JP2021181158A - Method for producing base material with film - Google Patents

Abstract

To provide a novel method for producing a base material with a film obtained by using a plurality of types of fluorine-containing ether compounds.SOLUTION: A method for producing a substrate 10 with a film comprises: a step of forming a first film 14 in a part of a region on a main surface of a substrate 12 using a first fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a hydrolyzable silyl group; and a step of forming a second film 16 in a region of a main surface of the base material 12 other than the region where the first film 14 is formed using a second fluorine-containing ether compound with the poly(oxyfluoroalkylene) chain and the hydrolyzable silyl group, wherein the first fluorine-containing ether compound and the second fluorine-containing ether compound are different.SELECTED DRAWING: Figure 2

Description

The present invention relates to a method for producing a substrate with a film.

Fluorine-containing compounds are preferably used as surface treatment agents because they exhibit high lubricity, water repellency, oil repellency and the like. When water and oil repellency is imparted to the surface of the base material by the surface treatment agent, it becomes easy to wipe off the dirt on the surface of the base material, and the dirt removal property is improved. Among the above-mentioned fluorine-containing compounds, the fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain in which an ether bond (-O-) is present in the middle of the fluoroalkylene chain is a compound having excellent flexibility, and particularly, oils and fats and the like. Excellent in removing dirt.
As the fluorine-containing ether compound, a compound having a poly (oxyperfluoroalkylene) chain and a hydrolyzable silyl group at the terminal is widely used (Patent Document 1).

International Publication No. 2014/069592

Patent Document 1 discloses a method of forming a film obtained by using one kind of fluorine-containing ether compound or a mixture of a plurality of kinds of fluorine-containing ether compounds on the entire main surface of a base material.
However, when a film is formed on the entire main surface of the base material using one type of fluorine-containing ether compound, the performance corresponding to the used fluorine-containing ether compound can be obtained, but the other required performance cannot be obtained. .. For example, when a film having both abrasion resistance and slip resistance is required, even if a film having excellent abrasion resistance is obtained based on the performance of the fluorine-containing ether compound used, the slip resistance performance is obtained. There is a problem such as not being able to meet.
Further, when a film is formed on the entire main surface of the base material using a mixture of two kinds of fluorine-containing ether compounds, the performance that should be obtained by one fluorine-containing ether compound is canceled by the other fluorine-containing ether compound. , There is a problem that the performance of each fluorine-containing ether compound cannot be fully exhibited.

In view of the above problems, it is an object of the present invention to provide a novel method for producing a substrate with a film obtained by using a plurality of types of fluorine-containing ether compounds.

As a result of diligent studies on the above problems, the present inventor has formed a first film using the first fluorine-containing ether compound in a part of the region of the main surface of the base material, and the group in which the first film is not formed is formed. We have found a novel production method for forming a second film using a second fluorine-containing ether compound in the region of the main surface of the material, and have reached the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.

[1] A step of forming a first film on a part of a region on the main surface of a substrate by using a first fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a hydrolyzable silyl group.
A part of the main surface of the base material using a second fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a hydrolyzable silyl group, which is a compound different from the first fluorine-containing ether compound. A method for producing a substrate with a film, which comprises a step of forming a second film in a region of the above, other than the region where the first film is formed.
[2] The number average molecular weight of the poly (oxyfluoroalkylene) chain of the first fluorine-containing ether compound and the number average molecular weight of the poly (oxyfluoroalkylene) chain of the second fluorine-containing ether compound. , Are different, the method for producing a substrate with a film according to [1].
[3] The number of the hydrolyzable silyl groups of the first fluorine-containing ether compound and the number of the hydrolyzable silyl groups of the second fluorine-containing ether compound are different, [1] or. The method for producing a substrate with a film according to [2].
[4] Of the first fluorine-containing ether compound and the second fluorine-containing ether compound, one of the fluorine-containing ether compounds is hydrolyzable only on one terminal side of the poly (oxyfluoroalkylene) chain. The method according to any one of [1] to [3], wherein the fluorinated ether compound having a silyl group and the other fluoroether compound has the hydrolyzable silyl group on both terminal sides of the poly (oxyfluoroalkylene) chain. A method for manufacturing a base material with a film.
[5] Both the first fluorine-containing ether compound and the second fluorine-containing ether compound have a linking group between the poly (oxyfluoroalkylene) chain and the hydrolyzable silyl group.
Of the linking group of the first fluorine-containing ether compound and the linking group of the second fluorine-containing ether compound, one linking group has a nitrogen atom or an amide group, and the other linking group is a Si atom or The method for producing a substrate with a film according to any one of [1] to [4], which has a group represented by the formula G1 described later.
[6] At least one unit of the poly (oxyfluoroalkylene) chain of the first fluorine-containing ether compound and at least one of the poly (oxyfluoroalkylene) chain of the second fluorine-containing ether compound. The method for producing a substrate with a film according to [1], wherein the unit is different from that of the unit.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel method for producing a substrate with a film obtained by using a plurality of types of fluorine-containing ether compounds.

It is a plane schematic diagram which shows an example of the substrate with a film obtained by the manufacturing method of the substrate with a film of this invention. It is a schematic perspective view which shows an example of the substrate with a film obtained by the manufacturing method of the substrate with a film of this invention. It is a plane schematic diagram which shows an example of the substrate with a film obtained by the manufacturing method of the substrate with a film of this invention. It is a plane schematic diagram which shows an example of the substrate with a film obtained by the manufacturing method of the substrate with a film of this invention. It is a plane schematic diagram which shows an example of the substrate with a film obtained by the manufacturing method of the substrate with a film of this invention. It is a plane schematic diagram which shows an example of the substrate with a film obtained by the manufacturing method of the substrate with a film of this invention.

In the present specification, the repeating unit represented by the formula 1 is referred to as a unit 1. Repeating units expressed by other formulas are also described in the same manner. The group represented by the formula 2 is referred to as a group 2. The groups expressed by other formulas are also described in the same manner. The compound represented by the formula 3 is referred to as compound 3. Compounds represented by other formulas are also described in the same manner.
In the present specification, "the alkylene group may have an A group" and "the alkylene group which may have an A group" have an A group between carbon atoms in the alkylene group. It means that it may have an A group at the end, such as an alkylene group-A group.

The meanings of the terms in the present invention are as follows.
The "divalent organopolysiloxane residue" is a group represented by the following formula. ^{R x} in the following formula is an alkyl group (preferably 1 to 10 carbon atoms) or a phenyl group. Further, g1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

The “sylphenylene skeleton group” is a group represented by −Si (R ^y ) ₂ PhSi (R ^y ) _2- (where Ph is a phenylene group and R ^y is a monovalent organic group). Is. As ^Ry , an alkyl group (preferably 1 to 10 carbon atoms) is preferable.
The "dialkylsilylene group" is a group represented by −Si (R ^z ) _2- (where R ^z is an alkyl group (preferably 1 to 10 carbon atoms)).
The "number average molecular weight" of a compound is calculated by obtaining the number (average value) of oxyfluoroalkylene groups with respect to the terminal groups by ¹ H-NMR and ^{19 F-NMR.}

The method for producing a substrate with a film of the present invention (hereinafter, also referred to as “the present production method”) uses a first fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a hydrolyzable silyl group. It has a step of forming a first film on a part of a region on the main surface of the base material, and a poly (oxyfluoroalkylene) chain and a hydrolyzable silyl group, which are compounds different from the first fluorine-containing ether compound. The present invention comprises a step of forming a second film in a part of the main surface of the base material other than the area where the first film is formed by using the second fluorine-containing ether compound.
In the following description, the primary surface of the substrate, which may be used in contact with other articles or human fingers, and / or may be held by human fingers during operation, the first membrane and The surface on which the second film is placed is called the "main surface".
Further, in the main surface of the base material, the region where the first film is arranged is also referred to as "first region", and the region where the second film is arranged is also referred to as "second region".
Further, the base material with a film obtained by this production method is also referred to as "base material with a main film".

〔Base material〕
The substrate may be another article (eg, stylus) or a substrate that may be used in contact with a person's fingers, a substrate that may be held by a person's fingers during operation, and / or other articles (eg, a stylus). , A base material that may be placed on a mounting table) and is not particularly limited as long as it is a base material that is required to be imparted with water and oil repellency. Specific examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and a composite material thereof. The glass may be chemically strengthened.
As the base material, a touch panel base material and a display base material are preferable, and a touch panel base material is particularly preferable. The base material for the touch panel preferably has translucency. "Having translucency" means that the vertically incident visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. As the material of the base material for the touch panel, glass or a transparent resin is preferable.
Further, as the base material, glass or a resin film used for an exterior portion (excluding a display portion) in a device such as a mobile phone (for example, a smartphone), a mobile information terminal, a game machine, or a remote controller is also preferable.

[1st and 2nd membranes]
The first film is a film formed by using a first fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a hydrolyzable silyl group, and is formed in the first region of the base material.
The second film is a film formed by using a second fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a hydrolyzable silyl group, and is formed in the second region of the base material.
The first film and the second film may be formed directly on the main surface of the base material, or may be formed on the base material via another film formed on the main surface of the base material. As a specific example of the above other film, a base film formed on the main surface of the base material by subjecting the base material with the compound described in paragraphs 809 to 0995 of International Publication No. 2011/016458, SiO _{2 or the like.} Can be mentioned.

(Fluorine-containing ether compound)
The first fluorine-containing ether compound used for forming the first film is a compound different from the second fluorine-containing ether compound used for forming the second film.
Hereinafter, preferred embodiments of the first fluorine-containing ether compound and the second fluorine-containing ether compound are shown. In the following description, the term "fluorine-containing ether compound" means both the first fluorine-containing ether compound and the second fluorine-containing ether.

The poly (oxyfluoroalkylene) chain contains a plurality of units represented by the formula 1.
(OX) Equation 1

X is a fluoroalkylene group having one or more fluorine atoms.
The number of carbon atoms of the fluoroalkylene group is preferably 2 to 6 and particularly preferably 2 to 3 from the viewpoint of more excellent weather resistance and corrosion resistance of the film.
The fluoroalkylene group may be linear or branched, but the linear group is preferable because the effect of the present invention is more excellent.
The fluoroalkylene group preferably has 1 or more fluorine atoms and is more excellent in corrosion resistance of the film, preferably 2 to 10 groups, and particularly preferably 2 to 4 groups.
The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group).

Specific examples of the unit _{1, -OCHF -, - OCF 2} CHF -, - OCHFCF 2 -, - OCF 2 CH 2 -, - OCH 2 CF 2 -, - OCF 2 CF 2 CHF -, - OCHFCF 2 CF 2 -, -OCF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- , -OCF _2- , -OCF ₂ CF _2- , -OCF ₂ CF ₂ CF _2- , -OCF (CF ₃ ) CF _2- , -OCF ₂ CF ₂ CF ₂ CF _2- , -OCF (CF ₃ ) CF ₂ CF ₂ -, -OCF ₂ CF ₂ CF ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- .

The number of repetitions m1 of the unit 1 contained in the poly (oxyfluoroalkylene) chain is 2 or more, an integer of 2 to 200 is more preferable, an integer of 5 to 150 is further preferable, and an integer of 5 to 100 is particularly preferable. An integer of 10 to 50 is most preferable.
The poly (oxyfluoroalkylene) chain may contain only one unit 1, or may contain two or more units 1. Examples of two or more units 1 include two or more units 1 having different carbon atoms, two or more units 1 having the same carbon number but different side chains and different types of side chains, and carbon atoms. Two or more kinds of units 1 having the same number but different numbers of fluorine atoms can be mentioned.
The binding order of two or more types of (OX) is not limited, and may be randomly, alternately, or arranged in blocks.

_{The (OX) m1} of the poly (oxyfluoroalkylene) chain is _{(OC 2} H _ma F _(4-ma) ) _m11 (OC ₃ H _mb F _(6-mb) ) _m12 (OC ₄ H _mc F _{(8). -Mc)} ) _m13 (OC ₅ H _md F _(10-md) ) _m14 (OC ₆ H _me F _(12-me) ) _m15 is preferable.
ma is an integer of 0 to 3, mb is an integer of 0 to 5, mc is an integer of 0 to 7, md is an integer of 0 to 9, and me is an integer of 0 to 11.
m11, m12, m13, m14 and m15 are each independently an integer of 0 or more, preferably 100 or less.
m11 + m12 + m13 + m14 + m15 are integers of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, further preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.
Among them, m11 is preferably an integer of 2 or more, and an integer of 2 to 200 is particularly preferable.
In addition, C ₃ H _mb F _(6-mb) , C ₄ H _mc F _(8-mc) , C ₅ H _md F _(10-md) and C ₆ H _me F _(12-me) are linear. However, it may be in the form of a branched chain, and a linear form is preferable from the viewpoint of having more excellent friction resistance of the film.

In addition, m11 (OC ₂ H _ma F _(4-ma) ), m12 (OC ₃ H _mb F _(6-mb) ), m13 (OC ₄ H _mc F _(8-mc) ), The binding order of m14 (OC ₅ H _md F _(10-md) ) and m15 (OC ₆ H _me F _(12-me) ) is not limited.
When m11 is 2 or more, a plurality of (OC ₂ H _ma F _(4-ma) ) may be the same or different.
When m12 is 2 or more, a plurality of (OC ₃ H _mb F _(6-mb) ) may be the same or different.
When m13 is 2 or more, a plurality of (OC ₄ H _mc F _(8-mc) ) may be the same or different.
When m14 is 2 or more, a plurality of (OC ₅ H _md F _(10-md) ) may be the same or different.
When m15 is 2 or more, a plurality of (OC ₆ H _me F _(12-me) ) may be the same or different.

The hydrolyzable silyl group is preferably a group represented by the formula 2.
-Si (R) _n L _3-n formula 2

The number of groups 2 of the fluorine-containing ether compound is 1 or more, and 2 or more is preferable, 2 to 10 is more preferable, and 2 to 5 is more preferable in that the friction resistance of the film is more excellent. Two or three are particularly preferred.
When there are a plurality of groups 2 in one molecule, the plurality of groups 2 may be the same or different. From the viewpoint of easy availability of raw materials and easy production of fluorine-containing ether compounds, they are preferably the same.

R is a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferable. The carbon number of R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

L is a hydrolyzable group or a hydroxyl group.
The hydrolyzable group of L is a group that becomes a hydroxyl group by the hydrolyzing reaction. That is, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH by the hydrolysis reaction. The silanol groups further react between the silanol groups to form a Si—O—Si bond. Further, the silanol group can form a chemical bond (base material-O-Si) by undergoing a dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material.

Specific examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
As L, an alkoxy group or a halogen atom having 1 to 4 carbon atoms is preferable because the fluorine-containing ether compound can be more easily produced. As L, an alkoxy group having 1 to 4 carbon atoms is preferable and a long-term storage stability of the fluorine-containing ether compound is required because there is little outgas during coating and the storage stability of the fluorine-containing ether compound is more excellent. The ethoxy group is particularly preferable, and the methoxy group is particularly preferable when the reaction time after coating is short.

n is an integer of 0 to 2.
n is preferably 0 or 1, and particularly preferably 0. The presence of a plurality of L makes the adhesion of the film to the substrate stronger.
When n is 1 or less, the plurality of Ls present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and easy production of fluorine-containing ether compounds, they are preferably the same. When n is 2, the plurality of Rs present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and easy production of fluorine-containing ether compounds, they are preferably the same.

As the fluorine-containing ether compound, the compound represented by the formula 3 is preferable because it is excellent in water and oil repellency and abrasion resistance of the film.
[A- (OX) _m1- ] _j Z [-Si (R) _n L _3-n ] _g formula 3

A is a perfluoroalkyl group or -Q [-Si (R) _n L _3-n ] _k .
The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint of more excellent friction resistance of the film.
The perfluoroalkyl group may be linear or branched.
However, when A is −Q [−Si (R) _n L _3-n ] _k , j is 1.

Examples of the perfluoroalkyl group include CF ₃ −, CF ₃ CF ₂ −, CF ₃ CF ₂ CF ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ −, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF (CF ₃ )-and the like can be mentioned.
_{As the perfluoroalkyl group, CF 3} −, CF ₃ CF ₂ −, and CF ₃ CF ₂ CF ₂ − are preferable because the water and oil repellency of the film is more excellent.

Q is a concatenated group of (k + 1) valence. As will be described later, k is an integer of 1 to 10. Therefore, as Q, a linking group having a valence of 2 to 11 can be mentioned.
The Q may be any group as long as it does not impair the effects of the present invention. For example, an alkylene group, a carbon atom, a nitrogen atom, or a silicon atom which may have an ethereal oxygen atom or a divalent organopolysiloxane residue. _{, 2-8 valent organopolysiloxane residues, and Si (R) n} L _3-n from formulas 3-1A, 3-1B, and 3-1A-1 to 3-1A-6 described below. The group can be mentioned.

The definitions of R, L, n, X and m1 are as described above.

Z is a (j + g) -valued linking group.
Z may be a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, which may have an ethereal oxygen atom or a divalent organopolysiloxane residue. _{Si (R) n} L _3-n was removed from 2-8 valent organopolysiloxane residues and formulas 3-1A, 3-1B and 3-1A-1 to 3-1A-6 described below. The group is mentioned.

j is an integer of 1 or more, and an integer of 1 to 5 is preferable from the viewpoint of more excellent water and oil repellency of the film, and 1 is particularly preferable from the viewpoint of easy production of compound 3.
g is an integer of 1 or more, and an integer of 2 to 4 is preferable, 2 or 3 is more preferable, and 3 is particularly preferable, because the friction resistance of the film is more excellent.

The compound 3 is preferably a compound represented by the formula 3-1 from the viewpoint that the water and oil repellency of the film is more excellent.
A- (OX) _m1- Z ³¹ formula 3-1
The definitions of A, X and m1 in Formula 3-1 are synonymous with the definitions of each group in Formula 3.

Z ³¹ is group 3-1A or group 3-1B.
-Q ^a- X ³¹ (-Q ^b- Si (R) _n L _3-n ) _h (-R ³¹ ) _i- type 3-1A
-Q ^c- [CH ₂ C (R ³² ) ( ^{-Q d} -Si (R) _n L _3-n )] _y- R ^{33 formula 3-1B}

Q ^a is a single bond or a divalent linking group.
The divalent linking group may be, for example, a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group. Divalent saturated hydrocarbon group. The hydrogen group may be linear, branched or cyclic, and examples thereof include an alkylene group. The carbon number is preferably 1 to 20, and the divalent aromatic hydrocarbon group has a carbon number of carbon. 5 to 20 is preferable, and examples thereof include a phenylene group. In addition, an alkenylene group having 2 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms may be used.) A divalent heterocyclic group. , -O-, -S-, -SO _2- , -N (R ^d )-, -C (O)-, -Si (R ^a ) _2-, and groups in which two or more of these are combined can be mentioned. .. Here, ^Ra is an alkyl group (preferably 1 to 10 carbon atoms) or a phenyl group. R ^d is a hydrogen atom or an alkyl group (preferably 1 to 10 carbon atoms).
Examples of the group in which two or more of these are combined include -OC (O)-, -C (O) N (R ^d )-, an alkylene group having an etheric oxygen atom, and -OC (O)-. Examples thereof include an alkylene group having an alkylene group-Si ( ^Ra ) ₂ -phenylene group-Si ( ^Ra ) ₂ .

X ³¹ is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom or a 2-8 valent organopolysiloxane residue.
The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.
The carbon number of the alkylene group represented by X ³¹ is preferably 1 to 20, and particularly preferably 1 to 10.
Examples of the 2-8-valent organopolysiloxane residue include a divalent organopolysiloxane residue and a (w + 1) -valent organopolysiloxane residue described later.

Q ^b is a single bond or a divalent linking group.
Definition of the divalent linking group are the same as those defined as described in the above-described Q ^a.

R ³¹ is a hydroxyl group or an alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.

When X ³¹ is a single bond or an alkylene group, h is 1 and i is 0.
When X ³¹ is a nitrogen atom, h is an integer of 1 to 2, i is an integer of 0 to 1, and h + i = 2 is satisfied.
When X ³¹ is a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, and h + i = 3 is satisfied.
When X ³¹ is a 2-8 valent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h + i = 1 to 7 is satisfied.
If _{^{(-Q b -Si (R) n}} L 3-n) is two or more, two or more _{^{(-Q b -Si (R) n}} L 3-n) are be the same or different May be. If R ³¹ is two or more, two or more ^{(-R 31)} may be be the same or different.

Q ^c is a single bond or an alkylene group which may have an ethereal oxygen atom, and a single bond is preferable from the viewpoint of easy production of a compound.
The number of carbon atoms of the alkylene group which may have an ethereal oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.

R ³² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is preferable because it is easy to produce a compound.
As the alkyl group, a methyl group is preferable.

Q ^d is a single bond or an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. From the viewpoint of easy production of a compound, Q ^d is preferably a single bond or −CH ₂ −.

R ³³ is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable because it is easy to produce a compound.

y is an integer of 1 to 10, and an integer of 1 to 6 is preferable.
Two or more [CH ₂ C (R ³² ) (−Q ^d − Si (R) _n L _3-n )] may be the same or different.

As the group 3-1A, the groups 3-1A-1 to 3-1A-6 are preferable.
-(X ³² ) _s1- Q ^b1 _{-SiR n} L _3-n formula 3-1A-1
-(X ³³ ) _s2- Q ^a2- N [-Q ^b2 -Si (R) _n3 L _3-n ] ₂ formula 3-1A-2
-Q ^a3 -G (R ^g ) [ ^{-Q b3} -Si (R) _n L _3-n ] ₂ formulas 3-1A-3
-[C (O) N (R ^d )] _s4 −Q ^a4- (O) _t4 −C [− (O) _u4 −Q ^b4 −Si (R) _n L _3-n ] ₃ equations 3-1A-4
-Q ^a5 -Si [-Q ^b5 -Si (R) _n L _3-n ] ₃ formulas 3-1A-5
-[C (O) N (R ^d )] _v −Q ^a6 −Z ^a [−Q ^b6 −Si (R) _n L _3-n ] _w Equation 3-1A-6
The definitions of R, L, and n in the formulas 3-1A-1 to 3-1A-6 are as described above.

X ³² is -O- or -C (O) N (R ^d )-(where N in the equation binds to ^{Q b1).}
The definition of R ^d is as described above.
s1 is 0 or 1.

Q ^b1 is an alkylene group. The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.
When the alkylene group has -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is preferable to have these groups between carbon atoms.

The carbon number of the alkylene group represented by Q ^b1 is preferably 1 to 10, and particularly preferably 2 to 6.

As for Q ^b1 , when s1 is 0, −CH ₂ OCH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ − is preferable. (X ³² ) When _s1 is −O−, −CH ₂ CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable. (X ³² ) When _s1 is −C (O) N (R ^d ) −, an alkylene group having 2 to 6 carbon atoms is preferable (however, N in the formula is bonded to ^{Q b1).} When Q ^b1 is these groups, the compound is easy to produce.

Specific examples of the group 3-1A-1 include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

X ³³ is −O−, −NH−, or −C (O) N ( ^Rd ) −.
The definition of R ^d is as described above.

Q ^a2 is a single bond, an alkylene group, -C (O)-, or an ethereal oxygen atom between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms, -C (O)-, and -C (O). ) A group having O-, -OC (O)-or -NH-.
Q ^a2 The alkylene group represented by 1 to 10 is preferred, 1 to 6 is particularly preferred.
^Ethereal oxygen atom, -C (O)-, -C (O) O-, -OC (O)-or -NH, between carbon atom and carbon atom of alkylene group having 2 or more carbon atoms represented by Qa2. The number of carbon atoms of the group having − is preferably 2 to 10, and particularly preferably 2 to 6.

The Q ^a2, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 -, - CH 2 NHCH 2 CH 2 -, -CH ₂ CH ₂ OC (O) CH ₂ CH _2- , -C (O)-is preferable (however, the right side is bound to N).

s2 is 0 or 1 (provided that ^{it is 0 when Q a2} is a single bond). 0 is preferable from the viewpoint that the compound can be easily produced.

Q ^b2 is an alkylene group or a group having a divalent organopolysiloxane residue, an ethereal oxygen atom or -NH- between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ^b2 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of a group having a divalent organopolysiloxane residue, an ethereal oxygen atom or -NH- between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms represented by ^{Q b2 is 2 to 10} Is preferable, and 2 to 6 are particularly preferable.

As Q ^b2 _{, −CH 2} CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound (however, the right side binds to Si).

The two [-Q ^b2- Si (R) _n L _3-n ] may be the same or different.

Specific examples of the group 3-1A-2 include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

Q ^a3 is a single bond or an alkylene group which may have an ethereal oxygen atom, and a single bond is preferable from the viewpoint of easy production of a compound.
The number of carbon atoms of the alkylene group which may have an ethereal oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.

G is a carbon atom or a silicon atom.
R ^g is a hydroxyl group or an alkyl group. The number of carbon atoms of the alkyl group represented by ^{R g is preferably 1 to 4.}
As G (R ^g ), C (OH) or Si (R ^ga ) (where R ^ga is an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, preferably methyl, from the viewpoint of easy production of a compound. The group is particularly preferable.) Is preferable.

Q ^b3 is an alkylene group or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ^b3 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom or a divalent organopolysiloxane residue between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by ^{Q b3 is preferably 2 to 10 and 2 to 10.} 6 is particularly preferable.
As Q ^b3 _{, −CH 2} CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound.

The two [−Q ^b3 −Si (R) _n L _3-n ] may be the same or different.

Specific examples of the group 3-1A-3 include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

^{The definition of R d} in Equation 3-1A-4 is as described above.
s4 is 0 or 1.
^Qa4 is an alkylene group which may have a single bond or an ethereal oxygen atom.
The number of carbon atoms of the alkylene group which may have an ethereal oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.
t4 is 0 or 1 (provided that ^{it is 0 when Q a4} is a single bond).
As for −Q ^a4 − (O) _t4 −, when s4 is 0, single bond, −CH ₂ O− _{, −CH 2} OCH ₂ −, −CH ₂ OCH ₂ CH ₂ O−, −CH ₂ OCH ₂ CH ₂ OCH ₂ −, −CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ − is preferable (however, the left side is ^{bonded to (R f} O) _m ), and s4 is 1. In the case of, single bond, −CH ₂ − _{, −CH 2} CH ₂ − is preferable.

Q ^b4 is an alkylene group, and the alkylene group is −O−, −C (O) N (R ^d ) − ( ^{the definition of R d} is as described above), a silphenylene skeleton group, and a divalent group. May have an organopolysiloxane residue or a dialkylsilylene group.
When the alkylene group has an —O— or sylphenylene skeletal group, it is preferable to have an —O— or sylphenylene skeletal group between carbon atoms. Further, when the alkylene group has a −C (O) N (R ^d ) −, a dialkylsilylene group or a divalent organopolysiloxane residue, the carbon atom-carbon atom or the terminal on the side to be bonded to _{(O) u4.} It is preferable to have these groups.
The carbon number of the alkylene group represented by Q ^b4 is preferably 1 to 10, and particularly preferably 2 to 6.

u4 is 0 or 1.
- _(O) u4 ^{-Q b4} - as it is from the viewpoint of easily producing the _{compound, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 CH 2 -, - CH 2 OCH ₂ CH ₂ CH ₂ CH ₂ CH _2- , -OCH ₂ CH ₂ CH _2- , -OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH _2- , -OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ PhSi (CH ₃ ) ₂ CH ₂ CH ₂ − are preferable (however, the right side is bonded to Si).

The three [-(O) _u4- Q ^b4- Si (R) _n L _3-n ] may be the same or different.

Specific examples of the group 3-1A-4 include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

^Qa5 is an alkylene group which may have an ethereal oxygen atom.
The number of carbon atoms of the alkylene group which may have an ethereal oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.
The Q ^a5, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH _2- is preferable (however, the right side is bonded to Si).

Q ^b5 is an alkylene group or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ^b5 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom or a divalent organopolysiloxane residue between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by ^{Q b5 is preferably 2 to 10 and 2 to 10.} 6 is particularly preferable.
As Q ^b5 _{, −CH 2} CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound (however, the right side is Si (R) _n L _3-n). Combine with.).

The three [-Q ^b5- Si (R) _n L _3-n ] may be the same or different.

Specific examples of the group 3-1A-5 include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

^{The definition of R d} in Equation 3-1A-6 is as described above.
v is 0 or 1.

^Qa6 is an alkylene group which may have an ethereal oxygen atom.
The number of carbon atoms of the alkylene group which may have an ethereal oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.
The Q ^a6, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH ₂ - is preferred (but the right side is attached to ^{Z a.).}

Z ^a is a (w + 1) -valent organopolysiloxane residue.
w is an integer of 2 to 7.
Examples of the (w + 1) -valent organopolysiloxane residue include the following groups. ^{However, Ra} in the following equation is as described above.

Q ^b6 is an alkylene group or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ^b6 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom or a divalent organopolysiloxane residue between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by ^{Q b6 is preferably 2 to 10 and 2 to 10.} 6 is particularly preferable.
As Q ^b6 _{, −CH 2} CH ₂ − and −CH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound.

The w [-Q ^b6- Si (R) _n3 L _3-n ] may be the same or different.

The compound 3 is preferably a compound represented by the formula 3-2 because the water and oil repellency of the film is more excellent.
[A- (OX) _m1- Q ^a- ] _j32 Z ³² [-Q ^b- Si (R) _n L _3-n ] _h32 formula 3-2
The definitions of A, X, m1, Q ^a , Q ^b , R, and L in Formula 3-2 are synonymous with the definitions of each group in Formula 3-1 and Formula 3-1A.

Z ³² is a (j32 + h32) -valent hydrocarbon group or a (j32 + h32) -valent hydrocarbon group having one or more ethereal oxygen atoms between the carbon atoms of the hydrocarbon group and having 2 or more carbon atoms.
As Z ³² , a residue obtained by removing the hydroxyl group from the polyhydric alcohol having a primary hydroxyl group is preferable.
As Z ³² , a group represented by the formulas Z-1 to Z-5 is preferable from the viewpoint of easy availability of raw materials. However, R ³⁴ is an alkyl group, preferably a methyl group or an ethyl group.

j32 is an integer of 2 or more, and an integer of 2 to 5 is preferable because the water and oil repellency of the film is more excellent.
h32 is an integer of 1 or more, and an integer of 2 to 4 is preferable, and 2 or 3 is more preferable, because the friction resistance of the film is more excellent.

Specific examples of the fluorine-containing ether compound include those described in the following documents.
Perfluoropolyether-modified aminosilane described in JP-A No. 11-029585,
Silicon-containing organic fluoropolymer described in Japanese Patent No. 2874715,
Organosilicon compounds described in JP-A-2000-144097,
Perfluoropolyether-modified aminosilane described in JP-A-2000-327772,
Fluorinated siloxane described in JP-A-2002-506887,
The organic silicone compound described in JP-A-2008-534696,
Fluorinated modified hydrogen-containing polymer according to Japanese Patent No. 4138936,
Compounds described in U.S. Patent Application Publication No. 2010/0129672,
Organosilicon compounds according to International Publication No. 2011/060047,
The organosilicon compound according to International Publication No. 2011/059430,
Fluorine-containing organosilane compound according to International Publication No. 2012/064694,
The fluorooxyalkylene group-containing polymer described in JP2012-72272,
Fluorine-containing ether compound according to International Publication No. 2013/042732,
Fluorine-containing ether compound according to International Publication No. 2013/121984,
Fluorine-containing ether compound according to International Publication No. 2013/121985,
Fluorine-containing ether compound according to International Publication No. 2013/121986,
Compounds according to International Publication No. 2014/126064,
Fluorine-containing ether compound according to International Publication No. 2014/163004,
Compounds described in JP-A-2014-070163,
Fluorine-containing ether compound described in JP-A-2014-080473,
Perfluoro (poly) ether-containing silane compound described in JP-A-2014-218639,
Fluorine-containing ether compound according to International Publication No. 2015/08792,
Fluoropolyether group-containing polymer-modified silanes described in JP-A-2015-199906. Fluoropolyether group-containing polymer-modified silanes described in JP-A-2016-204656.
Fluoropolyether group-containing polymer-modified silane described in JP-A-2016-210854,
Fluoropolyether group-containing polymer-modified silane described in JP-A-2016-222859,
Fluorine-containing ether compound according to International Publication No. 2017/038830,
Fluorine-containing ether compound according to International Publication No. 2017/038832,
Fluorine-containing ether compound according to International Publication No. 2017/187775,
Fluorine-containing ether compound according to Japanese Patent Application No. 2017-104731,
Fluorine-containing ether compound according to Japanese Patent Application No. 2017-159696,
Fluorine-containing ether compound according to Japanese Patent Application No. 2017-159697,
Fluorine-containing ether compound according to Japanese Patent Application No. 2017-159698,
Fluorine-containing ether compound according to Japanese Patent Application No. 2017-167973,
Fluorine-containing ether compound according to Japanese Patent Application No. 2017-167999,
The fluorine-containing ether compound according to Japanese Patent Application No. 2017-2516111.

Commercially available products of fluorine-containing ether compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by Asahi Glass Co., Ltd., and Daikin Industries Co., Ltd. Examples thereof include Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, and Optool (registered trademark) UD509.

<Preferable mode of combination of fluorine-containing ether compound>
A preferred embodiment of the combination of the first fluorine-containing ether compound and the second fluorine-containing ether compound will be described. In this production method, two or more of the following preferred embodiments may be satisfied.

The first preferred embodiment is the number average molecular weight of the poly (oxyfluoroalkylene) chain (hereinafter, also referred to as “first poly (oxyfluoroalkylene) chain”) contained in the first fluorine-containing ether compound, and the second. It is an embodiment different from the number average molecular weight of the poly (oxyfluoroalkylene) chain (hereinafter, also referred to as “second poly (oxyfluoroalkylene) chain”) contained in the fluorine-containing ether compound. The details of the poly (oxyfluoroalkylene) chain are as described above.
Here, as the number average molecular weight of the poly (oxyfluoroalkylene) chain increases, the slip resistance of the film formed by using the fluorine-containing ether compound decreases, but the friction resistance tends to improve. On the other hand, as the number average molecular weight of the poly (oxyfluoroalkylene) chain becomes smaller, the friction resistance of the film formed by using the fluorine-containing ether compound decreases, but the slip resistance tends to improve.
To solve this problem, when a film is formed using a fluorine-containing ether compound having a different number average molecular weight of poly (oxyfluoroalkylene) chains for each region (first preferred embodiment), the excellent properties of each fluorine-containing ether compound. A film having both slip resistance and abrasion resistance can be obtained without canceling the performance.
The absolute value of the difference in the number average molecular weight between the first poly (oxyfluoroalkylene) chain and the second poly (oxyfluoroalkylene) chain is that both slip resistance and abrasion resistance can be compatible at a higher level. , 1,000 to 10,000, more preferably 2,000 to 8,000, and particularly preferably 3,000 to 8,000.
Of the first poly (oxyfluoroalkylene) chain and the second poly (oxyfluoroalkylene) chain, the number average molecular weight of one of the poly (oxyfluoroalkylene) chains is 2, because it has better abrasion resistance. 500 to 10,000 is preferable, 3,000 to 8,000 is more preferable, and the number average molecular weight of the other poly (oxyfluoroalkylene) chain is 100 or more and less than 2,500 from the viewpoint of better slip resistance. Preferably, 300 to 1,500 is more preferable.

The second preferred embodiment is that the number of hydrolyzable silyl groups (hereinafter, also referred to as "first hydrolyzable silyl group") contained in the first fluorine-containing ether compound and the second fluorine-containing ether compound are present. The mode is different from the number of hydrolyzable silyl groups having (hereinafter, also referred to as “second hydrolyzable silyl group”).
Details of the hydrolyzable silyl group are as described above. The number of hydrolyzable silyl groups means the number of hydrolyzable silyl groups in one molecule.
Here, as the number of hydrolyzable silyl groups increases, the friction resistance of the film formed by using the fluorine-containing ether compound tends to improve, but the fingerprint stain removing property tends to decrease. On the other hand, as the number of hydrolyzable silyl groups decreases, the antifouling property and fingerprint stain removing property of the film formed by using the fluorine-containing ether compound tend to improve, but the friction resistance tends to decrease.
To solve this problem, when a film is formed using a fluorine-containing ether compound having a different number of hydrolyzable silyl groups for each region (second preferred embodiment), the excellent performance of each fluorine-containing ether compound is negated. A film having excellent abrasion resistance, antifouling property, and fingerprint stain removing property can be obtained.
The absolute value of the difference between the number of the first hydrolyzable silyl groups and the number of the second hydrolyzable silyl groups stands side by side with higher levels of abrasion resistance, antifouling property and fingerprint stain removing property. From the viewpoint that a film can be easily obtained, 1 or more is preferable, and 2 or more is more preferable.
Of the first hydrolyzable silyl group and the second hydrolyzable silyl group, the number of hydrolyzable silyl groups is preferably 2 or more, preferably 2 to 10 from the viewpoint of better abrasion resistance. Is more preferable, 2 to 5 is more preferable, 2 or 3 is particularly preferable, and the number of the other hydrolyzable silyl groups is 1 to 2 from the viewpoint of being more excellent in antifouling property and fingerprint stain removing property. Preferably, one is more preferred.

In the third preferred embodiment, of the first fluorine-containing ether compound and the second fluorine-containing ether compound, one of the fluorine-containing ether compounds is hydrolyzable only on one terminal side of the poly (oxyfluoroalkylene) chain. It is an embodiment having a silyl group and the other fluorine-containing ether compound having a hydrolyzable silyl group on both terminal sides of the poly (oxyfluoroalkylene) chain.
Details of the hydrolyzable silyl group are as described above. Further, "having a hydrolyzable silyl group only on one terminal side" means that when the fluorine-containing ether compound is the above-mentioned compound 3 (compound represented by the formula 3), A in the formula 3 is a perfluoroalkyl group. Is the embodiment of. Further, "having a hydrolyzable silyl group on both terminal sides" means that when the fluorine-containing ether compound is the above-mentioned compound 3 (compound represented by the formula 3), A in the formula 3 is −Q [−. Si (R) _n L _3-n ] This is an embodiment of _k.
Here, when a fluorine-containing ether compound having a hydrolyzable silyl group on only one terminal side is used, the fingerprint stain removing property and the abrasion resistance of the obtained film tend to be improved, but the slip resistance tends to be lowered. be. On the other hand, when a fluorine-containing ether compound having a hydrolyzable silyl group on both terminal sides is used, the slip resistance of the obtained film tends to be improved.
To solve this problem, when a film is formed by using a fluorine-containing ether compound having a hydrolyzable silyl group on one end side or both end sides for each region (third preferred embodiment), each fluorine-containing ether compound A film having excellent fingerprint stain removing property, abrasion resistance and slip resistance can be obtained without canceling out the excellent performance.

In the fourth preferred embodiment, both the first fluorine-containing ether compound and the second fluorine-containing ether compound have a linking group between the poly (oxyfluoroalkylene) chain and the hydrolyzable silyl group. Of the linking group of the fluorine-containing ether compound of 1 and the linking group of the second fluorine-containing ether compound, one linking group has a nitrogen atom or an amide group, and the other linking group is represented by a Si atom or the following formula G1. It is an embodiment having a group to be.

In the formula G1, * represents a bond position with a poly (oxyfluoroalkylene) chain or a bond position with a hydrolyzable silyl group. However, at least one of the three * is the bond position with the poly (oxyfluoroalkylene) chain, and at least one is the bond position with the hydrolyzable silyl group.

In a fourth preferred embodiment, the details of the poly (oxyfluoroalkylene) chain and the hydrolyzable silyl group are as described above.
Specific examples of the linking group having a nitrogen atom include ^{the case where X 31} in the group 3-1A is a nitrogen atom. Among them, the group 3-1A is the group 3-1A from the viewpoint of better friction resistance. In the case of -2, (X ³³ ) _s2- Q ^a2- N is preferable.
Specific examples of the linking group having an amide group include the case ^{where Q a} in the group 3-1A is −C (O) N (R ^d ) −, and among these, the friction resistance is more excellent. _{^{[C (O) N (R}} d)] s4 -Q a4 when group 3-1A is a group _{3-1A-4 - (O) t4} -C or a group 3-1A groups 3-1A- When it is 5, [C (O) N (R ^d )] _v −Q ^a6 −Z ^a is preferable.
Specific examples of the linking group having a Si atom include the case ^{where Q a} in the group 3-1A is −Si (R ^a ) ₂ −, and the X ³¹ in the group 3-1A is a silicon atom and a 2-8 valent organone. Examples thereof include a polysiloxane residue, a sylphenylene skeleton group, or an alkylene group having a divalent organopolysiloxane residue or a dialkylsilylene group. Among these, the group 3-1A is more excellent in light resistance. ^{Q a5} -Si when is a group 3-1A-5 is preferable.
Since the linking group having the group G1 is more excellent in light resistance, G (R ^g ) is C in ^{the portion of Q a3-} G (R ^{g) when the group 3-1A is of the formula 3-1A-3.} It is preferably (OH).

Here, when a fluorine-containing ether compound having a nitrogen atom or an amide group as a linking group is used, the friction resistance of the obtained film tends to be improved. Further, when a fluorine-containing ether compound having a Si atom or a group G1 as a linking group is used, the light resistance of the obtained film tends to be improved.
In this case, if a film is formed using a fluorine-containing ether compound having a specific linking group for each region (fourth preferred embodiment), the excellent performance of each fluorine-containing ether compound is not negated, and the friction resistance is not negated. A film having both light resistance and light resistance can be obtained.

A fifth preferred embodiment comprises at least a portion of the unit of the first poly (oxyfluoroalkylene) chain of the first fluorinated ether compound and the second poly (oxyfluoro) of the second fluorinated ether compound. An aspect different from that of at least a portion of the alkylene) chain. The details of the poly (oxyfluoroalkylene) chain are as described above.
Specific examples of the fifth preferred embodiment include a mode in which the poly (oxyfluoroalkylene) chain has a different carbon number, a mode in which the presence or absence of a side chain and a type of side chain are different even if the carbon number is the same, and a mode in which the carbon number is the same. However, there is an embodiment in which the number of fluorine atoms is different. Among these, an embodiment having a different number of carbon atoms in the poly (oxyfluoroalkylene) chain is preferable from the viewpoint of being more excellent in abrasion resistance and lubricity. Here, as a specific example of the embodiment in which the poly (oxyfluoroalkylene) chains have different carbon atoms, one of the poly (oxyfluoroalkylene) chains is represented by (OCF ₂ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ ). Examples thereof include an embodiment having a unit and the other poly (oxyfluoroalkylene) chain _{having a unit represented by (OCF 2} OCF ₂ CF _2).

Here, when a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain having a large number of carbon atoms is used, compared with a case where a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain having a small number of carbon atoms is used. The obtained film has excellent friction resistance, but tends to have poor lubricity.
On the other hand, when a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain having a small number of carbon atoms is used, compared with a case where a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain having a large number of carbon atoms is used. The obtained film has excellent lubricity, but tends to have poor abrasion resistance.
To solve this problem, when a film is formed using poly (oxyfluoroalkylene) chains having different carbon atoms for each region (an example of the fifth preferred embodiment), the excellent performance of each fluorine-containing ether compound is negated. A film having both abrasion resistance and lubricity can be obtained without this.

(Forms of 1st and 2nd membranes)
The form (shape) of the first film and the second film is not particularly limited, but shapes such as figures, letters and symbols can be mentioned, and from the viewpoint of being more superior to the effect of the present invention, any one of the following forms or a combination thereof can be used. preferable. Hereinafter, suitable forms of the first film and the second film will be described with reference to the drawings.
Here, in the following example, since the shape of the second film corresponds to the shape excluding the first film, the shape of the first film will be mainly described.

FIG. 1 is a schematic plan view showing an example of a substrate with a film of the present invention. As shown in FIG. 1, the film-attached base material 10 includes a base material 12, a first film 14 arranged in a plurality of dotted first regions 12a on the main surface of the base material 12, and a main base material 12. It has a second film 16 arranged in a second region 12b other than the first film 14 arranged on the surface.
Here, the main surface of the base material 12 means the surface of one of the plurality of surfaces constituting the base material 12. Specifically, as shown in FIG. 2 (schematic perspective view of the base material 10 with a film), when the base material 12 has a plate shape, two surfaces perpendicular to the thickness direction t of the base material 12 (Surface 12X, surface 12Y; in other words, two main surfaces), which means one surface (in the example of FIG. 2, surface 12X, in other words, one main surface). The case of the main surface of the base material in FIGS. 3 to 6 below is synonymous with the meaning of the main surface of the base material in FIG.
In the examples of FIGS. 1 to 6, the case where the first film and the second film are formed only on the main surface of the base material 12 is shown, but the present invention is not limited to this. For example, the first film and the second film may be formed on a surface other than the main surface of the base material 12 (hereinafter, also referred to as “another surface”). In this way, when the first film and the second film are formed on two or more surfaces of the base material 12, the arrangement patterns of the first film and the second film on each surface may be the same or different. good. Further, the film formed on the other surface may be a film formed by using the same fluorine-containing ether compound in both the first region and the second region.

The shape of the first film 14 is circular, but is not limited to, for example, an elliptical shape, an oval shape, a shape in which oval shapes intersect, a strip-shaped broken line (for example, herringbone), a fan shape, or an annular shape. , Semi-circular, semi-circular with rounded corners, polygon (eg triangle, square, pentagon, hexagon, cross, star), or the above polygon with rounded corners It may have a rounded corner or the like. Among these, a circular shape, an elliptical shape, or a quadrangular shape is preferable from the viewpoint of manufacturing efficiency of the first film 14.
The shapes of the plurality of first films 14 may be the same or different from each other, but are preferably the same as shown in FIG.
The size of the first film 14 is preferably 1 to 50 cm, more preferably 1 to 30000 μm, further preferably 1 to 10000 μm, and particularly preferably 20 to 1000 μm from the viewpoint of further excellent effects of the present invention. Here, the size of the first film 14 means the diameter of the first film 14 when it is circular, and when it is not circular, it means the equivalent circle diameter calculated from the area of the first film 14. do.
The sizes of the plurality of first films 14 may be the same or different from each other, but are preferably the same as shown in FIG.
The first film 14 is arranged in a square grid at equal intervals, but is not limited to this, and is arranged in a grid other than the square grid (for example, a hexagonal grid, a rectangular grid, or an orthorhombic grid). It may be arranged or it may be arranged randomly. The distance between the adjacent first films 14 is preferably 1 to 50 cm, more preferably 1 to 30000 μm, further preferably 1 to 10000 μm, and particularly preferably 20 to 1000 μm, because the effect of the present invention is more excellent.

FIG. 3 is a schematic plan view showing an example of the substrate with a film of the present invention, specifically, an embodiment in which the first film is arranged in a plurality of punctate first regions on the main surface of the substrate. It is a figure which shows the modification. The film-attached substrate 20 of FIG. 3 is different from the shapes of the first region and the second region of the film-attached substrate 10 of FIG. 1 except that the shapes of the first region and the second region of the film-attached substrate 20 of FIG. 3 are different. The configuration of the base material 10 with a film of FIG. 1 is substantially the same as that of the substrate 10 with a film.
As shown in FIG. 3, the first film 24 is arranged in the first region 22a arranged in a checkered flag shape (checkerboard pattern) on the main surface of the base material 22. Specifically, on the main surface of the base material 20 with a film, the first film 24 arranged in the first region 22a and the second film 26 arranged on the second region 22b are alternately arranged. There is.

FIG. 4 is a schematic plan view showing an example of the substrate with a film of the present invention. As shown in FIG. 4, the film-attached base material 30 includes a base material 32, a first film 34 arranged in a band-shaped first region 32a on the main surface of the base material 32, and a first film on the main surface of the base material 32. It has a second film 36 arranged in two regions 32b.

The shape of the first film 34 is a band-shaped straight line, but is not limited to this, and may be a band-shaped curve (for example, a wavy line) or a band-shaped polygonal line (for example, herringbone). The shapes of the plurality of first films 34 may be the same or different from each other, but are preferably the same as shown in FIG.
The width of the first film 34 is preferably 1-10000 μm (10 cm), more preferably 20 to 20000 μm (2 cm), from the viewpoint that the effect of the present invention is more excellent. The widths of the plurality of first films 34 may be the same or different from each other, but are preferably the same as shown in FIG.
The first film 34 is arranged at equal intervals, but the arrangement is not limited to this, and the arrangement intervals of the first film 34 may be different. The arrangement spacing of the first film 34 is preferably 1 to 3000 μm, more preferably 20 to 1000 μm, because the effect of the present invention is more excellent.

FIG. 5 is a schematic plan view showing an example of the substrate with a film of the present invention. The base material 42 has a peripheral region 42b (second region 42b) and a central region 42a (first region 42a) surrounded by the peripheral region 42b on its main surface. As shown in FIG. 5, the film-attached base material 40 has a base material 42, a first film 44 arranged in the central region 42a, and a second film 46 arranged in the peripheral region 42b.

The shape of the first film 44 is a polygon (more specifically, a polygon), but the shape is not limited to this, and for example, a circular shape, an elliptical shape, a fan shape, a semicircular ring shape, or a semicircular ring shape with rounded corners. , Oval, crossed oval, polygon (eg triangle, pentagon, hexagon, cross, star, etc.), or the above polygon has rounded corners. You may. Among these, a quadrangle is preferable because the effect of the present invention is more excellent.
The area of the first film 44 can be appropriately set according to the area of the main surface of the base material, but the area ratio between the area of the first film 44 and the area of the second film 46 will be described later. It is preferable to set it.

FIG. 6 is a schematic plan view showing an example of the substrate with a film of the present invention. The base material 52 has a plurality of point-like dispersion regions 52b (second region 52b) and continuous regions 52a (first region 52a) other than the dispersion region 52b on its main surface. As shown in FIG. 6, the film-attached base material 50 has a base material 52, a first film 54 arranged in the continuous region 52a, and a second film 56 arranged in the dispersion region 52b.
It can be said that the dispersed region 52b corresponds to the dispersed phase (island portion) in the sea island structure, and the continuous region 52a corresponds to the continuous phase (sea portion) in the sea island structure.

The shape of the dispersion region 52b is a cross (more specifically, the "X" shape of the alphabet), but is not limited to this, for example, a circle, an ellipse, a fan, a semicircular ring, or a semicircular ring-shaped corner. Rounded shapes, oval shapes, intersecting oval shapes or polygons (eg triangles, squares, pentagons, stars, etc.), or the above polygons with rounded corners. There may be. Among these, a quadrangle is preferable because the effect of the present invention is more excellent.
The shapes of the plurality of dispersion regions 52b may be the same or different from each other, but are preferably the same as shown in FIG.
The size of the dispersion region 52b is preferably 1 to 3000 μm, more preferably 20 to 1000 μm, because the effect of the present invention is more excellent. Here, the size of the dispersion region 52b means the diameter of the dispersion region 52b when the shape is circular, and means the equivalent circle diameter calculated from the area of the dispersion region 52b when the shape of the dispersion region 52b is not circular. ..
The sizes of the plurality of dispersion regions 52b may be the same or different from each other, but are preferably the same as shown in FIG.
The dispersion regions 52b are arranged at equal intervals, but the present invention is not limited to this, and the dispersion regions 52b may be randomly arranged. The distance between the adjacent dispersion regions 52b is preferably 1-10000 μm (10 cm), more preferably 20 to 20000 μm (2 cm), because the effect of the present invention is more excellent.

In FIGS. 1 to 6, the area ratio between the first film and the second film (area of the first film / area of the second film) is 0.01 to 50.0 in that the effect of the present invention is more excellent. Is preferable, 0.1 to 45.0 is more preferable, and 0.5 to 40.0 is particularly preferable.

In FIGS. 1 to 6, when the substrate is composed of a material containing silicon atoms (preferably glass), the coverage of the first film on the main surface of the substrate with a film is more effective in the present invention. In terms of exertion, 10 to 97% is preferable, 30 to 95% is more preferable, and 40 to 93% is particularly preferable.
In calculating the coverage, the main surface of the substrate with a film means the surface of the surface on which the first film is formed (for example, the surface 12X in FIG. 2).
Here, the coverage of the first film, the time-of-flight secondary ion mass spectrometry (TOF-SIMS), F ₂ of the main surface of the film-coated substrate ^- Retrieves the mapping image, which is image analysis Can be calculated by The value calculated in this way is used as the coverage of the first film.
It is preferable that the second film has a continuous constant area in a group in that the effect of the present invention is more excellent. The continuous area of the second film ^{is preferably 0.001 mm 2} or more and 1 cm ² or less, and ^{more preferably 0.01 mm 2} or more and 0.1 cm ² or less.

The film thickness of the first film and the film thickness of the second film are preferably 1 to 100 nm, and particularly preferably 1 to 50 nm, respectively. For the film thickness of the first film and the second film, an X-ray diffractometer for thin film analysis (ATX-G: product name, manufactured by RIGAKU) was used to obtain an interference pattern of reflected X-rays by the X-ray reflectivity method. , Can be calculated from the vibration cycle of this interference pattern.

[Manufacturing method of substrate with film]
In this production method, a step of forming a first film on the first region of the main surface of the base material using the first fluorine-containing ether compound and a step of forming the first film on the main surface of the base material using the second fluorine-containing ether compound are used. It has a step of forming a second film in the second region. In the present production method, the first film may be formed first or the second film may be formed first, but it is preferable to form the first film which occupies a large area first.

(Formation of the first film)
The first film is dry-coated and wet using a composition containing a first fluorine-containing ether compound or a first fluorine-containing ether compound and a liquid medium (hereinafter, also referred to as “first composition”). It can be formed under any manufacturing conditions of the coating.

Specific examples of the liquid medium contained in the first composition include water and an organic solvent. Specific examples of the organic solvent include a fluorinated organic solvent and a non-fluorinated organic solvent.
The organic solvent may be used alone or in combination of two or more.

Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, for example, C ₆ F ₁₃ H (AC-2000: product name, manufactured by Asahi Glass Co., Ltd.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name). , Asahi Glass Co., Ltd.), C ₂ F ₅ CHFCHFCF ₃ (Bertrel: product name, manufactured by DuPont).
Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, for example, CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by Asahi Glass Co., Ltd.), C ₄ F ₉ OCH ₃ (Novec-7100:). Product name, 3M company), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: Product name, 3M company), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (Novec-7300: Product name, 3M).
Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.

As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and specifically, a hydrocarbon-based organic solvent and a ketone-based organic solvent are used. , Ether-based organic solvent, ester-based organic solvent, alcohol-based organic solvent and the like.
Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.
Specific examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Specific examples of the ether-based organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.
Specific examples of the ester-based organic solvent include ethyl acetate and butyl acetate.
Specific examples of the alcohol-based organic solvent include isopropyl alcohol.

The content of the fluorine-containing ether compound in the first composition is preferably 0.01 to 50.00% by mass, preferably 1.0 to 30.00% by mass, based on the total mass of the first composition. Especially preferable.
The content of the liquid medium in the first composition is preferably 50.00 to 99.99% by mass, particularly preferably 70.00 to 99.00% by mass, based on the total mass of the first composition. ..

The first film can be produced, for example, by the following method.
A method of treating the main surface of a base material by a dry coating method using a first fluorine-containing ether compound or a first composition to form a first film in a first region of the main surface of the base material.
A method in which a first composition is applied to the main surface of a base material by a wet coating method and dried to form a first film in a first region of the main surface of the base material.

Specific examples of the dry coating method include a vacuum vapor deposition method, a CVD method, and a sputtering method. Among these, the vacuum vapor deposition method is preferable from the viewpoint of suppressing the decomposition of the first fluorine-containing ether compound and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a metal porous body such as iron or steel with a first fluorine-containing ether compound or a first composition may be used.
When the dry coating method is used, as a method of forming the first film in the first region of the main surface of the base material, a mask having a shape corresponding to the first film is placed on the main surface of the base material, and then the dry coating method is used. It is better to treat the main surface of the base material.
Specific examples of the mask include tapes processed into arbitrary shapes, resins and metals, metal meshes having openings, and punching sheets having holes.
The wire diameter of the metal mesh is preferably 10 to 5000 μm, and particularly preferably 10 to 1000 μm, in that the coverage of the first film can be easily set in the above range.
The opening of the metal mesh is preferably 1 to 5000 μm, particularly preferably 10 to 3000 μm, in that the coverage of the first film can be easily set in the above range.
The spacing between the holes of the punching sheet is preferably 10 to 5000 μm, and particularly preferably 10 to 1000 μm in that the coverage of the first film can be easily set in the above range.
The opening of the punching sheet is preferably 1 to 5000 μm, particularly preferably 10 to 3000 μm, in that the coverage of the first film can be easily set in the above range.

Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir brojet. The method, the gravure coat method can be mentioned.
When the wet coating method is used, as a method of forming the first film on the first region of the main surface of the base material, after placing a mask on the main surface of the base material, the first composition is based on the wet coating method. A method of applying to the main surface of the material can be mentioned.
Among the wet coating methods, if the inkjet method is used, the first film can be formed only in the first region of the main surface of the base material without using a mask.

The first film formed by the above procedure contains a compound obtained through a hydrolysis reaction and a condensation reaction of the first fluorine-containing ether compound.

(Formation of the second film)
The second film is dry-coated and wet using a composition containing a second fluorine-containing ether compound or a second fluorine-containing ether compound and a liquid medium (hereinafter, also referred to as “second composition”). It can be formed under any manufacturing conditions of the coating.
Specific examples of the liquid medium contained in the second composition are the same as specific examples of the liquid medium contained in the first composition.

The second film can be produced, for example, by the following method.
A method of treating the main surface of a base material by a dry coating method using a second fluorine-containing ether compound or a second composition to form a second film in a second region of the main surface of the base material.
A method in which a second composition is applied to the main surface of a base material by a wet coating method and dried to form a second film in a second region of the main surface of the base material.

Specific examples of the dry coating method and the wet coating method in the production of the second film are the same as the specific examples given in the production of the first film. When the second film is produced by vacuum deposition, a pellet-like substance obtained by impregnating a metal porous body such as iron or steel with a second fluorine-containing ether compound or a second composition may be used.
When the dry coating method is used, as a method of forming the second film on the second region of the main surface of the base material, the second fluorine-containing ether compound is contained in the entire main surface of the base material after the formation of the first film. After forming the film, the main surface of the base material is wiped with a cloth or the like impregnated with a liquid medium (preferably the above-mentioned fluorine-based organic solvent), and the second fluorine-containing ether compound formed on the first film is formed. A method of removing only the film containing the above is mentioned. The film containing the second fluorine-containing ether compound formed on the first film is already on the portion where the base material and the first film are sufficiently bonded, and the second fluorine-containing ether is present. It is presumed that the film containing the compound has a weak bond with the first film, and the film containing the second fluorine-containing ether compound formed on the first film is easily removed. On the other hand, in the second region, since the second fluorine-containing ether compound is bonded to the base material because there is no first film, the film containing the second fluorine-containing ether compound is difficult to remove.

When the wet coating method is used, after the formation of the first film, the second composition is applied to the entire main surface of the base material, and the main surface of the base material is wiped with a cloth or the like containing a liquid medium. Examples thereof include a method of removing only the film obtained by using the second fluorine-containing ether compound formed on the first film. Among the wet coating methods, if the inkjet method is used, the second film can be formed only in the second region of the main surface of the base material without using a mask.

The second film formed by the above procedure contains a compound obtained through a hydrolysis reaction and a condensation reaction of the second fluorine-containing ether compound.

Here, when the second fluoroether compound is applied to the entire main surface of the base material after the formation of the first film to remove a part of the film obtained by using the second fluoroether compound. As the first fluorine-containing ether compound, a fluorine-containing ether compound having a hydrolyzable silyl group only on one terminal side of the poly (oxyfluoroalkylene) chain is used, and as the second fluorine-containing ether compound, poly (oxyfluoro) is used. It is preferable to use a fluorine-containing ether compound having a hydrolyzable silyl group on both terminal sides of the alkylene) chain (an example of the above third preferred embodiment). This facilitates the removal of the film obtained by using the second fluorine-containing ether compound.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. The blending amount of each component indicates the mass standard. Of Examples 11 to 29, Examples 11 to 16 are Examples, and Examples 17 to 29 are Comparative Examples.

〔Evaluation method〕

(Coverage)
The main surface of the substrate with a film (the first film is placed) by a device (TOF.SIMS5: product name, manufactured by ION-TOF) based on the time-of-flight secondary ion mass spectrometry (TOF-SIMS). It was analyzed surface), using an analysis software _{(surface Lab 6.7), F 2} - a mapping image by binning (binning) in 64 pixels were ROI (Region of Interest) analysis. With the minimum value (Min) of the threshold value (Min) being 40% and the maximum value (Max) being 100%, the presence or absence of coating was determined for each binned region, and it was determined that the total number of binned regions was covered. The percentage of the number of regions was calculated. This ratio (%) was taken as the coverage of the first film.
The measurement conditions by TOF-SIMS are as follows.
Measurement mode: High Current Bunched Mode
Primary ion species: Bi ₅ ⁺⁺
Acceleration voltage of primary ion: 25kV
Current value of primary ion: 0.05pA @ 10kHz
Cycle time: 100 μs
Mapping mode: 2D Large Area Mode
Raster: sawtooth, 1 shots / pixel
Number of Scans: 1
Frames per Patch: 8
Field of Analysis: 5 x 5 mm ²
Pixel Density: 256 pixels / mm
Maximum Patch Side Length: 0.25mm
Detector Extractor without surface potential adjustment (Use Surface Potential): 2000V
Energy of detector without surface potential adjustment (Use Surface Potential): 2000V
Use of electron gun: Yes

(Anti-fouling property)
The contact angle (water contact angle) of about 2 μL of distilled water placed on the main surface (formation surface of the first film and the second film) of the substrate with a film is used as a contact angle measuring device (DM-500: product name, Kyowa). It was measured using (manufactured by Surface Science Co., Ltd.). Measurements were made at five different points on the main surface, and the average value was calculated. The 2θ method was used to calculate the contact angle.
◎ (excellent): The contact angle is 105 degrees or more.
◯ (Good): The contact angle is 100 degrees or more and less than 105 degrees.
Δ (possible): The contact angle is 80 degrees or more and less than 100 degrees.
X (defective): The contact angle is less than 80 degrees.

(Slip resistance)
A fully automatic contact angle meter (DMo-701; product name, manufactured by Kyowa Surface Chemical Co., Ltd.) in which the main surface was held horizontally was prepared. A group with a film so that the formation surface (main surface) of the first and second films is in contact with the surface (horizontal plane) of a polyethylene sheet (hard polyethylene sheet (high density polyethylene): product name, manufactured by Hagitech Co., Ltd.). After placing the material, gradually tilt it using a fully automatic contact angle meter, and the angle (sliding angle) between the main surface of the membrane-coated substrate and the horizontal plane when the membrane-coated substrate begins to slide down. Was measured. The judgment criteria are shown below. The contact area between the substrate with a film and the polyethylene sheet was 6 cm × 6 cm, and the measurement was performed under the condition that a load of 0.98 N was applied to the substrate with a film.
◎ (Good): The sliding angle is 5 degrees or more.
○ (possible): The sliding angle is 2 degrees or more and less than 5 degrees.
× (defective): The sliding angle is less than 2 degrees.

(Fingerprint stain removal property)
Wipe off the fingerprints on the main surface of the base material with a film (the surface on which the first and second films are formed) with a cellulose non-woven fabric (Bencot M-3: product name, manufactured by Asahi Kasei Corporation), and visually check the ease of removal. Judged by. The judgment criteria are shown below.
◎ (Good): Fingerprints can be completely wiped off.
○ (Yes): Fingerprints are left behind.
× (Defective): Fingerprints can not be wiped off due to widespread wiping marks.

(Light resistance)
A desktop xenon arc lamp type accelerated light resistance tester (SUNTEST XLS + manufactured by Toyo Seiki Co., Ltd.) was used on the main surface of the substrate with a film (the forming surface of the first film and the second film), and the black panel temperature was: After irradiating with a light beam (650 W / m ² , 300 to 700 nm) at 63 ° C. for 1,000 hours, the water contact angle was measured according to the above method. The closer the rate of change in the water contact angle before and after the accelerated light resistance test (= 100 x (water contact angle after the test) / (water contact angle before the test)) is to 100%, the smaller the deterioration in performance due to light, and the better the light resistance. Excellent. The evaluation criteria are as follows.
◎ (excellent): The rate of change is 90% or more and 100% or less.
○ (Good): The rate of change is 70% or more and less than 90%.
× (impossible): The rate of change is less than 70%.

(Abrasion resistance)
The evaluation test for fingerprint stain removal was carried out on the evaluation sample after the abrasion resistance test, and the fingerprint stain removal property was evaluated according to the same evaluation criteria. The better the fingerprint removal property after the friction resistance test, the smaller the deterioration of the performance due to friction, and the better the friction resistance.
<Abrasion resistance test>
For the main surface of the substrate with a film (formation surface of the first film and the second film), a reciprocating traverse tester (manufactured by KNT) was used in accordance with JIS L0849: 2013 (ISO 105-X12: 2001). A cellulose non-woven fabric (Bencot M-3: product name, manufactured by Asahi Kasei Co., Ltd.) was reciprocated 10,000 times at a load of 1 kg, a friction length of 4 cm, and a speed of 30 rpm.

(Lubricability)
The dynamic friction coefficient of the main surface (formation surface of the first film and the second film) of the base material with a film for artificial skin (PBZ13001: trade name, manufactured by Idemitsu Technofine Co., Ltd.) is determined by the load-variable friction and wear test system (HHS2000: product). The measurement was performed under the conditions of contact area: 3 cm × 3 cm and load: 0.98 N using the name (manufactured by Shinto Kagaku Co., Ltd.). The smaller the coefficient of dynamic friction, the better the lubricity. The evaluation criteria are as follows.
◎ (excellent): The coefficient of dynamic friction is 0.2 or less.
○ (Good): The coefficient of dynamic friction is more than 0.2 and 0.4 or less.
Δ (possible): The coefficient of dynamic friction is more than 0.4 and 0.5 or less.
× (impossible): The coefficient of dynamic friction is more than 0.5.

[Example 1: Synthesis example]
Compound 3A was obtained according to the method described in Example 2 of WO2009 / 008380.
Compound 3A: CF ₃ (OCF ₂ CF ₂ ) _nA OCF ₂ C (= O) NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃
Average value of repeating unit nA: 7.3, number average molecular weight of compound 3A: 1,100

[Example 2: Synthesis example]
Compound 3B was obtained by using the compound D3-1 obtained by the method of Example 1-1 of International Publication No. 2009/008380 and referring to the method described in Example 11 of International Publication No. 2017/038830.
Compound 3B: CF ₃ (OCF ₂ CF ₂ ) _nB OCF ₂ C (= O) NHCH _2- C [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₃
Average value of repeating unit nB: 7.3, number average molecular weight of compound 3B: 1,450

[Example 3: Synthesis example]
Compound 3C was obtained according to the method described in Example 1 of International Publication No. 2017/038832.
Compound _{3C: CF 3 CF 2 CF 2} -OCF 2 CF 2 -OCF 2 CF 2 - {(OCF 2) nC1 (OCF 2 CF 2) nC2} -OCF 2 -CH 2 -N [CH 2 CH 2 CH 2 - Si (OCH ₃ ) ₃ ] ₂
Average value of repeating unit nC1: 21, average value of repeating unit nC2: 20, number average molecular weight of compound 3C: 4,530

[Example 4: Synthesis example]
Compound 3D was obtained according to the method described in Example 7 of International Publication No. 2017/038832.
Compound _{3D: [(CH 3 O)} 3 Si-CH 2 CH 2 CH 2] 2 N-CH 2 -CF 2 - {(OCF 2) nD1 (OCF 2 CF 2) nD2} -OCF 2 -CH 2 -N [CH ₂ CH ₂ CH _2- Si (OCH ₃ ) ₃ ] ₂
The average value of the repeating unit nD1: 21, the average value of the repeating unit nD2: 20, the number average molecular weight of the compound 3D: 4,540.

[Example 5: Synthesis example]
Compound 3E was obtained according to the method described in Example 11 of International Publication No. 2015/08792.
Compound _{3E: CF 3 CF 2 CF 2} -OCHFCF 2 -OCH 2 CF 2 {(OCF 2) nE1 (OCF 2 CF 2) nE2} -OCF 2 CH 2 -OCH 2 CH 2 CH 2 -Si (OCH 3) 3
Average value of repeating unit nE1: 21, average value of repeating unit nE2: 21, number average molecular weight of compound 3E: 4,300

[Example 6: Synthesis example]
Compound 3F was obtained with reference to the method for producing compound (ii-2) described in International Publication No. 2014/126064.
Compound _{3F: CF 3 CF 2 -OCF 2} CF 2 - (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) nF -OCF 2 CF 2 CF 2 -C (O) NH-CH 2 CH 2 CH 2 -Si (OCH ₃ ) ₃
The average value of the number of repeating units nF: 13, the number average molecular weight of the compound 3F: 4,920.

[Example 7: Synthesis example]
Compound 3G was obtained with reference to the production method of Synthesis Example 15 described in Japanese Patent No. 5676305.
Compound 3G: CF ₃ (OCF ₂ CF ₂ ) ₁₅ (OCF ₂ ) ₁₆ OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si [CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] ₃
Number average molecular weight of compound 3G: 3,510.

[Example 8: Synthesis example]
Compound 3H was obtained according to the method described in Example 11 of International Publication No. 2017/038830.
Compound 3H: CF _3- (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _nH (OCF ₂ CF ₂ ) -OCF ₂ CF ₂ CF _2- C (O) NH-CH _2- C [CH ₂ CH _2] CH _2- Si (OCH ₃ ) ₃ ] ₃
The average value of the number of repeating units nH: 13, the number average molecular weight of the compound 3H: 5,400.

[Example 9: Synthesis example]
Compound 3I was obtained according to the method described in Example 1 of JP-A-2015-199906.
Compound _{3I: CF 3 - (OCF 2} ) nI1 (OC 2 F 4) nI2 -OCF 2 -C (OH) [CH 2 CH 2 CH 2 -Si (OCH 3) 3] 2
Total of number of repeating units nI1 and number of repeating units nI2: about 43, number of repeating units nI1 and ratio to number of repeating units nI2 (nI1 / nI2): 47/53, number average molecular weight of compound 3I: 4350

[Example 10: Synthesis example]
Compound 3J was obtained with reference to the method described in Example 2 of International Publication No. 2009/0083380.
Compound _{3J: CF 3 - (OCF 2} CF 2) nJ -OCF 2 -C (= O) NHCH 2 CH 2 Si (OCH 3) 3
Average value of repeating unit nJ: 23.7, number average molecular weight of compound 3J: 3,100

[Example 11]
Compound 3A and hydrofluoroether (Novec HFE7200: product name, manufactured by 3M) were mixed to obtain a first composition for forming a first film having a concentration of compound 3A of 20% by mass.
Using the first composition, the surface of the base material is treated by the following vacuum vapor deposition method to form a part of the main surface of the chemically strengthened glass (Dragontrail glass; product name, manufactured by Asahi Glass Co., Ltd.) which is the base material. The first film was formed. The first film was formed after a mask (copper foil punching sheet, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) having the openings and hole spacings shown in Table 1 was attached to the main surface of the base material. ..
Specifically, a silicon dioxide film (thickness 7 nm) is formed on the main surface of the base material under a pressure of 3.0 × 10 ^{-3 Pa for vacuum vapor deposition, followed by one chemically strengthened glass (55 mm).} 2 mg of the composition (ie, 0.4 mg of compound 3A) was deposited per x 100 mm). Next, the substrate with a vapor-deposited film was allowed to stand for 24 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 65%, and then washed with AK-225 (product name, manufactured by Asahi Glass Co., Ltd.) to cover the main surface of the substrate. The first film was formed in a part (first region).
Next, compound 3B and hydrofluoroether (Novec HFE7200: product name, manufactured by 3M) are mixed to obtain a second composition for forming a second film having a concentration of compound 3B of 20% by mass. rice field.
Using the second composition, a film obtained by using the second composition was formed on the entire main surface of the base material on which the first film was formed by a vacuum vapor deposition method. Then, the main surface of the substrate is wiped with a cloth containing hydrofluoroether (Novec HFE7200: product name, manufactured by 3M) to remove the film obtained by using the second composition on the first film. Then, an evaluation sample (base material with a film) in which the first film and the second film were formed on the main surface of the base material was obtained. The vacuum vapor deposition treatment conditions using the second composition are the same as the vacuum vapor deposition treatment conditions using the first composition, except that a mask is not used.
After the formation of the first film and before vacuum deposition using the second composition, the main surface (formation surface of the first film) was _{confirmed from the image analysis results of the F 2} ^- stage scan mapping image. Table 1 shows. It was confirmed that the first film having the described shape was formed. The shape of the first film is shown in Table 1.
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

[Examples 12 to 16]
The same as in Example 11 except that the types of the fluorine-containing ether compounds contained in the first composition and the second composition were changed to the combinations shown in Table 1 and the types of masks were changed as shown in Table 1. An evaluation sample (base material with a film) was obtained.
Specifically, in Examples 12 and 13, a metal mesh (manufactured by Misumi Co., Ltd.) having an opening and a wire diameter shown in Table 1 was used as a mask. In Examples 14 to 16, a copper foil punching sheet (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) having openings and hole spacings shown in Table 1 was used as a mask.
For example 12 to 16, after the formation of the first layer, before vacuum evaporation using the second composition, a major surface (formation surface of the first layer) F ₂ ^- seen from the image analysis results of the stage scan mapping image As a result, it was confirmed that the first film of each shape shown in Table 1 was formed. The shape of the first film is shown in Table 1.
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

[Example 17]
Except that the types of the fluorine-containing ether compound and the mask contained in the first composition were changed as described in Table 1 and the formation of the second film using the second composition was not carried out, as in Example 11. I did the same. In this way, the evaluation sample (base material with a film) in which the first film is formed only in the first region of the main surface of the base material and the film containing the fluorine-containing ether compound is not formed in the second region is prepared. Obtained.
For Example 17, the main surface (formation surface of the first layer) F ₂ ^- was confirmed from the image analysis results of the stage scan mapping image, confirmed to have been formed first film shape as described in Table 1 rice field. The shape of the first film is shown in Table 1.
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

[Examples 18 to 27]
Except that the type of the fluorine-containing ether compound contained in the first composition was changed as described in Table 1, no mask was used, and the formation of the second film using the second composition was not performed. , The same as in Example 11. In this way, an evaluation sample (base material with a film) in which a film obtained by using one kind of fluorine-containing ether compound was formed on the entire main surface (first region and second region) of the base material was obtained. ..
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

[Example 28]
A first film in which compound 3A, compound 3J, and hydrofluoroether (Novec HFE7200: product name, manufactured by 3M) are mixed and the concentration of compound 3A is 10% by mass and the concentration of compound 3J is 10% by mass. A first composition for formation was obtained.
Further, the compound 3A, the compound 3J, and the hydrofluoroether (Novec HFE7200: product name, manufactured by 3M) are mixed, and the concentration of the compound 3A is 10% by mass and the concentration of the compound 3J is 10% by mass. A second composition for forming two films (the same composition as the first composition) was obtained.
An evaluation sample (base material with a film) was obtained in the same manner as in Example 11 except that the first composition and the second composition thus prepared were used.
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

[Example 29]
An evaluation sample (base material with a film) was obtained in the same manner as in Example 28, except that the types of the fluorine-containing ether compounds contained in the first composition and the second composition were changed as shown in Table 1.
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

The compound 3A used for forming the first film and the compound 3B used for forming the second film used in Example 11 have different numbers of hydrolyzable silyl groups. Specifically, compound 3A has one hydrolyzable silyl group, and compound 3B has three hydrolyzable silyl groups.
According to the film-coated substrate of Example 11, the antifouling property, fingerprint stain removing property and the antifouling property and the fingerprint stain removing property are compared with the example 20 in which all the regions are formed by the compound 3A and the example 21 in which all the regions are formed by the compound 3B. It was found that the friction resistance can be arranged side by side.

The compound 3J used for forming the first film and the compound 3A used for forming the second film used in Example 12 have different number average molecular weights of poly (oxyfluoroalkylene) chains. Specifically, the number average molecular weight of the poly (oxyfluoroalkylene) chain of compound 3J is 2,900, and the number average molecular weight of the poly (oxyfluoroalkylene) chain of compound 3A is 1,000.
According to the substrate with a film of Example 12, both slip resistance and abrasion resistance are compatible with those of Example 27 in which all regions are formed of compound 3J and Example 20 in which all regions are formed of compound 3A. I found that I could do it.
Further, according to the substrate with a film of Example 12, it was found that the slip resistance was improved as compared with Example 28 in which all the regions were formed by the mixture of Compound 3J and Compound 3A.

In the compound 3C used for forming the first film and the compound 3D used for forming the second film used in Example 13, the hydrolyzable silyl group was bonded only to one end side of the poly (oxyfluoroalkylene) chain. Or they differ from each other in that hydrolyzable silyl groups are attached to both ends of the poly (oxyfluoroalkylene) chain. Specifically, in compound 3C, a hydrolyzable silyl group is bonded to one end of the poly (oxyfluoroalkylene) chain, and in compound 3D, the hydrolyzable silyl group is a molecule of the poly (oxyfluoroalkylene) chain. It is bound to both ends.
According to the film-coated substrate of Example 13, slip resistance, fingerprint stain removal property and comparison with Example 22 in which all the regions were formed by the compound 3C and Example 23 in which all the regions were formed by the compound 3D. It was found that the friction resistance can be arranged side by side.
Further, according to the substrate with a film of Example 13, it was found that both slip resistance and abrasion resistance can be achieved at the same time as compared with Example 29 in which all the regions are formed by a mixture of compound 3C and compound 3D.

The compound 3E used for forming the first film and the compound 3F used for forming the second film used in Example 14 have different units of at least a part of the poly (oxyfluoroalkylene) chain from each other. _{Specifically, compound 3E has a unit of (OCF 2} OCF ₂ CF ₂ ) as a poly (oxyfluoroalkylene) chain, and compound 3F has a unit of (OCF ₂ CF ₂ CF _{2) as a poly (oxyfluoroalkylene) chain.} It _{has a unit of CF 2} OCF ₂ CF ₂ ), and at least the number of carbon atoms in the unit is different from each other. According to the substrate with a film of Example 14, Example 19 in which all the regions were formed by the compound 3E, Example 18 in which all the regions were formed by the compound 3F, and Example 17 in which some regions were formed by the compound 3F. In comparison, it was found that both abrasion resistance and lubricity can be achieved at the same time.

The compound 3C used for forming the first film and the compound 3G used for forming the second film used in Example 15 have different types of linking groups. Specifically, the linking group of compound 3C has a nitrogen atom, and the linking group of compound 3G has a Si atom. According to the substrate with a film of Example 15, both light resistance and abrasion resistance can be achieved as compared with Example 22 in which all regions are formed of compound 3C and Example 25 in which all regions are formed of compound 3G. I understood.

The compound 3H used for forming the first film and the compound 3I used for forming the second film used in Example 16 have different types of linking groups. Specifically, the linking group of compound 3H has an amide group, and the linking group of compound 3I has the above group G1. According to the substrate with a film of Example 16, light resistance and abrasion resistance can be achieved at the same time as compared with Example 24 in which all the regions are formed by the compound 3H and Example 26 in which all the regions are formed by the compound 3I. I understood.

The film-coated substrate obtained by the method for producing a film-coated substrate of the present invention can be used for various applications in which water and oil repellency is required. For example, display input devices such as touch panels; transparent glass or transparent plastic members, antifouling members for kitchens; water- and moisture-repellent and antifouling members such as electronic devices, heat exchangers, and batteries; antifouling members for toiletries. A member that requires liquid repellency while conducting; a member for water repellency / waterproofing / sliding of a heat exchanger; a member for surface low friction such as a vibrating sieve or the inside of a cylinder. More specific examples of use include display front protective plates, antireflection plates, polarizing plates, antiglare plates, or those with antireflection film treatment applied to their surfaces, mobile phones (for example, smartphones), and mobile information terminals. , Various devices having a display input device that operates on the screen with human fingers or palms such as touch panel sheets and touch panel displays of devices such as game machines and remote controls (for example, glass or film used for display units, etc., and Glass or film used for exterior parts other than display parts), decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproof members for wiring boards, water-repellent / waterproof / sliding members for heat exchangers, sun Water-repellent members for batteries, waterproof / water-repellent members for printed wiring boards, waterproof / water-repellent members for electronic device housings and electronic parts, insulation improvement members for power transmission lines, waterproof / water-repellent members for various filters Parts, waterproofing materials for radio wave absorbing materials and sound absorbing materials, antifouling materials for baths, kitchen equipment, toiletries, surface low friction parts such as vibration sieves and cylinder interiors, mechanical parts, vacuum equipment parts, bearing parts, automobiles, etc. Examples include parts for transportation equipment, surface protection members such as tools, and the like.
When the base material with the main film is used as the member, the article having the member may have a plurality of the base materials with the main film. Further, the article having the above-mentioned member may have a base material having a coverage of more than 80 to 100% (preferably 100%) of the fluorine-containing ether compound in addition to the base material with the main film. In that case, the preferable range and examples of the fluorine-containing ether compound are the same as those of the fluorine-containing ether compound used for the substrate with this membrane.

10, 20, 30, 40, 50 Substrate with film 12 Substrate 12a, 22a, 32a First region 12b, 22b, 32b Second region 12X, 12Y Surface 14, 24, 34, 44, 54 First film 16, 26, 36, 46, 56 Second film 42a Central region (first region)
42b Peripheral area (second area)
52a Continuous region (first region)
52b Distributed region (second region)
t Thickness direction

Claims (6)

A step of forming a first film on a part of a region on the main surface of a substrate by using a first fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a hydrolyzable silyl group.
A part of the main surface of the base material using a second fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a hydrolyzable silyl group, which is a compound different from the first fluorine-containing ether compound. A method for producing a substrate with a film, which comprises a step of forming a second film in a region of the above, other than the region where the first film is formed. The number average molecular weight of the poly (oxyfluoroalkylene) chain of the first fluorine-containing ether compound and the number average molecular weight of the poly (oxyfluoroalkylene) chain of the second fluorine-containing ether compound are different. The method for producing a substrate with a film according to claim 1. The invention according to claim 1 or 2, wherein the number of the hydrolyzable silyl groups of the first fluorine-containing ether compound and the number of the hydrolyzable silyl groups of the second fluorine-containing ether compound are different. Method for manufacturing a substrate with a film. Of the first fluorine-containing ether compound and the second fluorine-containing ether compound, one of the fluorine-containing ether compounds has the hydrolyzable silyl group only on one terminal side of the poly (oxyfluoroalkylene) chain. The film-coated group according to any one of claims 1 to 3, wherein the other fluoroether compound has the hydrolyzable silyl group on both terminal sides of the poly (oxyfluoroalkylene) chain. Material manufacturing method. Both the first fluorinated ether compound and the second fluorinated ether compound have a linking group between the poly (oxyfluoroalkylene) chain and the hydrolyzable silyl group.
Of the linking group of the first fluorine-containing ether compound and the linking group of the second fluorine-containing ether compound, one linking group has a nitrogen atom or an amide group, and the other linking group is a Si atom or The method for producing a substrate with a film according to any one of claims 1 to 4, which has a group represented by the following formula G1.

In the formula G1, * represents a bond position with the poly (oxyfluoroalkylene) chain or the hydrolyzable silyl group. However, at least one of the three * is the bond position with the poly (oxyfluoroalkylene) chain, and at least one is the bond position with the hydrolyzable silyl group. At least a part of the unit of the poly (oxyfluoroalkylene) chain of the first fluorine-containing ether compound and at least a part of the poly (oxyfluoroalkylene) chain of the second fluorine-containing ether compound. The method for producing a substrate with a film according to claim 1, wherein the method is different from that of the above.

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