JP7074139B2 - Compositions and articles and methods for producing compositions - Google Patents

Description

The present invention relates to compositions and articles.

The fluorine-containing compound is preferably used as a surface treatment agent because it exhibits 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 (oxyperfluoroalkylene) chain in which an ether bond (—O—) is present in the middle of the perfluoroalkylene chain is a compound having excellent flexibility, and particularly, oils and fats and the like. Excellent in removing dirt.

The surface treatment agent containing the fluorine-containing ether compound has a performance that the water and oil repellency does not easily decrease even if it is repeatedly rubbed with a finger (friction resistance) and a performance that can easily remove fingerprints adhering to the surface by wiping (fingerprint stains). (Removability) is required to be maintained for a long period of time, for example, it is used as a surface treatment agent for a member constituting a surface touched by a finger of a touch panel.
The fluorine-containing ether compound includes a poly (oxyperfluoroalkylene) chain obtained by reacting a compound having a poly (oxyperfluoroalkylene) chain with an alkoxysilane in the presence of a hydrosilylation catalyst containing platinum or the like. Compounds having a hydrolyzable silyl group at the terminal are widely used (Patent Document 1).

JP-A-2015-199906

In recent years, the physical characteristics required for a surface layer formed by using a composition containing a fluorine-containing ether compound have been further improved.
When the present inventors formed a surface layer on the surface of the base material using the composition containing the fluorine-containing ether compound described in Patent Document 1, the abrasion resistance of the surface layer was increased depending on the components contained in the composition. It has been found that the appearance characteristics of the surface layer may be inferior when it is insufficient or when granules due to agglomerates are generated.

In view of the above problems, the present invention provides a composition capable of forming a surface layer having excellent friction resistance and suppressing the generation of granules, and an article having a surface layer formed by using the composition. With the goal.

The present invention provides compositions and articles having the following configurations [1] to [11].
[1] A composition containing a fluoroether compound having at least one of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom and a poly (oxyperfluoroalkylene) chain, and an iron atom-containing compound. The composition is characterized in that the content of iron atoms contained in the iron atom-containing compound is 15 to 1,500 mass ppm with respect to the fluorine-containing ether compound.
[2] The composition of [1], wherein the fluorine-containing ether compound has two or more hydrolyzable groups bonded to the silicon atom.
[3] The composition of [1] or [2], wherein the fluorine-containing ether compound has two or more groups composed of silicon atoms to which the hydrolyzable group is bonded.

[4] The composition according to any one of [1] to [3], wherein the fluorine-containing ether compound is a compound represented by the following formula (1).
[A-O-Z ^1- (R ^f O) _m- ] _j Z ² [-SiR _n L _3-n ] _q (1)
However, if A is a perfluoroalkyl group or -Q [-SiR _n L _3-n ] _k and A is -Q [-SiR _n L _3-n ] _k , j is 1.
Q is a concatenated group of (k + 1) valence, and k is an integer of 1 to 10.
Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom (however, the oxyperfluoroalkylene group is excluded. The oxygen atom in the oxyfluoroalkylene group is , (R ^f O) _m ), or a poly (oxyfluoroalkylene) group ((R ^f O) _m ) having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms. The oxygen atom in the oxyfluoroalkylene group to be bonded is attached to (R ^f O) _m . The oxyfluoroalkylene group bonded to (R ^f O) _m contains one or more hydrogen atoms. Poly (oxyfluoroalkylene). ) The group may contain both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms.)
R ^f is a perfluoroalkylene group, m is an integer of 2 to 200, and when two or more kinds of R ^f O having different carbon atoms are present in (R ^f O) _m , the bonding order of each R ^f O is present. Is not limited,
Z ² is a (j + q) -valent linking group, R is a hydrogen atom or a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, and j and q are integers of 1 or more, respectively. n is an integer of 0 to 2.

[5] The composition of [4], wherein A is a perfluoroalkyl group having 1 to 6 carbon atoms and q is 2 to 4.
[6] The composition of [4] or [5], wherein L is an alkoxy group having 1 to 4 carbon atoms and n is 0 or 1.
[7] The composition according to any one of [4] to [6], wherein the SiR _n L _3-n is Si (OCH ₃ ) ₃ .
[8] The composition according to any one of [1] to [7], wherein the iron atom-containing compound is a compound in which a ligand having an aromatic ring is coordinated to an iron atom.
[9] The composition according to any one of [1] to [8], further comprising a liquid medium.
[10] The composition of [9], wherein the liquid medium is a fluorinated organic solvent.
[11] An article characterized by having a base material and a surface layer formed of the composition according to any one of [1] to [10] on the surface of the base material.

According to the present invention, it is possible to provide a composition having excellent friction resistance and capable of forming a surface layer in which the generation of granules is suppressed, and an article having a surface layer formed by using the composition.

In the present specification, the compound represented by the formula (1) is referred to as compound 1. Compounds represented by other formulas are also described in the same manner. The group represented by the formula (1) is referred to as group 1. The groups expressed 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" means an A group between carbon atoms in the alkylene group. It may have an A group at the terminal, such as an alkylene group-A group.
The meanings of the terms in the present invention are as follows.
The "ethery oxygen atom" means an oxygen atom that forms an ether bond (-O-) between carbon atoms.
The "divalent organopolysiloxane residue" is a group represented by the following formula. Ra 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 ^b ) ₂ PhSi (R ^b ) _2- (where Ph is a phenylene group and R ^b is a monovalent organic group). Is. As R ^b , an alkyl group (preferably 1 to 10 carbon atoms) is preferable.
The "dialkylsilylene group" is a group represented by -Si (R ^c ) _2- (where R ^c is an alkyl group (preferably 1 to 10 carbon atoms)).
"Surface layer" means a layer formed on the surface of a substrate.
The "number average molecular weight" of the fluorine-containing ether compound is calculated by the following method using an NMR analysis method.
¹ Calculated by 1 H-NMR and ¹⁹ F-NMR by determining the number (average value) of oxyperfluoroalkylene groups with respect to the terminal group.

〔Composition〕
The composition of the present invention (hereinafter, also referred to as “the present composition”) contains a hydrolyzable group bonded to a silicon atom, at least one of a hydroxyl groups bonded to the silicon atom, and a poly (oxyperfluoroalkylene) chain. A composition containing a fluorine ether compound (hereinafter, also referred to as "specific fluorine-containing ether compound") and an iron atom-containing compound, wherein the content of iron atoms contained in the iron atom-containing compound is the specific fluorine-containing ether compound. It is 15 to 1,500 mass ppm with respect to the total mass of.
Hereinafter, a group composed of a silicon atom to which a hydrolyzable group is bonded is referred to as a "hydrolyzable silyl group", and a hydroxyl group bonded to the silicon atom is also referred to as a "silanol group".

According to this composition, it is possible to form a surface layer having excellent abrasion resistance and suppressing the generation of granules. The details of this reason have not been clarified yet, but it is presumed to be due to the following reasons.
That is, when the present composition having an iron atom content of 15% by mass or more with respect to the specific fluorine-containing ether compound is used when forming the surface layer, the iron atom-containing compound is hydrolyzed contained in the specific fluorine-containing ether compound. It is presumed that the sex silyl group exerts a function as a hydrolysis reaction catalyst and the surface layer and the base material are firmly bonded to each other. As a result, it is considered that a surface layer having excellent abrasion resistance could be formed.
Further, when the content of the iron atom with respect to the specific fluorine-containing ether compound is 1,500 mass ppm or less, the hydrolysis / condensation of the specific fluorine-containing ether compound during storage of the composition is suppressed, and the composition contains the specific fluorine-containing ether compound. It is considered that aggregates derived from the specific fluorine-containing ether compound are unlikely to be generated. As a result, it is considered that the surface layer obtained by using the present composition suppressed the generation of granules due to the agglomerates.

(Specific fluorine-containing ether compound)
The specific fluorine-containing ether compound in the present composition has a hydrolyzable silyl group or silanol group and a poly (oxyperfluoroalkylene) chain.

As the poly (oxyperfluoroalkylene) chain, (R ^f O) _m (where R ^f is a perfluoroalkylene group and m is an integer of 2 to 200) because the surface layer has more excellent water and oil repellency. , It may be composed of two or more kinds of R ^f O having different carbon atoms.) Is preferable.
The definition of (R ^f O) _m will be described in detail later.

The specific fluorine-containing ether compound preferably has a hydrolyzable silyl group from the viewpoint of better storage stability of the compound, and has two or more hydrolyzable silyl groups from the viewpoint of more excellent abrasion resistance of the surface layer. It is preferable to have. The number of hydrolyzable silyl groups is preferably 6 or less, more preferably 4 or less.

The number average molecular weight of the specific fluorine-containing ether compound is preferably 500 to 20,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 8,000. When the number average molecular weight is within the range, the surface layer has excellent abrasion resistance.

As the specific fluorine-containing ether compound, compound 1 is preferable because the surface layer has more excellent water and oil repellency.
[A-O-Z ^1- (R ^f O) _m- ] _j Z ² [-SiR _n L _3-n ] _q (1)

A is a perfluoroalkyl group or —Q [—SiR _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 surface layer.
The perfluoroalkyl group may be linear or branched.
However, when A is −Q [−SiR _n L _3-n ] _k , j is 1.

Examples of perfluoroalkyl groups 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 are preferable because the surface layer has more excellent water and oil repellency.

Q is a concatenated group of (k + 1) valence. k is an integer from 1 to 10. Therefore, as Q, a linking group having a valence of 2 to 11 can be mentioned.
Q includes, for example, an alkylene group which may have an ethereal oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a 2- to 8-valent organopolysiloxane residue, and , A group obtained by removing SiR _n L _3-n from the formulas (2-1), formula (2-2), and formulas (2-1-1) to (2-1-6) described later can be mentioned.

R is a hydrogen atom or a monovalent hydrocarbon group.
R is preferably a monovalent hydrocarbon group, and particularly preferably a monovalent saturated hydrocarbon group. The number of carbon atoms of the monovalent hydrocarbon group 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. SiR _n L _3-n , in which L is a hydrolyzable group, is a hydrolyzable silyl group.
The hydrolyzable group of L is a group that becomes a hydroxyl group by the hydrolysis reaction. That is, the hydrolyzable group of the hydrolyzable silyl group becomes a silanol group by the hydrolyzing 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.

Examples of L include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (-NCO) and the like. 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 from the viewpoint of easy industrial production. As L, an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgas during coating and the storage stability of the compound is more excellent, and an ethoxy group is particularly preferable when long-term storage stability of the compound is required. Preferably, a 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 surface layer to the base material stronger.
When n is 0 or 1, the plurality of Ls present in one molecule may be the same or different from each other. From the viewpoint of availability of raw materials and ease of production, they are preferably the same. When n is 2, the two Rs present in one molecule may be the same or different from each other.

Hydrolyzable silyl groups (SiR _n L _3-n ) include -Si (OCH ₃ ) ₃ , -SiCH ₃ (OCH ₃ ) ₂ , -Si (OCH ₂ CH ₃ ) ₃ , -SiCl ₃ , -Si ( OC (O) CH ₃ ) ₃ and −Si (NCO) ₃ are preferable. -Si (OCH ₃ ) ₃ is particularly preferable from the viewpoint of ease of handling in industrial manufacturing.

Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom (however, the oxyperfluoroalkylene group is excluded. The oxygen atom in the oxyfluoroalkylene group is , (R ^f O) _m ), or a poly (oxyfluoroalkylene) group ((R ^f O) _m ) having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms. The oxygen atom in the oxyfluoroalkylene group to be bonded is attached to (R ^f O) _m . The oxyfluoroalkylene group bonded to (R ^f O) _m contains one or more hydrogen atoms. Poly (oxyfluoroalkylene). ) The group may contain both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms.) The oxyfluoroalkylene group or the poly (oxyfluoroalkylene) group preferably has 1 to 10 carbon atoms.

Z ¹ has a single bond, -CHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CHFCF ₂ OCH ₂ CF ₂ CF ₂ O-, -CF ₂ CF ₂ CHFCF ₂ OCH ₂ CF because it is easy to produce a compound. ₂ O-, -CF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ OCF ₂ CF ₂ OCHFCF ₂ OCH ₂ CF ₂ O-, -CF ₂ CH ₂ OCH ₂ CF ₂ O-, -CF ₂ CF ₂ OCF ₂ CH ₂ OCH ₂ CF ₂ O- is preferable (however, the left side binds to A-O). As Z ¹ , a single bond, —CHFCF ₂ OCH ₂ CF ₂ O—, is particularly preferable.

R ^f is a perfluoroalkylene group.
The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6 from the viewpoint of more excellent water and oil repellency of the surface layer.
The perfluoroalkylene group may be linear or branched, but is preferably linear because it is more excellent in water and oil repellency of the surface layer.
The plurality of R ^fs may be the same or different. That is, (R ^f O) _m may be composed of two or more types of R ^f O having different carbon atoms.

m is an integer of 2 to 200, preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 100. When m is at least the lower limit of the above range, the water and oil repellency of the surface layer is more excellent. When m is not more than the upper limit of the above range, the friction resistance of the surface layer is more excellent.

When two or more kinds of R ^f O having different carbon atoms are present in (R ^f O) _m , the bonding order of each R ^f O is not limited. For example, when two types of R ^f O are present, the two types of R ^f O may be randomly, alternately, or arranged in blocks.
As (R ^f O) _m , {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 (CF ₂ CF ₂ CF ₂ O) _m13 (CF ₂ ) because the water and oil repellency of the surface layer is more excellent. CF ₂ CF ₂ CF ₂ O) _m14 }, (CF ₂ CF ₂ O) _m16, (CF ₂ CF ₂ CF ₂ O) _m17 , (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 ( CF ₂ CF ₂ O), (CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m18 (CF ₂ O) or (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m19 (CF ₂ CF ₂ O) is preferable, {(CF ₂ O) _m11 (CF ₂ CF ₂ O) _m12 (CF ₂ CF ₂ CF ₂ O) _m13 (CF ₂ CF ₂ CF ₂ CF ₂ O) _m14 }, (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _m15 (CF ₂ CF ₂ O), (CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m18 (CF ₂ O) ), (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) _m19 (CF ₂ CF ₂ O) is particularly preferable.
However, m11 and m12 are integers of 1 or more, m13 and m14 are integers of 0 or 1 or more, respectively, m11 + m12 + m13 + m14 are integers of ₂ to 200, and CF2O of m11 and m12. The binding order of CF ₂ CF ₂ O, m13 CF ₂ CF ₂ CF ₂ O, and m14 CF ₂ CF ₂ CF ₂ CF ₂ O is not limited. m16 and m17 are integers of 2 to 200, respectively, and m15, m18 and m19 are integers of 1 to 99, respectively.

Z ² is a (j + q) valence linking group.
Z ² may have, for example, an ethereal oxygen atom or a divalent organopolysiloxane residue, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a 2-8 valent organopolysiloxane residue, and , A group obtained by removing SiR _n L _3-n from the formulas (2-1), formula (2-2), and formulas (2-1-1) to (2-1-6) described later can be 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 surface layer, and 1 is particularly preferable from the viewpoint of easy production of a compound.
q 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 water and oil repellency of the surface layer is more excellent.

Compound 1 is preferably compound 1-1 because the surface layer has more excellent water and oil repellency.
A-O-Z ^1- (R ^f O) _m -Z ³ (1-1)
The definitions of A, Z ¹ , R ^f and m in the formula (1-1) are synonymous with the definitions of each group in the formula (1).

Z ³ is a group 2-1 or a group 2-2.
-R ^f7 -Q ^a -X (-Q ^b -SiR _n L _3-n ) _h (-R ⁷ ) _i (2-1)
-R ^f7 -Q ^71- [CH ₂ C (R ⁷¹ ) (-Q ⁷² -SiR _n L _3-n )] _y -R ⁷² (2-2)

In formulas (2-1) and (2-2), the definitions of R, L and n are synonymous with the definitions of each group in formula (1).

R ^f7 is a perfluoroalkylene group.
The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 30, particularly preferably 1 to 6. The perfluoroalkylene group may be linear or branched.
As R ^f7 , −CF ₂ CF ₂ CF ₂ CF ₂ − or − CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ − is preferable from the viewpoint of easy production of a compound.

Qa is ^a single bond or 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 may be used. 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-O-alkylene group, and an alkylene group-OC (O). -The alkylene group, the alkylene group-Si (R ^a ) ₂ -the phenylene group-Si (R ^a ) ₂ can be mentioned.

X 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 is preferably 1 to 20, and particularly preferably 1 to 10.
Examples of the 2 to 8-valent organopolysiloxane residue include a divalent organopolysiloxane residue and a (w + 1) -valent organopolysiloxane residue described later.

^Qb is a single bond or divalent linking group.
The definition of ^a divalent linking group is synonymous with the definition described in Qa above.

R ⁷ 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 is a single bond or an alkylene group, h is 1 and i is 0.
When X 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 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 is a 2- to 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.
When there are two or more (-Q ^b -SiR _n L 3- _n ), the two or more (-Q ^b -SiR _n L _3-n ) may be the same or different. When there are two or more ^R7s , the two or more ( ^-R7s ) may be the same or different.

^Q71 is a single bond, an alkylene group, or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, and a single bond is preferable from the viewpoint of easy production of a compound.
The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The carbon number of the group having an ethereal oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

R ⁷¹ 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 ⁷² 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. ^Q72 is preferably single-bonded or _-CH2- because it is easy to produce a compound.

R ⁷² 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 ⁷¹ ) (-Q ⁷² -SiR _n L _3-n )] may be the same or different.

As the group 2-1, groups 2-1-1 to 2-1-6 are preferable.
-R ^f7- (X ¹ ) _p -Q ¹ -SiR _n L _3-n (2-1-1)
-R ^f7- (X ² ) _r -Q ²¹ -N [-Q ²² -SiR _n L _3-n ] ₂ (2-1-2)
-R ^f7 -Q ³¹ -G (R ³ ) [-Q ³² -SiR _n L _3-n ] ₂ (2-1-3)
-R ^f7- [C (O) N (R ^d )] _s -Q ^41- (O) _t -C [-(O) _u -Q ⁴² -SiR _n L _3-n ] ₃ (2-1-4 )
-R ^f7 -Q ⁵¹ -Si [-Q ⁵² -SiR _n L _3-n ] ₃ (2-1-5)
-R ^f7- [C (O) N (R ^d )] _v -Q ⁶¹ -Z ³ [-Q ⁶² -SiR _n L _3-n ] _w (2-1-6)
In the equations (2-1-1) to (2-1-6), the definitions of R ^f7 , R, L, and n are as described above.

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

Q ¹ 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 ^Q1 is preferably 1 to 10, and particularly preferably 2 to 6.

As for Q ¹ , when p 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 − are preferable. (X ¹ ) When _p is −O—, −CH ₂ CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable. (X ¹ ) When _p 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 ^Q1 ). When Q ¹ is these groups, the compound is easy to produce.

Specific examples of the group 2-1-1 include the following groups.

X ² is -O-, -NH-, or -C (O) N (R ^d )-.
The definition of R ^d is as described above.

^Q21 is a single bond, an alkylene group, or an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, -C (O)-, -C (O) O-, -OC ( O) -or a group having -NH-.
The carbon number of the alkylene group represented by Q21 is preferably ¹ to 10, and particularly preferably 2 to 6.
Ethereal oxygen atom between carbon atom and carbon atom of alkylene group having 2 or more carbon atoms represented by Q21, -C ⁽ O)-, -C (O) O-, -OC (O)-or -NH The number of carbon atoms of the group having − is preferably 2 to 10, and particularly preferably 2 to 6.

As ^Q21 , from the viewpoint of easy production of compounds, -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 (OCH ₂ CH _2- is preferable (however, the right side binds to N).

r is 0 or 1 (where 0 if Q ²¹ is a single bond). 0 is preferable from the viewpoint that the compound can be easily produced.

Q ²² is an alkylene group or a group having a divalent organopolysiloxane residue, an ethereal oxygen atom or -NH- between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q22 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 ^Q22 is 2 to 10. Is preferable, and 2 to 6 are particularly preferable.

As Q22, -CH _{2 CH 2 CH 2-, -CH 2 CH 2 OCH 2 CH 2 CH 2 -- is preferable ( however , the} ^right side binds to Si) from the viewpoint of easy production of a compound.

The two [-Q ²² -SiR _n L _3-n ] may be the same or different.

Specific examples of the group 2-1-2 include the following groups.

Q ³¹ is a single bond, an alkylene group, or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, and a single bond is preferable from the viewpoint of easy production of a compound.
The carbon number of the alkylene group represented by ^Q31 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Q31 is preferably 2 to 10, and particularly preferably 2 to 6.

G is a carbon atom or a silicon atom.
R ⁶ is a hydroxyl group or an alkyl group. The number of carbon atoms of the alkyl group represented by R ³ is preferably 1 to 4.
As G (R ³ ), C (OH) or Si (R ^3a ) (where R ^3a is an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, and methyl is preferable, because it is easy to produce a compound. The group is particularly preferable.) Is preferable.

^Q32 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 ^Q32 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 atoms of the alkylene group having 2 or more carbon atoms represented by ^Q32 is preferably 2 to 10, preferably 2 to 10. 6 is particularly preferable.
As Q ³² , -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 ³² -SiR _n L _3-n ] may be the same or different.

Specific examples of the group 2-1-3 include the following groups.

The definition of R ^d in the formula (2-1-4) is as described above.
s is 0 or 1.
Q ⁴¹ is a single bond, an alkylene group, or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by ^Q41 is preferably 1 to 10, particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Q41 is preferably 2 to 10, and particularly preferably 2 to 6.
t is 0 or 1 (where 0 if Q ⁴¹ is a single bond).
As for -Q ^41- (O) _t- , when s is 0, it is a single bond, -CH ₂ O-, -CH _{2 OCH 2-, -CH 2 OCH 2 CH 2 because it is easy} to produce a compound. 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 binds to R ^f7 ), and when s is 1, Single bond, -CH _2- , -CH ₂ CH ₂ --is preferable.

Q ⁴² is an alkylene group, and the alkylene group is —O—, —C (O) N (R ^d )-[The definition of R ^d is as described above. ], It may have a silphenylene skeletal group, a divalent 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 -C (O) N (R ^d )-, a dialkylsilylene group or a divalent organopolysiloxane residue, it is between carbon atoms and the end on the side to be bonded to (O) _u1 . It is preferable to have these groups.
The carbon number of the alkylene group represented by ^Q42 is preferably 1 to 10, and particularly preferably 2 to 6.

u is 0 or 1.
-(O) _u -Q ^42- is -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ OCH ₂ CH ₂ CH _2- , -CH ₂ because it is easy to produce a compound. 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 --preferably (however, the right side is bonded to Si).

The three [-(O) _u -Q ⁴² -SiR _n L _3-n ] may be the same or different.

Specific examples of the group 2-1-4 include the following groups.

^Q51 is an alkylene group or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by ^Q51 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Q51 is preferably 2 to 10, and particularly preferably 2 to 6.
As ^Q51 , from the viewpoint of easy production of compounds, -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 binds to Si).

Q ⁵² 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 ⁵² 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 atoms of the alkylene group having 2 or more carbon atoms represented by ^Q52 is preferably 2 to 10, preferably 2 to 10. 6 is particularly preferable.
As ^Q52 , -CH _{2 CH 2 CH 2-, -CH 2 CH 2 OCH 2 CH 2 CH 2 -- is preferable ( however , the} right side binds to SiR _n L _3-n ) from the viewpoint of easy production of a compound. .).

The three [-Q ⁵² -SiR _n L _3-n ] may be the same or different.

Specific examples of groups 2-1-5 include the following groups.

The definition of R ^d in the formula (2-1-6) is as described above.
v is 0 or 1.

^Q61 is an alkylene group or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by ^Q61 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Q61 is preferably 2 to 10, and particularly preferably 2 to 6.
As ^Q61 , from the viewpoint of easy production of compounds, -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 (however, the right side binds to Z ³ ).

Z ³ 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.

^Q62 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 ^Q62 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 atoms of the alkylene group having 2 or more carbon atoms represented by ^Q62 is preferably 2 to 10, preferably 2 to 10. 6 is particularly preferable.
As ^Q62 , -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 ⁶² -SiR _n L _3-n ] may be the same or different.

The content of the specific fluorine-containing ether compound is preferably 0.01 to 99.8% by mass, more preferably 0.1 to 50% by mass, and 0.1 to 20% by mass with respect to the total mass of the present composition. Is particularly preferable.
The specific fluorine-containing ether compound may be used alone or in combination of two or more.

<Manufacturing method of specific fluorine-containing ether compound>
Specific examples of the method for producing a specific fluorine-containing ether compound include a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group (for example, an allyl group, a vinyl group, or a 3-butenyl group) in the presence of a hydrosilylation catalyst. And a silicon compound having at least one of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to the silicon atom and a hydrogen atom bonded to the silicon atom to obtain a specific fluorine-containing ether compound. Be done.

When an iron atom-containing compound is used as a hydrosilylation catalyst in the synthesis of the specific fluorine-containing ether compound, the synthesis of the specific fluorine-containing ether compound gives a mixture containing the iron atom-containing compound together with the specific fluorine-containing ether compound. The mixture thus obtained can be used as it is as the present composition. Further, other components described later may be added to the obtained mixture and used as the present composition.
On the other hand, when the iron atom-containing compound is not used as the hydrosilylation catalyst at the time of synthesizing the specific fluorine-containing ether compound, after the synthesis of the specific fluorine-containing ether compound, the specific fluorine-containing ether compound and the iron atom-containing compound are required. The present composition is obtained by mixing with other components accordingly.

(Iron atom-containing compound)
The iron atom-containing compound is preferably a catalyst described later. For example, the specific fluorine-containing ether compound is produced in the presence of a hydrosilylation catalyst. Therefore, when a catalyst containing an iron atom is used as the hydrosilylation catalyst, the composition contains the iron atom in the hydrosilylation catalyst together with the specific fluorine-containing ether compound.
Further, in order to promote the hydrolysis reaction of the hydrolyzable silyl group of the specific fluorine-containing ether compound at the time of forming the surface layer, the composition may contain a hydrolysis catalyst. At this time, if a hydrolysis catalyst containing an iron atom is used, the iron atom in the hydrolysis catalyst is contained in the composition.
The iron atom-containing compound may serve as both a hydrosilylation catalyst and a hydrolysis catalyst.

When the iron atom-containing compound is a hydrosilylation catalyst, the iron atom-containing compound includes a compound in which carbonyl, cyclopentadienyl, terpyridine, bistrimethylsilylmethyl, bisiminopyridine, bisiminoquinolin, isocyanide, etc. are coordinated with the iron atom. Can be mentioned. As the ligand coordinated to the iron atom, one having an aromatic ring (cyclopentadienyl ring, pyridine ring, benzene ring, etc.) is preferable. The ligand may be used alone or in combination of two or more. Specific examples of the hydrosilylation catalyst include an iron complex having a carbonyl ligand (Fe (CO) ₅ , Fe ₃ (CO) ₁₂ ), and an iron complex having a carbonyl ligand and a cyclopentadienyl ligand (). For example, C5 H5 _- Fe-CH ₃ (CO) ₂ ) described in International Publication _No. 2010/016416, an iron complex having a telpyridine ligand, a telpyridine ligand and a bistrimethylsilylmethyl ligand. Iron complex having, iron complex having bisiminopyridine ligand, iron complex having bisiminoquinoline ligand, iron complex having isocyanide ligand (Japanese Patent Laid-Open No. 2016-41414, International Publication No. 2016/024607) (Japanese Patent Laid-Open No. et al.), An iron complex having a carbonyl ligand and an isocyanide ligand, and a hydrosilylated iron catalyst described in International Publication No. 2016/027819.
When the iron atom-containing compound is a hydrolysis catalyst, specific examples of the hydrolysis catalyst include iron stearate.
The iron atom-containing compound may be used alone or in combination of two or more.

The content of the iron atom contained in the iron atom-containing compound is 15 to 1,500 mass ppm, particularly preferably 20 to 1,500 mass ppm with respect to the specific fluorine-containing ether compound. When the iron atom content is at least the lower limit of the above range, the surface layer has excellent friction resistance. Further, when the iron atom content is not more than the upper limit of the above range, a surface layer in which the generation of granules is suppressed can be obtained.

(Catalyst that does not contain iron atoms)
The present composition may contain a catalyst other than the iron atom-containing compound (that is, a catalyst containing no iron atom). Examples of the catalyst containing no iron atom include a hydrosilylation catalyst containing no iron atom and a hydrolysis catalyst containing no iron atom.

The hydrosilylation catalyst containing no iron atom is preferably a transition metal catalyst containing a transition metal other than the iron atom, more preferably a transition metal catalyst containing a group 8 to 10 transition metal other than the iron atom, and a platinum (Pt) catalyst. , A ruthenium (Ru) catalyst and a rhodium (Rh) catalyst are more preferable, and a platinum catalyst is particularly preferable from the viewpoint that the hydrosilylation reaction proceeds further. The 8th to 10th groups are group numbers according to the revised version of the IUPAC Inorganic Chemistry Nomenclature (1989).
Specific examples of the platinum catalyst include a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, a Pt complex of divinyltetramethyldisiloxane, and a Pt complex of tetramethyltetravinylcyclotetrasiloxane. Examples thereof include platinum chloride acid and platinum oxide.

Specific examples of the hydrolysis catalyst containing no iron atom include dibutyltin octate, lead octanate, tetraisopropyl titanate, tetrabutyl titanate, and acetylacetonato titanium.

(Other ingredients)
The present composition may contain components other than the above (hereinafter, also referred to as "other components"). Examples of other components include compounds that are impossibly contained in the production of a specific fluorine-containing ether compound, and a liquid medium.
When the composition contains a liquid medium, the composition may be a solution or a dispersion.

The present composition may contain impurities such as by-products produced in the process of producing the specific fluorine-containing ether compound. Further, the specific fluorine-containing ether compound contained in the present composition may be contained in a state where a part of the hydrolyzable silyl group is hydrolyzed, and the silanol group generated by the hydrolyzing reaction is partially contained. It may be contained in a condensed state.

Specific examples of the liquid medium include organic solvents. Specific examples of the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent, and it is preferable to use a fluorine-based organic solvent, and a fluoroalkyl ether is more preferable. 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 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.

The content of the liquid medium is preferably 0.01 to 99.99% by mass, particularly preferably 1 to 90% by mass, based on the total mass of the present composition.

[Article]
The article of the present invention has a base material and a surface layer formed from the present composition on the surface of the base material.

The surface layer contains a compound obtained through a hydrolysis reaction and a condensation reaction of a specific fluorine-containing ether compound.
The film thickness of the surface layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. The thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G: product name, manufactured by RIGAKU). It can be calculated from the vibration cycle.

The base material 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. The base material may be surface-treated with SiO ₂ or the like.
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.

The article can be manufactured, for example, by the following method.
-A method for obtaining the above-mentioned article by treating the surface of a base material by a dry coating method using the present composition.
-A method in which the present composition is applied to the surface of a base material by a wet coating method and dried to obtain the above-mentioned article.

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 specific 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 the present composition may be used.
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, and Langmuir brojet. The method, the gravure coat method can be mentioned.

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 1 to 8, Examples 1 to 4 and 8 are Examples, and Examples 5 to 7 are Comparative Examples.

〔Evaluation method〕
(Appearance characteristics)
The surface layer of the evaluation sample was visually observed, and the appearance characteristics were evaluated based on the presence or absence of granules in the surface layer. The evaluation criteria are as follows.
A: There are no granules of about 100 μm on the surface layer.
B: The surface layer contains granules of about 100 μm.

(Abrasion resistance)
The water contact angle was measured for the evaluation samples before and after the friction resistance test, and the rate of decrease in the water contact angle after the friction resistance test was calculated according to the following formula. The smaller the value of the reduction rate, the smaller the deterioration of the performance due to friction, and the better the friction resistance.
Decrease rate of water contact angle after friction resistance test (%) = 100- {100 x (water contact angle after friction resistance test) / (water contact angle before friction resistance test)}
<Measurement method of water contact angle>
The contact angle (water contact angle) of about 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500: product name, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at five different points on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.
<Test method for abrasion resistance>
For the surface layer, use a reciprocating traverse tester (manufactured by KNT) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), and use a steel wool bonster (# 0000) with a pressure of 98.07 kPa and a speed of 320 cm. It was reciprocated 10,000 times at / minute.

[Example 1]
(Example 1-1)
The following compound B-1 was obtained according to the methods described in Examples 1-1 and 1-2 of International Publication No. 2014/163004 (the average value of the number of units n1 is 21, and the average value of the number of units n2 is 20). , The number average molecular weight is 4,200.).
CF ₃ -CF ₂ CF ₂ -O-CHFCF ₂ -O-CH ₂ CF ₂ -O {(CF ₂ O) _n1 (CF ₂ CF ₂ O) _n2 } -CF ₂ CH ₂ -O-CH ₂ -CH = CH ₂ (B-1)

(Example 1-2)
In a screw vial, 2 g (0.5 mmol) of compound B-1 obtained in Example 1-1 was synthesized according to the method described in Synthesis Example 1 of International Publication No. 2016/027819 [Fe (mesityl) (μ-). methyl)] Add 1.5 mg (0.0025 mmol) of ₂ , 1 μL (0.10 mmol) of tert-butyl isocyanide (tBuNC), and 0.12 g (1.0 mmol) of trimethoxysilane, and after sealing, add 16 at 80 ° C. Stir for hours. ¹ After confirming the disappearance of compound B-1 by measuring the H-NMR spectrum, the low boiling component is removed by distillation under reduced pressure to obtain an iron atom-containing compound (hydrosilylation catalyst) and compound B-2 (unit). The composition 1 contains 21, the average value of the number n1 is 21, the average value of the unit number n2 is 20, and the number average molecular weight is 4,300.), And the content of the iron atom is 150 mass ppm with respect to the compound B-2. Was obtained in 2 g.
CF ₃ -CF ₂ CF ₂ -O-CHFCF ₂ -O-CH ₂ CF ₂ -O {(CF ₂ O) _n1 (CF ₂ CF ₂ O) _n2 } -CF ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ -Si (OCH ₃ ) ₃ (B-2)

(Example 1-3)
The composition 1 obtained in Example 1-2 was prepared according to the method described in Example 1 of International Publication No. 2017/022437, and the obtained compound B-2 was added to a concentration of 20% by mass. It was dissolved in 7200 (manufactured by 3M) to obtain 10 g of the composition 1-1.

[Example 2]
(Example 2-1)
An iron atom-containing compound (hydrosilylation catalyst) is used in the same manner as in Example 1 except that compound C-1 synthesized according to the method described in Synthesis Example 1 of JP-A-2015-199906 is used instead of compound B-1. ) And compound C-2, and 2 g of the composition 2 having an iron atom content of 150 mass ppm with respect to compound C-2 was obtained.

(Example 2-2)
The composition 2 obtained in Example 2-1 was prepared by using the method described in Example 1 of International Publication No. 2017/022437, and the obtained compound C-2 was added to a concentration of 20% by mass. It was dissolved in 7200 (manufactured by 3M) to obtain 10 g of the composition 2-1.

[Examples 3 to 6]
[Fe (mesityl) (μ-mesityl)] The iron atom-containing compound (hydrosilylation catalyst), compound C-2, and Novec are in the same manner as in Example 2 except that the amount of ₂ used is changed as shown in Table 1. A composition containing -7200 (manufactured by 3M) was obtained.

[Example 7]
(Example 7-1)
According to the method described in Example 6 of WO2013 / 121984, 96 g of the fluorine-containing ether compound A-1 (the average value of the number of units n is 7, the number average molecular weight is 2,900) and the fluorine-containing ether compound A-2 (units). A mixed solution consisting of 3 g of the number n having an average value of 7 and a number average molecular weight of 2,722) and 1 g of methanol was obtained.
CF ₃ -O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ C (= O) NHCH ₂ CH ₂ CH ₂ -Si ( OCH ₃ ) ₃ (A-1)
CF ₃ -O- (CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ C (= O) OCH ₃ (A-2)

(Example 7-2)
1 g of the mixed solution obtained in Example 7-1 and 0.80 mg of dibutyltin dilaurate are mixed to contain a tin atom-containing compound (hydrosilylation catalyst), compound A-1 and compound A-2, and compound A-1. And 1 g of the composition 7 having a tin atom content of 150 mass ppm with respect to the total amount of the compound A-2 was obtained.

(Example 7-3)
The composition 7 obtained in Example 7-2 was subjected to the method described in Example 1 of International Publication No. 2017/022437, and the total amount of the obtained compound A-1 and the compound A-2 was 20 mass by mass. It was dissolved in Novell 7200 (manufactured by 3M) to obtain 10 g of the composition 7-2.
(Example 8)
(Example 8-1)
In a screw vial, 2 g (0.5 mmol) of compound B-1 obtained in Example 1-1, Bull. Chem. Soc. Jpn. 1.3 mg (0. 0025 mmol), 0.12 g (1.0 mmol) of trimethoxysilane, and sodium triethylborohydride (1.0 M in toluene, 0.01 mmol) were added, and the mixture was stirred at 30 ° C. for 24 hours after sealing. ¹ After confirming the disappearance of compound B-1 by measuring the H-NMR spectrum, the low boiling component is removed by distillation under reduced pressure to obtain an iron atom-containing compound (hydrosilylation catalyst) and compound B-2 (unit). The composition 8 contains 21, the average value of the number n1 is 21, the average value of the unit number n2 is 20, and the number average molecular weight is 4,300.), And the content of the iron atom is 60 mass ppm with respect to the compound B-2. Was obtained in 2 g.
CF ₃ -CF ₂ CF ₂ -O-CHFCF ₂ -O-CH ₂ CF ₂ -O {(CF ₂ O) _n1 (CF ₂ CF ₂ O) _n2 } -CF ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ -Si (OCH ₃ ) ₃ (B-2)
(Example 8-2)
The composition 8 obtained in Example 8-1 was prepared by using the method described in Example 1 of International Publication No. 2017/022437, and the obtained compound B-2 was added to a concentration of 20% by mass. It was dissolved in 7200 (manufactured by 3M) to obtain 10 g of the composition 8-1.

[Preparation of evaluation sample]
Using the composition finally obtained by each example, the surface treatment of the base material is performed by the following wet coating method, and an evaluation sample in which a surface layer is formed on the surface of the base material (chemically strengthened glass) is prepared. Obtained.
That is, the composition finally obtained by each example and Novec-7200 (manufactured by 3M) are mixed to obtain a composition for wet coating in which the concentration of the fluorine-containing ether compound is 0.05% by mass. Obtained.
A base material was dipped into each composition, left for 30 minutes, and then the base material was pulled up (dip coat method). The coating film was dried at 200 ° C. for 30 minutes and washed with AK-225 to obtain an evaluation sample (article) having a surface layer on the surface of the substrate.

The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.
The hydrosilylation catalysts shown by abbreviations in Table 1 are as follows.
CAT1: [Fe (mesityl) (μ-mesityl)] Reaction product of ₂ and tBuNC CAT2: N-([2,2'-bipyridin] -6-ylmethylene) -2,4,6-trimethylbenzenamine iron (II) ) Bromide
CAT3: Dibutyltin dilaurate

As shown in Table 1, when a composition having an iron atom content of 15 to 1,500 mass ppm with respect to the total mass of the fluorine-containing ether compound is used, the friction resistance is excellent and the generation of granules is suppressed. It was confirmed that the surface layer could be formed.
On the other hand, it was confirmed that when the iron atom content is less than 15 mass ppm with respect to the total mass of the fluorine-containing ether compound, the friction resistance of the surface layer formed by using the iron atom is inferior (Example 5).
Further, it was confirmed that when the iron atom content exceeds 1,500 mass ppm with respect to the total mass of the fluorine-containing ether compound, granules are generated in the surface layer formed by using the iron atom (Example 6). ..
Further, when a composition containing a tin atom was used, it was confirmed that granules were generated in the surface layer formed by using the composition (Example 7). It is presumed that the reason for this is that the hydrolysis of the fluorine-containing ether compound proceeded too much by the tin atom.

The fluorine-containing ether compound of the present invention can be used in various applications in which lubricity and water / oil repellency are required. For example, coats for display input devices such as touch panels, surface protective coats for transparent glass or transparent plastic members, antifouling coats for kitchens, water-repellent and moisture-proof coats for electronic devices, heat exchangers, batteries, etc. It can be used as an antifouling coat for toiletries, a coat for members that require liquid repellency while conducting, a water repellent / waterproof / water-sliding coat for heat exchangers, a vibration sieve, a surface low friction coat for the inside of cylinders, and the like. As a more specific example of use, a display front protective plate, an antireflection plate, a polarizing plate, an antiglare plate, an antiglare plate on the surface thereof, a touch panel of a device such as a mobile phone or a mobile information terminal. Coats of various devices with display input devices that operate on the screen with human fingers or palms such as sheets and touch panel displays, coats of decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproofing for wiring boards Coating, water-repellent / waterproof / sliding coat for heat exchangers, water-repellent coat for solar cells, waterproof / water-repellent coat for printed wiring boards, waterproof / water-repellent coat for electronic equipment housings and electronic parts, insulation of transmission lines Improved properties, waterproof / water-repellent coats for various filters, waterproof coats for radio wave absorbers and sound-absorbing materials, antifouling coats for baths, kitchen equipment, toiletries, low-friction coats on the surface of vibration sieves and cylinders, mechanical parts, etc. Examples include surface protective coats for vacuum equipment parts, bearing parts, automobile parts, tools and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-15877 filed on August 18, 2017 are cited here and incorporated as the disclosure of the specification of the present invention. Is.

Claims (13)

A composition comprising a fluoroether compound having at least one of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom and a poly (oxyperfluoroalkylene) chain, and an iron atom-containing compound.
The content of iron atoms contained in the iron atom-containing compound is 15 to 1,500 mass ppm with respect to the fluorine-containing ether compound.
A composition characterized in that the iron atom-containing compound is a compound in which a ligand having an aromatic ring is coordinated to an iron atom . The composition according to claim 1, wherein the fluorine-containing ether compound has two or more hydrolyzable groups bonded to the silicon atom. The composition according to claim 1 or 2, wherein the fluorine-containing ether compound has two or more groups composed of silicon atoms to which the hydrolyzable group is bonded. The composition according to any one of claims 1 to 3, wherein the fluorine-containing ether compound is a compound represented by the following formula (1).
[A-O-Z ^1- (R ^f O) _m- ] _j Z ² [-SiR _n L _3-n ] _q (1)
However, if A is a perfluoroalkyl group or -Q [-SiR _n L _3-n ] _k and A is -Q [-SiR _n L _3-n ] _k , j is 1.
Q is a concatenated group of (k + 1) valence, and k is an integer of 1 to 10.
Z ¹ is a single bond, an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom (however, the oxyperfluoroalkylene group is excluded. The oxygen atom in the oxyfluoroalkylene group is , (R ^f O) _m ), or a poly (oxyfluoroalkylene) group ((R ^f O) _m ) having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms. The oxygen atom in the oxyfluoroalkylene group to be bonded is attached to (R ^f O) _m . The oxyfluoroalkylene group bonded to (R ^f O) _m contains one or more hydrogen atoms. Poly (oxyfluoroalkylene). ) The group may contain both an oxyperfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms and an oxyfluoroalkylene group containing one or more hydrogen atoms.)
R ^f is a perfluoroalkylene group, m is an integer of 2 to 200, and when two or more kinds of R ^f O having different carbon atoms are present in (R ^f O) _m , the bonding order of each R ^f O is present. Is not limited,
Z ² is a (j + q) -valent linking group, R is a hydrogen atom or a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, and j and q are integers of 1 or more, respectively. n is an integer of 0 to 2. The composition according to claim 4, wherein A is a perfluoroalkyl group having 1 to 6 carbon atoms and q is 2 to 4. The composition according to claim 4 or 5, wherein L is an alkoxy group having 1 to 4 carbon atoms and n is 0 or 1. The composition according to any one of claims 4 to 6, wherein the SiR _n L _3-n is Si (OCH ₃ ) ₃ . The aromatic ring is at least one of a cyclopentadienyl ring, a pyridine ring and a benzene ring .
The composition according to any one of claims 1 to 7. The composition according to any one of claims 1 to 8, further comprising a liquid medium. The composition according to claim 9, wherein the liquid medium is a fluorinated organic solvent. An article characterized by having a base material and a surface layer formed from the composition according to any one of claims 1 to 10 on the surface of the base material. A composition comprising a fluoroether compound having at least one of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom and a poly (oxyperfluoroalkylene) chain, and an iron atom-containing compound.
The content of iron atoms contained in the iron atom-containing compound is 15 to 1,500 mass ppm with respect to the fluorine-containing ether compound.
A composition characterized in that the iron atom-containing compound is a hydrosilylation catalyst. In the presence of a hydrosilylation catalyst, a compound having a poly (oxyperfluoroalkylene) chain and an ω-alkenyl group, a hydrolyzable group bonded to a silicon atom, at least one of a hydroxyl groups bonded to a silicon atom, and hydrogen bonded to a silicon atom. The method for producing the composition according to any one of claims 1 to 10 by reacting with a silicon compound having an atom.
The hydrosilylation catalyst is the iron atom-containing compound and is
The content of iron atoms contained in the iron atom-containing compound shall be 15 to 1,500 mass ppm with respect to the fluorine-containing ether compound.
Method.