side and R f2 Connection, Q 22 Q 23 Q 24 、 or Q 25 The side is connected to T, Q 32 Q 33 Q 34 Or Q 35 With the help of Si and R f1 connect, A 11 For single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2-, Q 11 For single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2-, alkylene; or alkylene groups having a -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups, Q 12 It is a single bond, an alkylene group; or an alkylene group having a -C(O)NR bond between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups, Q 13 It is a single bond, alkylene; in alkylene groups with 2 or more carbon atoms, there is a -C(O)NR bond between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 A group consisting of SO2-; or a group having a -C(O)- group at the N-terminus of the alkylene group, wherein Q 13 When it is a single bond, A 11 For -C(O)-, In Q 14 When the atom in the bonded Z is a carbon atom, Q 14 For Q 12 In Q 14 When the atom in the bonded Z is a nitrogen atom, Q 14 For Q 13 , Q 15 It is an alkylene group; or an alkylene group having a -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups, Q 22 and Q 32 Each is independently an alkylene group; in alkylene groups having two or more carbon atoms, there is a -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups; with -C(O)NR at the end of the alkylene group on the side not connected to Si. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 A group consisting of SO2-; or a -C(O)NR group between carbon atoms in an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- and has -C(O)NR at the end on the side not connected to Si. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 The SO2- group contains multiple Q groups. 22 At that time, there are multiple Qs. 22 Choose either the same or different. Q 23 and Q 33 Each is independently an alkylene group; or has a -C(O)NR between carbon atoms in an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 SO2- groups, In Q 24 Or Q 34 When the atom in the bonded Z is a carbon atom, Q 24 and Q 34 Each independently for Q 22 Or Q 32 In Q 24 Or Q 34 When the atom in the bonded Z is a nitrogen atom, Q 24 and Q 34 Each independently for Q 23 Or Q 33 There are multiple Qs 24 At that time, there are multiple Qs. 24 Choose either the same or different. Q 25 and Q 35 Each is independently an alkylene group; or has a -C(O)NR between carbon atoms in an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -、-O-、-SO2NR 6 -or-NR 6 The SO2- group contains multiple Q groups. 25 At that time, there are multiple Qs. 25 Choose either the same or different. Z is a group with a d4+2 valence ring structure, and the d4+2 valence ring structure has the same characteristics as Q. 14 Q 24 and Q 34 The carbon or nitrogen atoms are directly bonded, and the ring structure is selected from one of the following groups: aliphatic rings of 3-8 members, aromatic rings of 3-8 members, heterocyclic rings of 3-8 members, and fused rings formed by two of these rings. R e1 It is an alkyl group having 1 to 6 carbon atoms, and contains multiple R groups. 1 At that time, there are multiple R 1 Choose either the same or different. R e2 It is a hydrogen atom, a hydroxyl group, and an alkyl or acyloxy group having 1 to 6 carbon atoms, wherein the alkyl portion of the acyloxy group has 1 to 6 carbon atoms. R e3 Alkyl groups having 1 to 6 carbon atoms R 6 It is an alkyl or phenyl group with 1 to 6 carbon atoms and hydrogen atoms. d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, and d1+d2 is an integer from 1 to 6. d3 is 1 or 2. d4 is an integer from 1 to 5. d5 is 1 or 2. d6 is an integer from 1 to 3. d7 is 1 or 2. Among them, Q 11 Q 12 Q 13 Q 14 Q 15 Q 22 Q 23 Q 24 Q 25 Q 32 Q 33 Q 34 and Q 35 Alkylenes are straight-chain alkylenes with 1 to 10 carbon atoms, while alkylenes with 2 or more carbon atoms are straight-chain alkylenes with 2 to 10 carbon atoms.

2. A fluorinated ether composition comprising the fluorinated ether compound of claim 1 and other fluorinated ether compounds.

3. A coating liquid containing the fluorinated ether compound of claim 1 or the fluorinated ether composition of claim 2, and containing a liquid medium.

4. An article having a surface layer formed of a fluorinated ether compound of claim 1 or a fluorinated ether composition of claim 2 on the surface of a substrate.

5. A method for manufacturing an article, wherein, A surface layer is formed by using the fluorinated ether compound of claim 1, the fluorinated ether composition of claim 2, or the coating liquid of claim 3, by a dry coating method or a wet coating method.

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