JP6127438B2 - Fluorinated ether composition, substrate having surface layer formed from the composition, and method for producing the same - Google Patents

Description

  The present invention relates to a fluorine-containing ether composition, a substrate having a surface layer formed from the composition, and a method for producing the same.

  Surfaces of base materials such as eyeglass lenses, camera lenses, touch panels, furniture, and the like are likely to be contaminated with fingerprints, sebum, sweat, cosmetics, foods, and the like. The dirt adversely affects visibility, operability, and appearance. Therefore, the surface of the base material is required to have antifouling properties that have excellent water and oil repellency, are less likely to adhere dirt, and can be easily removed even if attached. In consideration of actual use, the surface of the substrate is also required to have antifouling properties and wear resistance.

As a method for imparting antifouling properties and wear resistance to the surface of a substrate, a method of forming a surface layer on the surface of the substrate using the following surface treatment agent is known.
(I) A surface treatment agent containing a perfluoropolyether compound, an acid, water and an organic solvent (Patent Document 1).
(Ii) A surface treatment agent containing a perfluoropolyether compound having a number average molecular weight of 1,100 (Patent Document 2).

International Publication No. 2002/030848 International Publication No. 2009/008380

  However, the surface treatment agents (i) and (ii) may have insufficient surface layer abrasion resistance.

An object of this invention is to provide the fluorine-containing ether composition which can form the surface layer excellent in water / oil repellency, antifouling property, and abrasion resistance.
An object of this invention is to provide the base material which has a surface layer excellent in water and oil repellency, antifouling property, and abrasion resistance, and the manufacturing method of the base material which has this surface layer.

The present invention provides a fluorinated ether composition having the following configurations [1] to [ 7 ], a substrate having a surface layer formed from the composition, a method for producing the same, and a touch panel.
[1] The following fluorinated ether compound (A1), a partially hydrolyzed condensate thereof (A2), or a mixture of the fluorinated ether compound (A1) and the partially hydrolyzed condensate (A2), and the following medium (B) And a fluorine-containing ether composition.
Fluorinated ether compound (A1): having a poly (oxyperfluoroalkylene) chain in the main chain, and having a hydrolyzable silyl group at least at one end of the main chain, A fluorine-containing ether compound in which the hydrolyzable silyl group is bonded to a linking group having an amide bond or a urethane bond, and the number average molecular weight per hydrolyzable silyl group is 2,000 or more.
Medium (B) : a fluorine- containing organic solvent and a non-fluorinated alcohol, the volume average value of the polar term (dP) of the Hansen solubility parameter of the contained solvent is 2 to 6, and the volume of the hydrogen bond term (dH) A medium having an average value of 4 to 12.
[2] The fluorine-containing ether composition according to [1], wherein the fluorine-containing ether compound (A1) is a compound represented by the following formula (1).
X-O- ^Rf- Y (1)
However, the symbols in formula (1) are as follows.
R ^f : poly (oxyperfluoroalkylene) chain.
X: C1-C6 perfluoroalkyl group or Y.
Y: a group represented by any one of the following formulas (Y1) to (Y3).
_{^{-Q 1 -C (O) NH (}} CH 2) n1 -Si (L 1) m1 (R 1) 3-m1 ··· (Y1)
_{^{-Q 2 -CH 2 OC (O)}} NH (CH 2) n2 -Si (L 2) m2 (R 2) 3-m2 ··· (Y2)
_{^{-Q 3 -C (O) N (}} (CH 2) n3 -Si (L 3) m3 (R 3) 3-m3) 2 ··· (Y3)
Q ^{1 to} Q ³ : a divalent linking group.
L ^{1 to} L ³ : hydrolyzable groups.
R ^{1 to} R ³ : a hydrogen atom or a monovalent hydrocarbon group.
m1 to m3: an integer of 1 to 3.
n1 to n3: an integer of 1 to 6 .

[ 3 ] A method for producing a substrate having a surface layer, wherein the medium (B) is removed after the fluorine-containing ether composition of [1] or [2] is applied to the surface of the substrate. .
[ 4 ] A method of applying the fluorine-containing ether composition to the surface of the substrate is a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a dip coating method, a die coating method, an ink jet method, or a flow coating method. The manufacturing method of the base material which has a surface layer of [ 3 ] which is a roll coat method, a cast method, a Langmuir-Blodget method, or a gravure coat method.
[ 5 ] The method for producing a substrate having a surface layer of [ 3 ] or [ 4 ], wherein the material of the substrate is metal, resin, glass, ceramic, stone, or a composite material thereof.

[ 6 ] A substrate having a surface layer formed from the fluorine-containing ether composition of [1] or [2] .
[ 7 ] A touch panel having a surface layer formed of the fluorine-containing ether composition of [1] or [2] on an input surface.

The fluorine-containing ether composition of the present invention can form a surface layer excellent in water / oil repellency, antifouling property and abrasion resistance.
The base material having the surface layer of the present invention has a surface layer excellent in water / oil repellency, antifouling property and abrasion resistance.
According to the method for producing a substrate having a surface layer of the present invention, a substrate having a surface layer excellent in water / oil repellency, antifouling property and abrasion resistance can be produced.

In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
In this specification, a group represented by the formula (Y1) is referred to as a group (Y1). Groups represented by other formulas are also described in the same manner.
The main chain in the present invention is a linear molecular chain in which all molecular chains other than the main chain are regarded as side chains.
The hydrolyzable silyl group in the present invention is a group capable of forming a silanol group (Si—OH) by a hydrolysis reaction.

[Fluorine-containing ether composition]
The fluorinated ether composition of the present invention comprises a fluorinated ether compound (A1), a partially hydrolyzed condensate thereof (A2), or a mixture of the fluorinated ether compound (A1) and a partially hydrolyzed condensate (A2). And medium (B). The fluorine-containing ether composition of the present invention may further contain a catalyst (C) and other additives (D) as necessary.

(Fluorine-containing ether compound (A1))
The fluorine-containing ether compound (A1) has a poly (oxyperfluoroalkylene) chain in the main chain, and has a hydrolyzable silyl group at at least one end of the main chain. The fluorine-containing ether compound (A1) has a poly (oxyperfluoroalkylene) chain in the main chain, and thus does not have a poly (oxyperfluoroalkylene) chain, but has a group compared to a conventional silane compound having a perfluoroalkyl group. A surface layer having excellent water and oil repellency, antifouling properties and abrasion resistance can be formed on the material.
The fluorine-containing ether compound (A1) may be a single compound, or may be a mixture of two or more different poly (oxyperfluoroalkylene) chains, terminal groups, linking groups and the like.

The fluorine-containing ether compound (A1) may have a hydrolyzable silyl group only at one end of the main chain, or may have a hydrolyzable silyl group at both ends of the main chain. From the viewpoint of sufficiently imparting antifouling properties and abrasion resistance to the surface layer, it is preferable to have a hydrolyzable silyl group only at one end of the main chain.
The hydrolyzable silyl group possessed by the fluorine-containing ether compound (A1) can form a chemical bond with the hydroxyl group on the surface of the substrate as described later. When the fluorinated ether compound (A1) has a hydrolyzable silyl group only at one end of the main chain, the fluorinated ether compound (A1) binds to the substrate only at the end. On the other hand, when the fluorine-containing ether compound (A1) has hydrolyzable silyl groups at both ends of the main chain, the fluorine-containing ether compound (A1) binds to the substrate at both ends. As a result, the poly (oxyperfluoroalkylene) chain in the surface layer formed from the fluorine-containing ether compound (A1) having a hydrolyzable silyl group only at one end of the main chain is hydrolyzed at both ends of the main chain. Compared with the poly (oxyperfluoroalkylene) chain in the surface layer formed from the fluorine-containing ether compound (A1) having a decomposable silyl group, it is easy to move on the substrate. Therefore, the surface layer formed using the fluorine-containing ether compound (A1) having a hydrolyzable silyl group only at one end of the main chain can efficiently release the force even when the surface is worn, Excellent wear resistance.

The poly (oxyperfluoroalkylene) chain of the fluorinated ether compound (A1) imparts water / oil repellency to the surface layer and provides good antifouling properties.
The poly (oxyperfluoroalkylene) chain may be composed of only one oxyperfluoroalkylene unit, or may be composed of two or more oxyperfluoroalkylene units having different carbon numbers.

  The oxyperfluoroalkylene unit may have no side chain or may have a side chain. As the oxyperfluoroalkylene unit, an oxyperfluoroalkylene unit having 1 to 10 carbon atoms is preferable, and an oxyperfluoroalkylene unit having 1 to 6 carbon atoms is preferable from the viewpoint of sufficiently imparting antifouling properties and abrasion resistance to the surface layer. More preferred is an oxyperfluoroalkylene unit having 1 to 4 carbon atoms.

When the fluorine-containing ether compound (A1) has a perfluoroalkyl group at the terminal, the water and oil repellency in the surface layer is particularly excellent.
As the fluorine-containing ether compound (A1), a perfluoroalkyl group having 1 to 6 carbon atoms is bonded to one end of a poly (oxyperfluoroalkylene) chain via an oxygen atom, and the other end of the poly (oxyperfluoroalkylene) chain. A compound in which a hydrolyzable silyl group is bonded via a linking group is preferred. The surface layer formed from the compound is more excellent in antifouling property and wear resistance.

  The poly (oxyperfluoroalkylene) chain and the hydrolyzable silyl group are bonded by a linking group having an amide bond or a urethane bond. In the fluorinated ether compound (A1), it is preferable that the poly (oxyperfluoroalkylene) chain and the hydrolyzable silyl group are bonded with a linking group having an amide bond. The combination of the linking group and the medium (B) facilitates contact between the hydrolyzable silyl group and the substrate, and the resulting surface layer has good wear resistance.

The number average molecular weight (Mn) per hydrolyzable silyl group of the fluorine-containing ether compound (A1) is 2,000 or more. Specifically, in the case of the fluorinated ether compound (A1) having a hydrolyzable silyl group only at one end of the main chain, the number average molecular weight (Mn) of the fluorinated ether compound (A1) is 2,000. That's it. In the case of the fluorinated ether compound (A1) having hydrolyzable silyl groups at both ends of the main chain, the number average molecular weight (Mn) of the fluorinated ether compound (A1) is 4,000 or more.
When the number average molecular weight (Mn) per one hydrolyzable silyl group is not less than the lower limit, a surface layer excellent in antifouling properties and wear resistance can be easily formed.

The number average molecular weight (Mn) per hydrolyzable silyl group of the fluorine-containing ether compound (A1) is preferably 2,000 to 10,000, more preferably 2,000 to 7,000, and 3,000 to 5,000 is particularly preferred. In addition, if the number average molecular weight (Mn) per one hydrolyzable silyl group is not more than the upper limit value, the appearance of the surface layer is excellent, and it is used on the outermost surface of electronic members such as cover glass and the surface of various articles. When this is done, the field of view is improved and the operability and design are improved.
The number average molecular weight (Mn) of the fluorinated ether compound in the present invention is measured by gel permeation chromatography (hereinafter referred to as “GPC”) according to the method described in JP-A No. 2001-208736.

  The fluorine-containing ether compound (A1) can be produced by the same method as known fluorine-containing ether compounds. For example, a method of producing a precursor which is a fluorine-containing ether compound having an allyl group at the terminal of the main chain, hydrosilylating the precursor and introducing a hydrolyzable silyl group at the terminal can be mentioned. Moreover, the method of manufacturing the precursor which is a fluorine-containing ether compound which has an ester group at the terminal of a principal chain, and making this precursor react with the compound which has an amino group and a hydrolyzable silyl group is mentioned.

As the fluorine-containing ether compound (A1), the compound (1) is preferable.
X-O- ^Rf- Y (1)
However, the symbols in formula (1) are as follows.
R ^f : poly (oxyperfluoroalkylene) chain.
X: C1-C6 perfluoroalkyl group or Y.
Y: any one of groups (Y1) to (Y3).
_{^{-Q 1 -C (O) NH (}} CH 2) n1 -Si (L 1) m1 (R 1) 3-m1 ··· (Y1)
_{^{-Q 2 -CH 2 OC (O)}} NH (CH 2) n2 -Si (L 2) m2 (R 2) 3-m2 ··· (Y2)
_{^{-Q 3 -C (O) N (}} (CH 2) n3 -Si (L 3) m3 (R 3) 3-m3) 2 ··· (Y3)
Q ^{1 to} Q ³ : a divalent linking group.
L ^{1 to} L ³ : hydrolyzable groups.
R ^{1 to} R ³ : a hydrogen atom or a monovalent hydrocarbon group.
m1 to m3: an integer of 1 to 3.
n1 to n3: an integer of 1 to 6.

R ^f may be composed of only one oxyperfluoroalkylene unit, or may be composed of two or more oxyperfluoroalkylene units having different carbon numbers.
Specific examples of the oxyperfluoroalkylene unit include the following units.
(CF ₂ O),
(CF ₂ CF ₂ O),
(CF ₂ CF ₂ CF ₂ O),
(CF (CF ₃ ) CF ₂ O),
(CF ₂ CF ₂ CF ₂ CF ₂ O) and the like.

As R ^f , when X is a perfluoroalkyl group having 1 to 6 carbon atoms, a molecular chain represented by the following formula (2) is preferable from the viewpoint of sufficiently imparting antifouling property and wear resistance to the surface layer. .
_{- (CF 2 CF 2 O)} d (CF 2 CF 2 CF 2 CF 2 O) e - ··· (2)

However, d is an integer greater than or equal to 0, e is an integer greater than or equal to 0, and d + e is an integer of 5-15. Note that the bonding order of the (CF ₂ CF ₂ O) unit and the (CF ₂ CF ₂ CF ₂ CF ₂ O) unit is not limited. That is, the (CF ₂ CF ₂ O) unit and the (CF ₂ CF ₂ CF ₂ CF ₂ O) unit may be arranged at random, and the (CF ₂ CF ₂ O) unit and the (CF ₂ CF ₂ CF ₂ CF _2). O) Units may be arranged alternately, and two or more blocks composed of a plurality of units may be connected.

As R ^f , when X is Y, a molecular chain represented by the following formula (3) is preferable from the viewpoint of sufficiently imparting antifouling properties and wear resistance to the surface layer.
_{- (CF 2 CF 2 O)} f (CF 2 O) h - ··· (3)
However, f is an integer greater than or equal to 0, h is an integer greater than or equal to 0, and f + h is an integer of 5-25. _{Incidentally,} the order of linking (CF 2 _CF 2 O) units and _(CF 2 O) units is not limited. That is, (CF ₂ CF ₂ O) units and (CF ₂ O) units may be randomly arranged, and (CF ₂ CF ₂ O) units and (CF ₂ O) units may be alternately arranged. Two or more blocks composed of a plurality of units may be connected.

  X is preferably a C 1-6 perfluoroalkyl group from the viewpoint of sufficiently imparting antifouling properties and abrasion resistance to the surface layer. The perfluoroalkyl group may be linear or branched.

Specific examples of the perfluoroalkyl group of X include the following groups.
CF ₃ −,
CF ₃ CF _2- ,
CF ₃ (CF ₂ ) ₂ −,
CF ₃ (CF ₂ ) ₃ −,
CF ₃ (CF ₂ ) ₄ −,
CF ₃ (CF ₂ ) _5- ,
CF ₃ CF (CF ₃₎ - and the like.

X is preferably the following group from the viewpoint of sufficiently imparting friction resistance and antifouling property to the surface layer.
CF ₃ −,
CF ₃ CF _2- ,
_{CF 3 (CF 2) 2 -} .

Y is any one of groups (Y1) to (Y3).
Y is preferably a group (Y1) or a group (Y2), particularly preferably a group (Y1), from the viewpoint of improving the storage stability of the fluorine-containing ether composition and the antifouling property and appearance of the surface layer. .
When two Y are present in the compound (1), that is, when X is Y, the two Ys may be the same or different.

The Q ¹ to Q ^3, from the viewpoint of antifouling property of the surface layer becomes good is preferably a perfluoroalkylene group having 1 to 20 carbon atoms, particularly preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

L ^{1 to} L ³ are hydrolyzable groups.
The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. Compound (1) and Si-L ^{1 at} the end of the partially hydrolyzed condensate thereof (the same applies to Si-L ² and Si-L ³ ) become silanol groups (Si-OH) by hydrolysis reaction. The silanol group further undergoes a condensation reaction between molecules to form a Si—O—Si bond. Further, the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material to form a chemical bond (base material-O-Si). Since the compound (1) has a hydrolyzable silyl group at the terminal, the reactivity with the base material is good, and water and oil repellency can be imparted to the surface of the base material.

Examples of L ^{1 to} L ³ include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (—NCO), and an amino group.
L ^{1 to} L ³ are preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of easy industrial production. As the halogen atom, a chlorine atom is particularly preferable. As L < ¹ > -L < ³ >, a C1-C4 alkoxy group is preferable from the point which is excellent in the storage stability of a compound (1). Further, if necessary long-term storage stability of the compound (1) is, L ¹ ~L ³ is an ethoxy group is particularly preferred. When the reaction time after application of the fluorine-containing ether composition is short, L ^{1 to} L ³ are particularly preferably methoxy groups.

R ^{1 to} R ³ are a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group.
As R < ¹ > -R < ³ >, a monovalent hydrocarbon group is preferable and a monovalent saturated hydrocarbon group is particularly preferable. The number of carbon atoms of the monovalent saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy synthesis.

m1 to m3 are preferably 2 or 3, and particularly preferably 3. The presence of a plurality of L ^{1 to} L ^{3 in} the molecule of compound (1) improves the reactivity between the surface layer and the surface of the substrate.
When m1 to m3 are 2 or more, the plurality of L ^{1 to} L ³ present in one molecule of the compound (1) may be the same as or different from each other. From the viewpoint of availability of raw materials and ease of production, the plurality of L ^{1 to} L ³ present in one molecule of the compound (1) are preferably the same as each other.
n1 to n3 are preferably an integer of 2 to 4, and 2 or 3 is particularly preferable.

Hydrolyzable silyl group ^{_{(-Si (L 1) m1 (}} R 1) 3-m1, -Si (L 2) m2 (R 2) 3-m2, -Si (L 3) m3 (R 3) 3-m3 ) Include —Si (OCH ₃ ) ₃ , —SiCH ₃ (OCH ₃ ) ₂ , —Si (OCH ₂ CH ₃ ) ₃ , —SiCl ₃ , —SiCH ₃ Cl ₂ , —Si (OCOCH ₃ ) ₃ , — Si (NCO) ₃ is preferred. From the viewpoint of ease of handling in industrial production, the hydrolyzable silyl group is particularly preferably —Si (OCH ₃ ) ₃ .

(Partial hydrolysis condensate (A2))
The partially hydrolyzed condensate (A2) is a silanol formed by hydrolyzing a part of the hydrolyzable groups (L ^{1 to} L ³ ) of the hydrolyzable silyl group in the fluorine-containing ether compound (A1). The group (Si—OH) is an oligomer formed by dehydration condensation reaction between molecules. In the partial hydrolysis-condensation product (A2), at least one hydrolyzable group or a hydroxyl group generated by the hydrolysis is present.

The partial hydrolysis-condensation product (A2) is obtained by hydrolyzing a part of the hydrolyzable group of the fluorine-containing ether compound (A1) in the presence of water and a catalyst.
Examples of the catalyst include an acid catalyst and a base catalyst. Examples of the catalyst include inorganic catalysts and organic catalysts. Examples of the inorganic acid catalyst include hydrochloric acid and nitric acid. Examples of the organic acid catalyst include a compound having a carboxy group, a compound having a sulfo group (p-toluenesulfonic acid, etc.) and the like. Examples of the inorganic base catalyst include ammonia. Examples of the organic base catalyst include phenylamine.

The amount of water used for hydrolysis is preferably 0.1 to 3 times in terms of moles relative to the hydrolyzable group of the fluorine-containing ether compound (A1). If the amount of water is not less than the lower limit, partial hydrolysis of the fluorine-containing ether compound (A1) proceeds sufficiently. If the amount of water is less than or equal to the upper limit, the fluorine-containing ether compound (A1) and its partially hydrolyzed condensate (A2) and water are difficult to phase separate.
The hydrolysis of the hydrolyzable group is preferably performed in an organic solvent. As the organic solvent, alcohol-based organic solvents such as methanol are preferable.

(Medium (B))
The medium (B) contains at least a fluorine-containing organic solvent. The fluorine-containing organic solvent is an organic solvent having a fluorine atom in the molecule. When the medium (B) contains the fluorine-containing organic solvent, the fluorine-containing ether compound (A1) or the partial hydrolysis-condensation product (A2) is easily dissolved uniformly in the fluorine-containing ether composition.
The volume average value of the polar term (dP) of the Hansen solubility parameter of the solvent contained in the medium (B) is 2-6. Specifically, when the medium (B) is one kind of fluorine-containing organic solvent, the polar term (dP) of the Hansen solubility parameter of the fluorine-containing organic solvent is in the range of 2-6. When the medium (B) contains two or more solvents, the volume average value of the polar terms (dP) of the Hansen solubility parameter of each solvent is in the range of 2-6.
The volume average value of the polar term (dP) of the Hansen solubility parameter of the solvent contained in the medium (B) is particularly preferably from 3 to 6. When the volume average value of the polar term (dP) is within the above range, it is easy to form a surface layer excellent in antifouling property and wear resistance.
The volume average value of the hydrogen bond term (dH) of the Hansen solubility parameter of the solvent contained in the medium (B) is 4 to 12. Specifically, when the medium (B) is one kind of fluorine-containing organic solvent, the hydrogen bond term (dH) of the Hansen solubility parameter of the fluorine-containing organic solvent is in the range of 4-12. When the medium (B) contains two or more solvents, the volume average value of the hydrogen bond term (dH) of the Hansen solubility parameter of each solvent is in the range of 4-12.
The volume average value of the hydrogen bond term (dH) of the Hansen solubility parameter of the solvent contained in the medium (B) is particularly preferably 7-12. When the volume average value of the hydrogen bond term (dH) is within the above range, it is easy to form a surface layer excellent in antifouling property and wear resistance.

The Hansen solubility parameter is a solubility parameter introduced by Hildebrand. Hansen is divided into three components: a dispersion term (dD), a polar term (dP), and a hydrogen bond term (dH). This is shown in a three-dimensional space. The dispersion term (dD) indicates the effect of dispersion power. The polarity term (dP) indicates the effect due to the force between the dipoles. The hydrogen bond term (dH) indicates the effect of hydrogen bond strength.
The definition and calculation method of the Hansen solubility parameter is described in the following literature.
Charles M. Hansen, “Hansen Solubility Parameters: A Users Handbook”, CRC Press, 2007.

For solvents for which the Hansen solubility parameter literature values are not known, the Hansen solubility parameter can be easily estimated from its chemical structure by using computer software (Hansen Solubility Parameters in Practice (HSPiP)).
In the present invention, the value is used for the solvent registered in the database, and the estimated value according to HSPiP version 3 is used for the solvent not registered.

  Examples of the fluorine-containing organic solvent include fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, fluoroalkylamines, fluoroalcohols and the like. Among these, from the viewpoint of solubility of the fluorine-containing ether compound (A1), fluoroalkanes, fluoroaromatic compounds, and fluoroalkyl ethers are preferable, and fluoroalkyl ethers are particularly preferable.

As the fluoroalkane, a compound having 4 to 8 carbon atoms is preferable. As commercial products, C ₆ F ₁₃ H (AC-2000: product name, manufactured by Asahi Glass Co., Ltd., dP = 0, dH = 0.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name, Asahi Glass Co., Ltd.) Manufactured, dP = 0, dH = 0.), C ₂ F ₅ CHFCHFCF ₃ (Bertrel: product name, manufactured by DuPont, dP = 0, dH = 0) and the like.

  Examples of fluoroaromatic compounds include hexafluorobenzene (dP = 0, dH = 0.), Trifluoromethylbenzene (dP = 5.2, dH = 3.5), perfluorotoluene (dP = 1.7, dH). = 0.2.), Bis (trifluoromethyl) benzene (dP = 6.8, dH = 0.) And the like.

As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. Examples of commercially available _{products, CF 3 CH 2 OCF 2 CF} 2 H (AE-3000:. Product name, manufactured by Asahi Glass _{Company, dP = 4.3, dH = 2.8} ), C 4 F 9 OCH 3 ( Novec -7100 : Product name, manufactured by 3M, dP = 2.2, dH = 1.), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M, dP = 1.3, dH = 1. 5.), C ₆ F ₁₃ OCH ₃ (Novec-7300: product name, manufactured by 3M, dP = 0.2, dH = 0), and the like.

  Examples of the fluoroalkylamine include perfluorotripropylamine (dP = 1, dH = 0.7), perfluorotributylamine (dP = 0, dH = 0.3), and the like.

  As the fluoroalcohol, 2,2,3,3-tetrafluoropropanol (dP = 5.2, dH = 12.1), 2,2,2-trifluoroethanol (dP = 8.3, dH = 16). .4.), Hexafluoroisopropanol (dP = 4.5, dH = 14.7), and the like.

The medium (B) may contain a non-fluorine-based organic solvent and water (dP = 16, dH = 42.3) as necessary in addition to the fluorine-containing organic solvent. The non-fluorine organic solvent is an organic solvent having no fluorine atom in the molecule.
The medium (B) preferably contains water from the viewpoint of promoting the hydrolysis of the hydrolyzable silyl group of the fluorine-containing ether compound (A1) and the partial hydrolysis-condensation product (A2) thereof.

As the non-fluorine 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. Specifically, examples of the non-fluorine organic solvent include hydrocarbon organic solvents, non-fluorine alcohols, non-fluorine ketones, non-fluorine ethers, and non-fluorine esters. A non-fluorinated alcohol is an alcohol having no fluorine atom in the molecule. The same applies to non-fluorinated ketones, non-fluorinated ethers, and non-fluorinated esters.
The non-fluorine-based organic solvent is particularly preferably a non-fluorine-based alcohol in that the fluorine-containing ether compound (A1) can be easily dissolved.

As the hydrocarbon organic solvent, hexane (dP = 0, dH = 0.), Heptane (dP = 0, dH = 0.), And cyclohexane (dP = 0, dH = 0.2) are preferable.
Non-fluorinated alcohols include methanol (dP = 12.3, dH = 22.3), ethanol (dP = 8.8, dH = 19.4), propanol (dP = 6.8, dH = 17). .4), isopropanol (dP = 6.1, dH = 16.4).
Non-fluorinated ketones include acetone (dP = 10.4, dH = 7), methyl ethyl ketone (dP = 9, dH = 5.1), methyl isobutyl ketone (dP = 6.1, dH = 4.1). .) Is preferred.
Non-fluorinated ethers include diethyl ether (dP = 2.9, dH = 4.6), tetrahydrofuran (dP = 5.7, dH = 8), tetraethylene glycol dimethyl ether (dP = 4.2, dH). = 7.3.) Is preferred.
As the non-fluorinated ester, ethyl acetate (dP = 5.3, dH = 7.2) and butyl acetate (dP = 3.7, dH = 6.3) are preferable.

  The medium (B) is selected from the group consisting of at least one selected from the group consisting of fluoroalkanes, fluoroaromatic compounds and fluoroalkyl ethers and a non-fluorine organic solvent consisting only of hydrogen atoms, carbon atoms and oxygen atoms. An organic solvent mixed with at least one selected from the above is preferable.

  10-90 mass% is preferable, as for content of the fluorine-containing organic solvent in a medium (B), 20-80 mass% is more preferable, and 30-70 mass% is especially preferable. If content of the said fluorine-containing organic solvent is more than a lower limit, the solubility of a fluorine-containing ether compound (A1) will be excellent. If content of the said fluorine-containing organic solvent is below an upper limit, the reactivity of a fluorine-containing ether compound (A1) and the hydroxyl group of the surface of a base material will become favorable, and the abrasion resistance of a surface layer will become favorable.

  The total content of the fluorinated organic solvent and the non-fluorinated organic solvent in the medium (B) is preferably 90% by mass or more, and particularly preferably 98% by mass or more. If the said content is more than a lower limit, the solubility of a fluorine-containing ether compound (A1) will be excellent. The upper limit of the content is 100% by mass.

(Catalyst (C))
The fluorine-containing ether composition of the present invention may further contain a catalyst (C) as necessary.
The catalyst (C) promotes the hydrolysis reaction and dehydration condensation reaction of the fluorine-containing ether compound (A1) and the partial hydrolysis-condensation product (A2) thereof. That is, by using the catalyst (C), generation of silanol groups, formation of a partial hydrolysis condensate, and adhesion between the surface of the substrate and the surface layer are promoted.

  Examples of the catalyst (C) include those described in the section of the partial hydrolysis-condensation product (A2), and preferred embodiments thereof are also the same.

(Other additives (D))
The fluorine-containing ether composition of the present invention may further contain another additive (D) as necessary.
Other additives (D) include UV absorbers, light stabilizers, thermosetting stabilizers, antioxidants, leveling agents, antifoaming agents, thickeners, antisettling agents, pigments, dyes, dispersants, charging Examples thereof include an inhibitor, a surfactant (antifogging agent, leveling agent, etc.), metal oxide particles, various resins (epoxy resin, unsaturated polyester resin, polyurethane resin, etc.).

(composition)
The total content of the fluorinated ether compound (A1) and the partially hydrolyzed condensate (A2) thereof in the fluorinated ether composition of the present invention is preferably 0.005 to 1% by mass, and preferably 0.005 to 0.001. 5 mass% is more preferable and 0.005-0.1 mass% is especially preferable. If the said content is more than a lower limit, a surface layer is excellent in friction resistance and antifouling property. If the content is not more than the upper limit, the surface layer has excellent appearance, and when used on the outermost surface of an electronic member, such as a cover glass, or the surface of various articles, the field of view is good and the operability and design are good. Become. The fluorine-containing ether composition is excellent in storage stability.

  The content of the medium (B) in the fluorine-containing ether composition of the present invention is preferably 99 to 99.995% by mass, more preferably 99.5 to 99.995% by mass, and 99.9 to 99.995% by mass. % Is particularly preferred. When the content of the medium (B) is in the above range, the surface layer has excellent appearance, and when used on the outermost surface of an electronic member such as a cover glass or the surface of various articles, the field of view is improved, operability, and design. Sexuality is improved. Further, the surface layer is excellent in antifouling property and wear resistance.

  When the catalyst (C) is included in the fluorine-containing ether composition of the present invention, the content of the catalyst (C) with respect to 100 parts by mass in total of the fluorine-containing ether compound (A1) and the partial hydrolysis-condensation product (A2) is It is preferably 20 to 2,000 parts by mass, more preferably 20 to 1,000 parts by mass, and particularly preferably 20 to 200 parts by mass.

  When the fluorine-containing ether composition of the present invention contains another additive (D), the content of the other additive (D) in the fluorine-containing ether composition of the present invention is 0.001% by mass or less. Preferably, 0.000001-0.001 mass% is especially preferable.

  The solid content concentration of the fluorine-containing ether composition of the present invention is preferably 0.005 to 1% by mass, more preferably 0.005 to 0.5% by mass, and particularly preferably 0.005 to 0.1% by mass. When the solid content concentration is in the above range, the appearance of the surface layer is excellent, and the surface layer is excellent in antifouling property and wear resistance.

Since the fluorine-containing ether composition of the present invention uses at least one of the fluorine-containing ether compound (A1) and the partially hydrolyzed condensate (A2), the surface layer has excellent water and oil repellency and antifouling properties on the substrate. Can be formed.
Further, the fluorinated ether composition of the present invention comprises a fluorinated ether compound (A1), a partially hydrolyzed condensate (A2), or a mixture of the fluorinated ether compound (A1) and a partially hydrolyzed condensate (A2). And a medium (B) in combination, a surface layer having excellent wear resistance can be formed. This is considered as follows.
In a fluorinated ether compound in which a poly (oxyperfluoroalkylene) chain and a hydrolyzable silyl group are bonded with a linking group having an amide bond or a urethane bond, the non-polar poly (oxyperfluoroalkylene) chain is It has a linking group having an amide bond or urethane bond. Therefore, the fluorine-containing ether compound tends to be non-uniformly dissolved in the medium. As a result, the reactivity between the hydrolyzable silyl group of the fluorine-containing ether compound and the hydroxyl group on the substrate surface is lowered, and there are cases where sufficient abrasion resistance cannot be imparted to the surface layer. In contrast, in the fluorine-containing ether composition of the present invention, the medium (B) in which the volume average value of the polar term (dP) and the volume average value of the hydrogen bond term (dH) of the Hansen solubility parameter are within a specific range. ), The fluorine-containing ether compound (A1) and its partial hydrolysis-condensation product (A2) are uniformly dissolved in the medium (B). Therefore, the reactivity between the hydrolyzable silyl group of the fluorinated ether compound (A1) and its partially hydrolyzed condensate (A2) and the hydroxyl group on the substrate surface is increased, and a surface layer having excellent wear resistance is formed. It is considered possible.
Further, as described above, the fluorine-containing ether compound (A1) used in the fluorine-containing ether composition has a number average molecular weight (Mn) per hydrolyzable silyl group of 2,000 or more. The mobility of the poly (oxyperfluoroalkylene) chain in the fluorine-containing ether compound (A1) is high. Therefore, it is easy to release the force when the surface of the surface layer is worn, and excellent wear resistance is obtained.

[Base material having surface layer]
The base material having the surface layer of the present invention has a surface layer formed from the fluorine-containing ether composition of the present invention.

(Base material)
The base material that is the target for forming the surface layer is not particularly limited as long as the base material is required to be imparted with water and oil repellency. Examples of the material for the surface of the substrate include metals, resins, glasses, ceramics, stones, and composite materials thereof.

By forming a surface layer on the surface of the substrate using the fluorine-containing ether composition of the present invention, the substrate is provided with good water and oil repellency, and even when the surface is repeatedly worn, It is provided with excellent wear resistance in which oiliness is not easily lowered and antifouling property that can easily remove fingerprint stains on the surface of the substrate.
The substrate having the surface layer of the present invention is suitable as a member constituting a touch panel because it has good water and oil repellency and excellent antifouling properties and wear resistance. The touch panel means an input device of an input / display device (touch panel device) that combines a display device and a device that inputs contact position information by contact with a finger or the like. The touch panel is composed of a base material and a transparent conductive film, an electrode, a wiring, an IC, and the like depending on the input detection method. By using the surface having the surface layer of the substrate having the surface layer of the present invention as the input surface of the touch panel, a touch panel having good fingerprint removability can be obtained.
The material of the base material for touch panels has translucency. “Having translucency” means that the normal incidence visible light transmittance according to JIS R 3106 is 25% or more.

As a material of the base material for touch panels, glass or transparent resin is preferable.
As the glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically strengthened. Borosilicate glass is particularly preferred.
As a transparent resin base material, an acrylic resin and a polycarbonate are preferable.

  Further, as the base material, a display base material constituting the outermost surface of various displays such as a liquid crystal display, a CRT display, a projection display, a plasma display, and an EL display is also suitable.

1-100 nm is preferable and, as for the film thickness of the surface layer formed in the surface of a base material, 1-50 nm is especially preferable. If the film thickness of the surface layer is not less than the lower limit value, a surface layer excellent in water / oil repellency, antifouling property and abrasion resistance can be easily obtained. If the film thickness of the surface layer is not more than the upper limit value, the utilization efficiency is high.
The film thickness is calculated from the vibration period of the interference pattern obtained by obtaining a reflection X-ray interference pattern by the X-ray reflectivity method using, for example, an X-ray diffractometer ATX-G for thin film analysis (manufactured by RIGAKU). it can.

(Production method)
As a method for producing a substrate having a surface layer of the present invention, a method of removing the medium (B) after applying the fluorine-containing ether composition of the present invention to the surface of the substrate is preferable.

As a method for applying the fluorine-containing ether composition, a known method can be appropriately used.
As a method for applying the fluorine-containing ether composition, a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a dip coating method, a die coating method, an ink jet method, a flow coating method, a roll coating method, a casting method, Langmuir A blow jet method or a gravure coating method is preferred.

As a method for removing the medium (B) in the applied fluorine-containing ether composition, a known method can be appropriately used. Examples of the removal method include heating, reduced pressure, and heating under reduced pressure.
10-300 degreeC is preferable and the temperature in the case of heating has especially preferable 20-200 degreeC.

When producing a substrate having a surface layer, an operation for promoting the reaction between the hydrolyzed silyl group and the substrate may be performed as necessary in order to improve the abrasion resistance of the surface layer. Good. Examples of the operation include heating, humidification, and light irradiation.
Moreover, you may remove the compound in the formed surface layer and which is not chemically combined with another compound and a base material as needed. Specific methods include, for example, a method of pouring a solvent over the surface layer and a method of wiping with a cloth soaked with a solvent.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
Examples 1 to 6 are examples, and examples 7 to 13 are comparative examples.
Abbreviations, measurement methods and evaluation methods are shown below.

(Abbreviation)
Mn: Number average molecular weight.
Mw: mass average molecular weight.
TMS: Tetramethylsilane.
R-225: Dichloropentafluoropropane.
HFIP: hexafluoroisopropanol.
_{R-113: CCl 2 FCClF 2} .
_{CFE-419: CClF 2 CClFCF 2} OCF 2 CClF 2.
TFEO: trifluoroethanol.
PFA: tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer.
DBTDL: Dibutyltin dilaurate.
IPA: isopropanol.
AE3000: Asahiklin AE-3000 (product name, manufactured by Asahi Glass Co., Ltd.).
Vertrel XF (HFC-43-10mee): 2H, 3H-decafluoropentane.
HFE7200: Novec-7200 (product name, manufactured by 3M).
MeOH: methanol.
t-BME: methyl-tert-butyl ether.
AA: acetic acid.
HFC365: 1,1,1,3,3-pentafluorobutane.
MEK: methyl ethyl ketone.
ACT: Acetone.
a: The number of oxyperfluoroalkylene units, and the compound with a is composed of two or more compounds having different values of a. The average value of a is a value obtained from Mn of the compound.

(Measurement of Mn)
Mn of the fluorine-containing ether compound was measured by GPC. GPC was measured under the following conditions according to the method described in JP-A No. 2001-208736.
Mobile phase: R-225 (Asahi Glass Co., Ltd., Asahi Clin AK-225 SEC grade 1) and HFIP mixed solvent (R-225 / HFIP = 99/1 (volume ratio)).
Analytical column: Two PLgel MIXED-E columns (manufactured by Polymer Laboratories) connected in series.
Standard sample for molecular weight measurement: 4 types of perfluoropolyethers having a molecular weight distribution (Mw / Mn) of less than 1.1, Mn of 2,000 to 10,000, and a molecular weight distribution (Mw / Mn) of 1.1 or more One perfluoropolyether having a Mn of 1,300.
Detector: Evaporative light scattering detector.
Mobile phase flow rate: 1.0 mL / min.
Column temperature: 37 ° C.

(Water contact angle)
The substrate having the surface layer was held horizontally, 5 drops of 2 μL of water were placed on the surface of the surface layer, the contact angle was measured, and the average of the five values was determined. The greater the water contact angle, the better the water repellency.

(Hexadecane contact angle)
The substrate having the surface layer was held horizontally, 5 drops of 2 μL of normal hexadecane were placed on the surface of the surface layer, the contact angle was measured, and the average value of the 5 values was obtained. The larger the hexadecane contact angle, the better the oil repellency.

(Abrasion resistance evaluation)
A steel wool bonster (# 0000) was used, and the surface layer surface of the substrate having the surface layer was subjected to 3,000 reciprocating wear at a load of 1 kg / cm ² and a speed of 320 cm / min. Thereafter, the water contact angle was measured by the method described above. The case where the water contact angle after wear was 80 ° or more was evaluated as ◎ (good), the case where the water contact angle was 60 ° or more and less than 80 ° was evaluated as ◯ (possible), and the case where the water contact angle was less than 60 ° was evaluated as × (impossible).

(Storage stability evaluation)
The produced fluorine-containing ether composition was stored at room temperature (20 to 25 ° C.) for 3 months. Then, this fluorine-containing ether composition was apply | coated to the base material by the dip coating method, and the base material which has a surface layer was obtained by heating for 30 minutes and drying in 120 degreeC hot-air circulation oven. Thereafter, the water contact angle of the formed surface layer was measured by the method described above.
○ (possible if the change in water contact angle when using a fluorine-containing ether composition stored for 3 months and the water contact angle when using a fluorine-containing ether composition not stored is less than 5 ° ) X (impossible) when the angle is 5 ° or more.

[Synthesis Example 1: Synthesis of Compound (1-1)]
Compound (1-1) was synthesized by the following method.
CF ₃ CF ₂ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _a CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ C (O) NH (CH ₂ ) ₃ —Si ( OCH ₃ ) ₃ (1-1)
However, a is an integer of 4 to 10, and the average value of a is 7.

In a 300 mL three-necked round bottom flask was charged 14.1 g of sodium borohydride and 350 g of R-225 was added. The mixture was stirred while cooling in an ice bath, and a solution in which 100 g of compound (4), 15.8 g of methanol, and 22 g of R-225 were mixed dropwise so that the internal temperature of the flask did not exceed 10 ° C. in a nitrogen atmosphere. Slowly dropped from the funnel.
_{CF 2 = CFO-CF 2 CF} 2 CF 2 COOCH 3 ··· (4)

After the whole amount was dropped, a solution in which 10 g of methanol and 10 g of R-225 were mixed was further dropped. Thereafter, the ice bath was removed, and stirring was continued while slowly raising the internal temperature of the flask to room temperature. After stirring at room temperature for 12 hours, the reaction solution was cooled again using an ice bath, and an aqueous hydrochloric acid solution was added dropwise until the reaction solution became acidic. After completion of the reaction, the reaction solution was washed once with water and once with saturated brine, and the organic phase was recovered. After the collected organic phase was dried with magnesium sulfate, the solid content was filtered through a filter and concentrated with an evaporator. The collected concentrated liquid was distilled under reduced pressure to obtain 80.6 g (yield 88%) of the compound (5).
_{CF 2 = CFO-CF 2 CF} 2 CF 2 CH 2 OH ··· (5)

NMR spectrum of compound (5);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 2.2 (1H), 4.1 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −85.6 (2F), −114.0 (1F), −122.2 (1F), −123 .3 (2F), -127.4 (2F), -135.2 (1F).

6.64 g of TFEO was placed in a 100 mL eggplant flask connected to a reflux condenser, and 7.32 g of potassium carbonate was added. Furthermore, 19.87 g of compound (5) was added with stirring at 75 ° C. under a nitrogen atmosphere, and the mixture was stirred for 1 hour. Subsequently, the internal temperature of the eggplant flask was raised to 120 ° C., and 113.34 g of Compound (5) was slowly added dropwise while controlling the temperature to be 130 ° C. or lower. After the entire amount was dropped, the mixture was further stirred for 1 hour while maintaining the internal temperature of the eggplant flask at 120 ° C., and the heating was stopped and stirring was continued until the temperature decreased to room temperature. A hydrochloric acid aqueous solution was added to treat excess potassium carbonate, and water and R-225 were added to carry out a liquid separation treatment. After the reaction solution was washed with water three times, the organic phase was recovered and concentrated with an evaporator to obtain a highly viscous oligomer. The obtained oligomer was diluted with 150 g of R-225, separated by silica gel column chromatography (developing solvent: R-225). For each fraction, the average value of the number of units (a + 1) was determined from the integrated value of ¹⁹ F-NMR. In the following formula (6), 48.5 g of the compound (6i) in which the fractions in which the average value of (a + 1) is 7 to 10 are combined, and the compound (6ii) in which the fractions in which the average value of (a + 1) is 13 to 16 are combined. Of 13.2 g was obtained.
_{CF 3 CH 2 -O- (CF 2} CFHO-CF 2 CF 2 CF 2 CH 2 O) a + 1 -H ··· (6)

NMR spectrum of compound (6i);
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS) δ (ppm): 4.1 (2H), 4.8 (16H), 6.7 to 6.9 (8H).
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ ) δ (ppm): −74.2 (3F), −84.3 to −85.1 (16F), −89.4 to -90.5 (16F), -120.2 (14F), -122.0 (2F), -126.6 (14F), -127.0 (2F), -145.1 (8F).
Average number of units (a + 1): 8.

NMR spectrum of compound (6ii);
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS) δ (ppm): 4.1 (2H), 4.8 (28H), 6.7 to 6.9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ ) δ (ppm): −74.2 (3F), −84.3 to −85.1 (28F), −89.4 to -90.5 (28F), -120.2 (26F), -122.0 (2F), -126.6 (26F), -127.0 (2F), -145.1 (14F).
Average number of units (a + 1): 14.

To a 300 mL eggplant flask connected with a reflux condenser, 113.33 g of compound (6i), 5.0 g of sodium fluoride, and 150 g of R-225 were added, and 84.75 g of compound (7) was further added. .
CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF (7)

The solution was stirred at 50 ° C. for 13 hours under a nitrogen atmosphere, and then stirred at 70 ° C. for 3 hours. After removing sodium fluoride from the reaction solution with a pressure filter, excess compound (7) and R-225 were distilled off under reduced pressure. Silica gel chromatography (developing solvent: R-225) was used to remove highly polar impurities, and in the following formula (8), the average number of units (a + 1) was 8, and 10.67 g (yield) of compound (8i). 80%).
_{CF 3 CH 2 -O- (CF 2} CFHO-CF 2 CF 2 CF 2 CH 2 O) a + 1 -C (O) CF (CF 3) OCF 2 CF 2 CF 3 ··· (8)

NMR spectrum of compound (8i);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 4.4 (16H), 4.9 (2H), 6.0-6.2 (8H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −75.2 (3F), −80.0 (1F), −81.9 (3F), −82 .7 (3F), -84.7 to -85.0 (16F), -86.0 (1F), -90.5 to -93.0 (16F), -121.1 (2F), -121 .5 (14F), -128.0 (16F), -130.3 (2F), -132.5 (1F), -145.3 (8F).
Average number of units (a + 1): 8.

An autoclave (made of nickel, internal volume 1 L) was prepared, and a cooler maintained at 0 ° C., a sodium fluoride pellet packed layer, and a cooler maintained at −10 ° C. were installed in series at the gas outlet of the autoclave. Moreover, the liquid return line which returns the liquid aggregated from the cooler hold | maintained at -10 degreeC to an autoclave was installed. The autoclave was charged with 750 g of R-113 and stirred while maintaining at 25 ° C. After nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter referred to as “20% fluorine gas”) was supplied at 25 ° C. and a flow rate of 3.2 L / hour. Blowed for 1 hour. While 20% fluorine gas was blown into the autoclave at the same flow rate, a solution of 130 g of compound (8i) dissolved in 448 g of R-113 was injected over 22 hours. While blowing 20% fluorine gas into the autoclave at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). While heating the interior of the autoclave from 25 ° C. to 40 ° C., 8 mL of a benzene solution containing 0.015 g / mL benzene was injected into R-113, and the benzene solution inlet of the autoclave was closed. After stirring for 20 minutes, while maintaining the inside of the autoclave at 40 ° C., 4 mL of the benzene solution was again injected and the inlet was closed. The same operation was further repeated 7 times. The total amount of benzene injected was 0.6 g. While 20% fluorine gas was blown into the autoclave at the same flow rate, stirring was continued for 1 hour. The pressure in the autoclave was set to atmospheric pressure, and nitrogen gas was blown for 1 hour. The content of the autoclave was concentrated with an evaporator to obtain 152.1 g (yield 99%) of the compound (9i) having an average number of units (a) of 7 in the following formula (9).
_{CF 3 CF 2 -O- (CF 2} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) a CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O-C (O) CF (CF 3) OCF ₂ CF ₂ CF ₃ (9)

NMR spectrum of compound (9i);
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −80.0 (1F), −82.0 to −82.5 (6F), −84.0 ( 30F), -86.7-87.8 (6F), -89.2 (34F), -126.5 (32F), -130.4 (2F), -132.4 (1F).
Average number of units (a): 7.

A 500 mL PFA round bottom eggplant flask was charged with 120 g of compound (9i) and 240 g of R-225. The mixture was stirred while being cooled in an ice bath, and 6.1 g of methanol was slowly dropped from the dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated with an evaporator to obtain 108.5 g (yield: 100%) of compound (10i) having the average number of units (a) of 7 in the following formula (10).
_{CF 3 CF 2 -O- (CF 2} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) a CF 2 CF 2 O-CF 2 CF 2 CF 2 C (O) OCH 3 ··· (10)

NMR spectrum of compound (10i);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 3.9 (3H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −84.0 (30F), −88.2 (3F), −89.2 (34F), −119 .8 (2F), -126.5 (30F).
Average number of units (a): 7.

In a 300 mL eggplant flask, 92.5 g of compound (10i) and 6.51 g of compound (11) were added and stirred for 12 hours.
NH ₂ (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ (11)

  After the completion of stirring, a composition containing 97% by mass of compound (1-1) was obtained. From NMR, it was confirmed that 98% of the compound (9i) was converted to the compound (1-1). In addition, it was confirmed that all of the compound (11) had reacted and methanol as a by-product was produced. It was 2,900 when Mn of the obtained compound (1-1) was measured.

NMR spectrum of compound (1-1);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 0.6 (2H), 1.6 (2H), 2.8 (1H), 3.3 (2H) 3.5 (9H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): -84.1 (30F), -87.9 (3F), -89.3 (34F), -120 .8 (2F), -126.6 (28F), -127.2 (2F).

[Synthesis Example 2: Synthesis of Compound (1-2)]
Compound (1-2) was synthesized by the following method.
CF ₃ CF ₂ —O— (CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) _a CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ C (O) NH (CH ₂ ) ₃ —Si ( OCH ₃ ) ₃ (1-2)
However, a is an integer of 10 to 16, and the average value of a is 13.

In a 200 mL eggplant flask connected to a reflux condenser, 114.72 g of the compound (6ii) obtained in Synthesis Example 1; 8.1 g of sodium fluoride; and 101.72 g of R-225 were added. 95.18 g of compound (7) was added. The solution was stirred at 50 ° C. for 12 hours under a nitrogen atmosphere and then stirred overnight at room temperature. After removing sodium fluoride from the reaction solution with a pressure filter, excess compound (7) and R-225 were distilled off under reduced pressure. Furthermore, high-polarity impurities were removed by silica gel chromatography (developing solvent: R-225), and in the following formula (8), 94.57 g (yield of compound (8ii) having an average number of units (a + 1) of 14). Rate 77%).
_{CF 3 CH 2 -O- (CF 2} CFHO-CF 2 CF 2 CF 2 CH 2 O) a + 1 -C (O) CF (CF 3) OCF 2 CF 2 CF 3 ··· (8)

NMR spectrum of compound (8ii);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 4.4 (28H), 4.9 (2H), 6.0-6.2 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −75.2 (3F), −80.0 (1F), −81.9 (3F), −82 .7 (3F), -84.7 to -85.0 (28F), -86.0 (1F), -90.5 to -93.0 (28F), -121.1 (2F), -121 .5 (26F), -128.0 (28F), -130.3 (2F), -132.5 (1F), -145.3 (14F).
Average number of units (a + 1): 14.

An autoclave (made of nickel, internal volume 3 L) was prepared, and a cooler maintained at 0 ° C., a sodium fluoride pellet packed layer, and a cooler maintained at −10 ° C. were installed in series at the gas outlet of the autoclave. Moreover, the liquid return line which returns the liquid aggregated from the cooler hold | maintained at -10 degreeC to an autoclave was installed. 2,350 g of R-113 was added to the autoclave and stirred while maintaining at 25 ° C. After nitrogen gas was blown into the autoclave at 25 ° C. for 1 hour, 20% fluorine gas was blown in at 25 ° C. and a flow rate of 4.2 L / hour for 1 hour. While blowing 20% fluorine gas at the same flow rate, a solution of 213 g of compound (8ii) dissolved in 732 g of R-113 was injected into the autoclave over 29 hours. While blowing 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure). While heating the interior of the autoclave from 25 ° C. to 40 ° C., 4 mL of a benzene solution containing 0.009 g / mL benzene was injected into R-113, and the benzene solution inlet of the autoclave was closed. After stirring for 20 minutes, while maintaining the inside of the autoclave at 40 ° C., 5 mL of the benzene solution was again injected, and the inlet was closed. The same operation was further repeated 7 times. The total amount of benzene injected was 0.4 g. While 20% fluorine gas was blown into the autoclave at the same flow rate, stirring was continued for 1 hour. The pressure in the autoclave was set to atmospheric pressure, and nitrogen gas was blown for 1 hour. The content of the autoclave was concentrated with an evaporator to obtain 250.1 g (yield 99%) of the compound (9ii) having the average number of units (a) of 13 in the following formula (9).
_{CF 3 CF 2 -O- (CF 2} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) a CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O-C (O) CF (CF 3) OCF ₂ CF ₂ CF ₃ (9)

NMR spectrum of compound (9ii);
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −80.3 (1F), −82.0 to −82.5 (6F), −84.2 ( 54F), -86.9-88.0 (6F), -89.4 (58F), -126.6 (56F), -130.4 (2F), -132.4 (1F).
Average number of units (a): 13.

A 500 mL PFA round bottom eggplant flask was charged with 110 g of compound (9ii) and 220 g of R-225. The mixture was stirred while being cooled in an ice bath, and 3.5 g of methanol was slowly dropped from the dropping funnel under a nitrogen atmosphere, followed by stirring for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated with an evaporator to obtain 103 g (yield: 100%) of the compound (10ii) having the average number of units (a) of 13 in the following formula (10).
_{CF 3 CF 2 -O- (CF 2} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) a CF 2 CF 2 O-CF 2 CF 2 CF 2 C (O) OCH 3 ··· (10)

NMR spectrum of compound (10ii);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 3.9 (3H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −84.0 (54F), −88.2 (3F), −89.2 (58F), −119 .8 (2F), -126.5 (54F).
Average number of units (a): 13.

In a 300 mL eggplant flask, 100.5 g of the compound (10ii) and 4.38 g of the compound (11) of Synthesis Example 1 were added and stirred for 12 hours.
After the completion of stirring, a composition containing 97% by mass of compound (1-2) was obtained. From NMR, it was confirmed that 98% of the compound (10ii) was converted to the compound (1-2). In addition, it was confirmed that all of the compound (11) had reacted and methanol as a by-product was produced. It was 4,900 when Mn of the obtained compound (1-2) was measured.

NMR spectrum of compound (1-2);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 0.6 (2H), 1.6 (2H), 2.8 (1H), 3.3 (2H) 3.5 (9H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): -84.1 (54F), -87.9 (3F), -89.3 (58F), -120 .8 (2F), -126.6 (52F), -127.2 (2F).

[Synthesis Example 3: Synthesis of Compound (1-3)]
Compound (1-3) was synthesized by the following method.
_{(CH 3 O) 3 Si- (} CH 2) 3 NHC (O) O (CH 2) 2 O- (CF 2 CF 2 O) p - (CF 2 O) q CF 2 CH 2 O-C (O) _{NH (CH 2) 3 -Si (} OCH 3) 3 ··· (1-3)
However, p is an integer of 15 to 33, q is an integer of 8 to 25, the average value of p is about 26, and the average value of q is 13.

A solution prepared by dissolving 10 g of D4000 (manufactured by Solvay Solexis, trade name: D4000) and 0.03 g of DBTDL as a catalyst in 25.0 g of CFE-419 was placed in a 300 mL eggplant flask under a nitrogen atmosphere. The internal temperature of the flask was kept below 5 ° C. In the eggplant flask, a solution of 1.2 g of compound (12) dissolved in 10.0 g of CFE-419 was gently added dropwise over 1 hour and stirred for about 12 hours. Excess compound (12) and CFE-419 were distilled off under reduced pressure to obtain 11.0 g of a liquid compound at room temperature.
As a result of NMR analysis of the compound, 99.1 mol% of —CF ₂ CH ₂ OH in D4000 was converted to —CF ₂ CH ₂ OC (O) NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ It was confirmed that. That is, the compound (1-3) was the main product. It was 4,400 when Mn of the obtained compound (1-3) was measured.
O = C = NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (12)

NMR spectrum of compound (1-3);
¹ H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ (ppm): 0.9 (4H), 1.8 (4H), 3.2 (4H), 3.8 (18H) 7.0 (2H).
¹⁹ F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl ₃ ) δ (ppm): −52.1 (11F), −53.7 (11F), −55.4 (4F), −81 .3 (8F), -83.3 (4F), -89.1 (34F), -90.7 (18F).

[Synthesis Example 4: Synthesis of fluorinated ether compound (F)]
Compound (A1-1) of International Publication No. 2009/008380 (CF ₃ O [CF ₂ CF ₂ O] _a CF ₂ C (O) NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , a is 7.3 ), A fluorinated ether compound (F) having a hydrolyzable silyl group only at one end of the main chain was synthesized. It was 1,100 when Mn of the obtained fluorine-containing ether compound (F) was measured.

[Example 1]
(Production of fluorine-containing ether composition)
As a medium (B), a medium in which R-225 and IPA are mixed at a volume ratio of 34.5 / 65.5 (volume average value of polar term (dP): 5.1, volume average of hydrogen bond term (dH)) 300 g of value: 11.2.) Was prepared. Thereafter, 0.15 g of the compound (1-2) produced in Synthesis Example 2 was dissolved in the medium as the fluorinated ether compound (A1) to produce a fluorinated ether composition (X1).

(Manufacture of a substrate having a surface layer)
A surface layer was formed by applying the fluorine-containing ether composition (X1) to the surface of a glass having a thickness of 1 mm by a dip coating method and heating and drying in a 120 ° C. hot air circulating oven for 30 minutes.
Table 2 shows the measurement results of the water contact angle and the hexadecane contact angle of the formed surface layer, and the evaluation results of the abrasion resistance and storage stability.

[Examples 2 to 13]
Fluorinated ether compositions (X2) to (X13) were produced in the same manner as in Example 1 except that the types of the fluorinated ether compound and the medium were changed as shown in Table 1.
A substrate having a surface layer was produced in the same manner as in Example 1 except that the type of the fluorinated ether composition was changed as shown in Table 1.
Table 2 shows the measurement results of the water contact angle and the hexadecane contact angle of the formed surface layer, and the evaluation results of the abrasion resistance and storage stability.
In Table 1, the numerical value in parentheses in the composition of the medium is the volume ratio of each solvent.

The surface layers formed using the fluorine-containing ether compositions (X1) to (X6) of Examples 1 to 6 have a large water contact angle and hexadecane contact angle, exhibit excellent water and oil repellency, and antifouling properties. Excellent wear resistance. The reason why excellent wear resistance was obtained is assumed as follows. Poly (oxyperfluoroalkylene) chain of the fluorinated ether compound (A1) is obtained by using the medium (B) in which the volume average value of the polar term (dP) and the hydrogen bond term (dH) of the solubility parameter is in a specific range. And the polar linking group are considered to be easily dissolved together. For this reason, it is considered that the end of the hydrolyzable silyl group is better dissolved and the reactivity between the end and the substrate is increased.
On the other hand, the surface layers formed using the fluorine-containing ether compositions (X7) to (X13) of Examples 7 to 13 had insufficient wear resistance. The fluorine-containing ether composition (X7) of Example 7 is considered because the number average molecular weight per hydrolyzable silyl group of the fluorine-containing ether compound is less than 2,000. The fluorine-containing ether compositions (X8) to (X10) of Examples 8 to 10 are considered to be because the volume average values of the polar term (dP) and the hydrogen bond term (dH) of the solubility parameter of the medium were not within a specific range. It is done. It is considered that the fluorinated ether composition (X11) of Example 11 did not contain a fluorinated organic solvent in the medium. In the fluorine-containing ether compositions (X12) to (X13) of Examples 12 to 13, it is considered that the polarity term (dP) of the solubility parameter of the medium was out of a specific range.

Claims (7)

The following fluorinated ether compound (A1), a partially hydrolyzed condensate thereof (A2), or a mixture of the fluorinated ether compound (A1) and the partially hydrolyzed condensate (A2), and the following medium (B): A fluorine-containing ether composition.
Fluorinated ether compound (A1): having a poly (oxyperfluoroalkylene) chain in the main chain, and having a hydrolyzable silyl group at least at one end of the main chain, A fluorine-containing ether compound in which the hydrolyzable silyl group is bonded to a linking group having an amide bond or a urethane bond, and the number average molecular weight per hydrolyzable silyl group is 2,000 or more.
Medium (B) : a fluorine- containing organic solvent and a non-fluorinated alcohol, the volume average value of the polar term (dP) of the Hansen solubility parameter of the contained solvent is 2 to 6, and the volume of the hydrogen bond term (dH) A medium having an average value of 4 to 12. The fluorine-containing ether composition according to claim 1, wherein the fluorine-containing ether compound (A1) is a compound represented by the following formula (1).
X-O- ^Rf- Y (1)
However, the symbols in formula (1) are as follows.
R ^f : poly (oxyperfluoroalkylene) chain.
X: C1-C6 perfluoroalkyl group or Y.
Y: a group represented by any one of the following formulas (Y1) to (Y3).
_{^{-Q 1 -C (O) NH (}} CH 2) n1 -Si (L 1) m 1 (R 1) 3-m1 ··· (Y1)
_{^{-Q 2 -CH 2 OC (O)}} NH (CH 2) n2 -Si (L 2) m2 (R 2) 3-m2 ··· (Y2)
_{^{-Q 3 -C (O) N (}} (CH 2) n3 -Si (L 3) m3 (R 3) 3-m3) 2 ··· (Y3)
Q ^{1 to} Q ³ : a divalent linking group.
L ^{1 to} L ³ : hydrolyzable groups.
R ^{1 to} R ³ : a hydrogen atom or a monovalent hydrocarbon group.
m1 to m3: an integer of 1 to 3.
n1 to n3: an integer of 1 to 6. A method for producing a substrate having a surface layer, wherein the medium (B) is removed after the fluorine-containing ether composition according to claim 1 or 2 is applied to the surface of the substrate. The method of applying the fluorine-containing ether composition to the surface of the substrate includes spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, ink jet, flow coating, and roll coating. The manufacturing method of the base material which has a surface layer of Claim 3 which is a method, a cast method, a Langmuir-Blodget method, or a gravure coat method. The manufacturing method of the base material which has a surface layer of Claim 3 or 4 whose material of the said base material is a metal, resin, glass, a ceramic, a stone, or these composite materials. Substrate having a surface layer formed by forming a fluorine-containing ether composition according to claim 1 or 2. The touch panel which has a surface layer formed from the fluorine-containing ether composition of Claim 1 or 2 in an input surface.