JP6107659B2 - Fluorine-containing ether compound, coating liquid, and method for producing substrate having surface treatment layer - Google Patents

Description

  The present invention relates to a fluorine-containing ether compound that can be suitably used for surface treatment for imparting water / oil repellency to a substrate surface, a coating liquid, a group having a surface treatment layer using the fluorine-containing ether compound or the coating liquid. The present invention relates to a method of manufacturing a material.

Since the fluorine-containing compound exhibits high lubricity, water / oil repellency, and the like, it is preferably used as a surface treatment agent. When water and oil repellency is imparted to the surface of the base material, it becomes easy to wipe off dirt, and the dirt removal property is improved.
For example, in a touch panel, water and oil repellency is unlikely to deteriorate even when repeatedly rubbed with a finger, and it is required that the performance of easily removing a fingerprint by wiping is maintained for a long period of time.

Among the fluorine-containing compounds, a compound having a main chain of a perfluoropolyether chain having an ether bond (-O-) in the middle of the perfluoroalkyl chain is a compound having excellent flexibility, and particularly excellent in removing fat and oil stains. .
It is known that a fluorine-containing ether compound having a perfluoropolyether chain as a main chain and a hydrolyzable silyl group at the terminal is used as a surface treatment agent such as an antifouling agent, a lubricant, and a water / oil repellent (patents). Literature 1-5).
The fluorine-containing ether compound having a hydrolyzable silyl group at the end is likely to obtain good durability because the hydrolyzable silyl group chemically bonds to the surface of the substrate.

Patent Documents 1 to 3 describe fluorine-containing ether compounds in which a trimethylene group is bonded to a hydrolyzable silyl group, and an alkylene group having no fluorine atom is bonded to the trimethylene group via an ether bond. Yes.
In Examples of Patent Document 4, a fluorine-containing ether compound in which a trimethylene group is bonded to a hydrolyzable silyl group and an alkylene group is bonded to the trimethylene group via an amide bond or an ether bond is described. The molecular weight of the fluorine-containing ether compound is about 1,100.
Patent Document 5 discloses an organosilicon compound represented by the formula (V), in which a trimethylene group is bonded to a silicon chloride group, and a perfluoroalkylene group is bonded to the trimethylene group via an ether bond. Have been described. It describes that the chlorine atom of the silicon chloride group can be substituted with an alkoxy group. In the organosilicon compound represented by the formula (V), the molecular weight of the fluorine-containing ether compound when n is maximum (n = 4) and three methoxy groups are bonded to the silicon atom is 1,172. is there.

Special table 2008-534696 gazette International Publication No. 2011/060047 International Publication No. 2011/059430 International Publication No. 2009/008380 Japanese Patent Publication No. 4-28273

According to the knowledge of the present inventors, a fluorine-containing ether compound in which an alkylene group is bonded to a trimethylene group via an ether bond as described in Patent Documents 1 to 3 is produced with high purity. In order to achieve high purity, purification or separation work is required. However, the purification or separation operation is difficult for the following reasons.
Generally, as the molecular weight increases, the amount of heat required for atmospheric distillation increases. For example, a compound having a molecular weight of 4,000 requires heating at about 280 ° C. even if the pressure is reduced to 0.1 Pa. Further, when a compound having a hydrolyzable silyl group is to be separated and purified by silica gel chromatography, the hydrolyzable silyl group is adsorbed on the silica gel and the compound does not flow out. As described above, it is very difficult to purify and separate the compounds described in Patent Documents 1 to 3.

The fluorine-containing ether compound having a polar group such as an amide group near the hydrolyzable silyl group as described in Patent Document 4 is applied to a substrate having a polar group on the surface such as a glass substrate. In some cases, the polar groups in the fluorinated ether compound are adsorbed on the surface of the base material by attracting polar groups, and as a result, the reaction between the surface of the base material and the hydrolyzable silyl group may be insufficient. Think.
Further, according to the knowledge of the present inventors, the base material surface-treated with the fluorine-containing ether compound described in Patent Document 5 has water and oil repellency due to repeated friction, for example, by long-term use. We think that it may decline.

The present invention has been made in view of the above circumstances, and can impart good water / oil repellency to the surface of the base material, and is excellent in friction resistance. It aims at providing the fluorine-containing ether compound which can be manufactured.
Another object of the present invention is to provide a method for producing a substrate having a surface treatment layer using the fluorine-containing ether compound.
Another object of the present invention is to provide a coating liquid containing the fluorine-containing ether compound and a medium, and a method for producing a substrate having a surface treatment layer using the coating liquid.

The present invention includes a fluorine-containing ether compound having the following configurations [1] to [1 1 ], a coating liquid, and a method for producing a substrate having a surface treatment layer.
[1] represented by the following formula (1), a number average molecular weight of Ri der 1,500 to 10,000, a purity not less than 98 wt%, the fluorine-containing ether compound.
A-O-R ^f -B (1)
Symbols in the formula (1) indicate the following.
A: C1-C6 perfluoroalkyl group, or B.
R ^f : a linking group represented by the following formula (2).
_{- (CF 2 CF 2 O)} b (CF (CF 3) CF 2 O) c (CF 2 O) d (CF 2 CF 2 CF 2 O) e - ··· (2)
Symbols in the formula (2) indicate the following.
b, c, d and e are each independently an integer of 0 or more, and b + c + d + e is 6 to 147. However, in the formula (2), the bonding order of repeating units of (CF ₂ CF ₂ O), (CF (CF ₃ ) CF ₂ O), (CF ₂ O), and (CF ₂ CF ₂ CF ₂ O) is It is not limited, You may couple | bond with a block at random or a block mutually.
B: Group represented by the following formula (3).
_{- (CH 2) 3 SiL m} R n ··· (3)
The symbol in Formula (3) shows the following.
L: C1-C4 alkoxy group .
R: a hydrogen atom or a monovalent hydrocarbon group.
m and n: m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n = 3.

[2] represented by the following formula (1-2), the number-average molecular weight of Ri der 1,500 to 10,000, a purity of 98 mass% or more, the fluorine-containing ether compound as described in [1].
_{F (CF 2) a11 -O- (} CF 2 CF 2 O) b11 - (CH 2) 3 SiL m R n ··· (1-2)
The symbol in Formula (1-2) shows the following.
L: C1-C4 alkoxy group .
R: a hydrogen atom or a monovalent hydrocarbon group.
a11: An integer of 1 to 6.
b11: An integer of 8 to 84.
m and n: m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n = 3.

[ 3 ] The fluorine-containing ether compound according to [1] or [ 2 ], wherein m is 3 and n is 0 .

[ 4 ] A coating liquid comprising the fluorinated ether compound according to any one of [1] to [ 3 ] and a liquid medium.
[5] The liquid medium, fluorinated alkanes, fluorinated aromatic compound and containing at least one fluorine-based organic solvent is selected from the group consisting of fluoroalkyl ether, coating liquid according to [4].

[ 6 ] A method for producing a substrate having a surface treatment layer, wherein the fluorine-containing ether compound according to any one of [1] to [ 3 ] is vacuum-deposited on the surface of the substrate.
[ 7 ] A method for producing a substrate having a surface treatment layer, wherein the liquid medium is removed after the coating liquid according to [ 4 ] or [ 5 ] is applied to the surface of the substrate.
[ 8 ] The method of applying the coating liquid to the surface of the substrate is spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, ink jet, flow coating, or roll. The manufacturing method of the base material which has a surface treatment layer as described in [ 7 ] which is a coating method, a casting method, a Langmuir-Blodgett method, or a gravure coating method.
[ 9 ] The method for producing a substrate having a surface treatment layer according to any one of [ 6 ] to [ 8 ], wherein the material of the substrate is metal, resin, glass, ceramic, or a composite material thereof.
[ 10 ] A substrate having a surface treatment layer treated with the fluorine-containing ether compound according to any one of [1] to [ 3 ].
[ 11 ] A touch panel having a surface treatment layer treated with the fluorine-containing ether compound according to any one of [1] to [ 3 ] on an input surface.

The fluorine-containing ether compound of the present invention can be easily produced, and can impart good water and oil repellency to the substrate surface. By performing surface treatment on the surface of the substrate using the fluorine-containing ether compound or the coating liquid, a substrate having a surface-treated layer that has excellent friction resistance and is less likely to be deteriorated in water and oil repellency even by repeated friction. can get.
The fluorine-containing ether compound or coating liquid of the present invention can impart good water and oil repellency to the surface of the substrate.
By using the fluorine-containing ether compound or the coating liquid of the present invention to produce a substrate having a surface treatment layer, the surface has excellent water and oil repellency, excellent friction resistance, and surface repellency even by repeated friction. A base material having a surface-treated layer, in which water / oil repellency is hardly lowered, is obtained.

The value of the number average molecular weight of the fluorinated ether compound in the present invention is a value obtained by the following method using NMR analysis. That is, it can be calculated by determining the number of repeating units (average value) from ¹ H-NMR and ¹⁹ F-NMR with reference to the terminal group. A terminal group is A or B in Formula (1).

The surface treatment layer in this invention is a layer formed on the surface of a base material by surface-treating a base material with the fluorine-containing ether compound or coating liquid of this invention.
In the surface treatment with the fluorine-containing ether compound or the coating liquid, as described later, a hydrolyzable silyl group (—SiL _m R _n ) in the fluorine-containing ether compound of the present invention undergoes a hydrolysis reaction to cause Si—OH. Group (silanol group) is formed, and the silanol group reacts between molecules to form a Si—O—Si bond, or the silanol group reacts with a hydroxyl group (substrate—OH) on the surface of the substrate. Thus, a chemical bond (base material-O-Si) is formed.
That is, the surface treatment layer in the present invention is a layer composed of fluorine-containing ether residues on the substrate surface formed by bonding the fluorine-containing ether compound of the present invention to each other and to the substrate surface by the above reaction. Say.

  In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds, precursors and intermediates represented by other formulas.

[Fluorine-containing ether compound]
The fluorine-containing ether compound of the present invention is a compound (1) represented by the following formula (1).
A-O-R ^f -B (1)
Symbols in the formula (1) indicate the following.
A: C1-C6 perfluoroalkyl group, or B.
R ^f : a linking group represented by the following formula (2).
_{- (CF 2 CF 2 O)} b (CF (CF 3) CF 2 O) c (CF 2 O) d (CF 2 CF 2 CF 2 O) e - ··· (2)
Symbols in the formula (2) indicate the following.
b, c, d and e are each independently an integer of 0 or more, and b + c + d + e is 6 to 147. However, in the formula (2), the bonding order of repeating units of (CF ₂ CF ₂ O), (CF (CF ₃ ) CF ₂ O), (CF ₂ O), and (CF ₂ CF ₂ CF ₂ O) is It is not limited, You may couple | bond with a block at random or a block mutually.
B: Group represented by the following formula (3).
_{- (CH 2) 3 SiL m} R n ··· (3)
The symbol in Formula (3) shows the following.
L: Hydrolyzable group.
R: a hydrogen atom or a monovalent hydrocarbon group.
m and n: m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n = 3.

Compound (1) has B at one or both ends. B is a group represented by the above formula (3), and the compound (1) has a hydrolyzable silyl group represented by —SiL _m R _n at the terminal.
In the formula (3), L is a hydrolyzable group. The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, Si-L at the terminal of the compound (1) becomes a Si—OH group (silanol group) by hydrolysis reaction. The silanol group further reacts 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 adhesion to the substrate is good, the durability by repeated friction is good, and the water and oil repellency of the surface of the substrate is improved. It is a possible compound.
Examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (—NCO). As an alkoxy group, a C1-C4 alkoxy group is preferable.
L is 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.
The hydrolyzable group L is particularly preferably an alkoxy group having 1 to 4 carbon atoms in that the outgassing during coating is small and the storage stability of the compound (1) is excellent. Among these, an ethoxy group is particularly preferable when long-term storage stability of the compound (1) is required, and a methoxy group is particularly preferable when the reaction time after coating is short.

In the formula (3), m is an integer of 1 to 3, 2 or 3 is preferable, and 3 is particularly preferable. By the presence of a plurality of L in the molecule, the bond with the surface of the substrate becomes stronger.
When m is 2 or more, the plurality of L present in one molecule may be the same as or different from each other. It is preferable that the raw materials are the same from the viewpoint of easy availability and production.

In the formula (3), R is 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.
R is preferably a monovalent hydrocarbon group, particularly preferably a monovalent saturated hydrocarbon group. 1-6 are preferable, as for carbon number of a monovalent saturated hydrocarbon group, 1-3 are more preferable, and 1-2 are especially preferable.
R is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms. This is preferable because the synthesis is simple.
In the formula (3), n is an integer of 0 to 2, and m + n = 3. n is preferably 0 or 1, particularly preferably 0. When R is 0 or 1 in the molecule, a bond between the silanol group and the surface of the substrate is likely to be formed.

Preferred as the hydrolyzable silyl group (—SiL _m R _n ) are —Si (OCH ₃ ) ₃ , —SiCH ₃ (OCH ₃ ) ₂ , —Si (OCH ₂ CH ₃ ) ₃ , —SiCl ₃ , —Si. (OCOCH _{3) 3,} include -Si _{(NCO) 3.} In view of ease of handling in industrial production, —Si (OCH ₃ ) ₃ is particularly preferable.

  In Formula (1), A is a C1-C6 perfluoroalkyl group or B. A is preferably a C 1-6 perfluoroalkyl group, and particularly preferably a C 1-3 perfluoroalkyl group, since it is excellent in wear resistance and water / oil repellency is less likely to be lowered by repeated wear.

In the formula (1), R ^f is a linking group represented by the above formula (2) and consists of a perfluoropolyether chain.
In R ^f represented by the formula (2), b, c, d and e are each independently 0 or an integer of 1 or more, and b + c + d + e is 6 to 147. As for b + c + d + e, 8-80 are more preferable, and 10-50 are especially preferable. When b + c + d + e is within the above range, the friction resistance is good.
R ^f _is (referred to hereinafter also as the repeating units _{(CF 2 CF 2 O).} ) (CF 2 CF 2 O) recurring units _{of, (CF (CF 3) CF} 2 O) recurring units (hereinafter, the repeating units of ( CF (CF ₃ ) CF ₂ O)), (CF ₂ O) repeating units (hereinafter also referred to as repeating units (CF ₂ O)), and (CF ₂ CF ₂ CF ₂ O) repeating units (Hereinafter also referred to as a repeating unit (CF ₂ CF ₂ CF ₂ O)).

Bonding order of repeating unit (CF ₂ CF ₂ O), repeating unit (CF (CF ₃ ) CF ₂ O), repeating unit (CF ₂ O), and repeating unit (CF ₂ CF ₂ CF ₂ O) in R ^f Is not limited, and may be combined with each other randomly or may be combined with a block.
The compound (1) in that the easily produced stably, it is preferable that Compound (1) does not contain a _{-O-CF 2 -O-CH 2} CH 2 CH 2 Si- structure. That is, in the compound (1), the repeating unit bonded to the trimethylene group of B is a repeating unit (CF ₂ CF ₂ O), a repeating unit (CF (CF ₃ ) CF ₂ O), or a repeating unit (CF ₂ CF ₂ CF ₂ O) is preferably.

Preferable AO—R ^f — in formula (1) is a group represented by the following formulas (4-1) to (4-5) (hereinafter referred to as (4-1) group to (4-5). Group)).
F (CF ₂ ) _a1 —O— (CF ₂ CF ₂ O) _b1 − (4-1)
(A1 is an integer of 1 to 6, b1 is an integer of 8 to 84),
F (CF ₂ ) _a1 —O— (CF (CF ₃ ) CF ₂ O) _c1 − (4-2)
(A1 is an integer of 1 to 6, c1 is an integer of 6 to 58),
F (CF ₂ ) _a1 —O— (CF ₂ CF ₂ CF ₂ O) _e1 − (4-3)
(A1 is an integer of 1 to 6, e1 is an integer of 6 to 58),
_{F (CF 2) a1 -O- (} CF 2 CF 2 O) b2 - (CF 2 O) d1 -CF 2 CF 2 O- ··· (4-4) (a1 is an integer from 1 to 6, b2 is An integer of 5 to 53, d1 is an integer of 5 to 53),
_{F (CF 2) a1 -O- (} CF (CF 3) CF 2 O) c2 - (CF 2 O) d2 - ··· (4-5) (a1 is an integer from 1 to 6, c2 is 4-42 And d2 is an integer of 4 to 42).
Among these, the (4-1) group is preferable in that the ratio of oxygen atoms per unit molecular weight is large, the flexibility is good, and the performance for removing oily and dirt is high. In the (4-1) group, a1 is particularly preferably an integer of 1 to 3, and b1 is an integer of 8 to 40. In the (4-2) group, a group in which a1 is an integer of 1 to 3 and c1 is an integer of 7 to 28 is particularly preferable. In the (4-3) group, a group in which a1 is an integer of 1 to 3 and e1 is an integer of 7 to 28 is particularly preferable. In the (4-4) group, a group in which a1 is an integer of 1 to 3, b2 is an integer of 6 to 26, and d1 is an integer of 6 to 26 is particularly preferable. In the (4-5) group, a group in which a1 is an integer of 1 to 3, c2 is an integer of 5 to 20, and d2 is an integer of 5 to 20 is particularly preferable.

As the compound (1), a fluorine-containing ether compound (1-2) represented by the following formula (1-2) is particularly preferable.
_{F (CF 2) a11 -O- (} CF 2 CF 2 O) b11 - (CH 2) 3 SiL m R n ··· (1-2)
The symbol in Formula (1-2) shows the following.
L: Hydrolyzable group.
R: a hydrogen atom or a monovalent hydrocarbon group.
a11: An integer of 1 to 6.
b11: An integer of 8 to 84.
m and n: m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n = 3.
The preferable range of L and R in Formula (1-2) is the same as the preferable range of the compound (1) described above. a11 is particularly preferably an integer of 1 to 3, and b11 is particularly preferably an integer of 8 to 40.

The number average molecular weight of the compound (1) is 1,300 to 10,000. When the number average molecular weight is in the above range, excellent friction resistance that hardly deteriorates in performance due to repeated friction is easily obtained.
The number average molecular weight of the compound (1) is preferably 1,400 to 7,000, more preferably 1,400 to 5,000, and particularly preferably 1,500 to 4,000.

Since the compound (1) has a perfluoropolyether chain, the content of fluorine atoms is large. By treating the surface of the substrate with the compound (1), the surface of the substrate has good water and oil repellency. Can be granted.
When the number average molecular weight of the compound (1) is in the above range, excellent friction resistance can be obtained. In general, in a fluorine-containing ether compound, the smaller the number average molecular weight, the greater the number of hydrolyzable silyl groups present per unit molecular weight. Therefore, it is considered that the chemical bond with the substrate is stronger. However, the present inventors have confirmed that when the number average molecular weight is less than the lower limit of the above range, the water / oil repellency tends to be reduced by repeated friction. On the other hand, when the number average molecular weight of the compound (1) exceeds the upper limit of the above range, the influence of the decrease in the number of hydrolyzable silyl groups present per unit molecular weight increases, so that the friction resistance decreases.
Furthermore, since compound (1) does not have a polar group, even when applied to a substrate having a polar group, the chemical bond between the hydrolyzable silyl group of compound (1) and the surface of the substrate becomes strong.

[Method for producing fluorine-containing ether compound]
The compound (1) of the present invention introduces a hydrolyzable silyl group into the terminal by hydrosilylating a precursor represented by the following formula (5) and a hydrosilane compound represented by the following formula (7). It can be manufactured by the method. The hydrosilylation reaction is preferably performed using a transition metal catalyst such as platinum (Pt).
A ¹ —O—R ^f —B ¹ (5)
HSiL ¹ _m R _n (7)
Symbols in formulas (5) and (7) indicate the following.
A ¹ : The same C 1-6 perfluoroalkyl group as A in the formula (1), or B ¹ .
R ^f : the same group as R ^f in the formula (1).
B ¹ : Allyl group.
L ¹ : Hydrolyzable group.
R: the same group as R in the formula (1).
m and n: the same numerical values as m and n in the formula (1), respectively.

For example, in the compound (1), when A is a C 1-6 perfluoroalkyl group, the precursor (5-1) represented by the following formula (5-1) is hydrosilylated and hydrolyzed at the terminal. It can manufacture by the method of introduce | transducing a functional silyl group.
A—O—R ^f —CH ₂ CH═CH ₂ (5-1)
In the formula (1), when A is B, the precursor (5-2) represented by the following formula (5-2) is hydrosilylated, and a hydrolyzable silyl group is introduced into the terminal. can do.
^{_{CH 2 = CHCH 2 -O-R}} f -CH 2 CH = CH 2 ··· (5-2)
Precursor (5-1) or (5-2) is, ^{A-O-R f} - can be prepared by known methods depending on the structure of the. A method for producing the precursor (5-1) or (5-2) will be described later.

In the hydrosilylation reaction, allyl group transfer is likely to occur, and there is a risk that a compound having R ^f other than the compound (1) is produced as a by-product. 1-propenyl group is generated by transfer of the allyl group (that is, 2-propenyl group), and the hydrosilane compound reacts with the unsaturated group of 1-propenyl group, which is different from B of compound (1). A group is generated. When the precursor (5-1) is reacted with a hydrosilane compound (7) in which L ¹ is L, a compound (6-2) represented by the following formula (6-2) is generated by transfer of the allyl group. However, it is considered that the compound (6-1) represented by the following formula (6-1) is by-produced by the hydrosilylation reaction.
_{^{A-O-R f -CH 2}} CH (SiL m R n) CH 3 ··· (6-1)
A—O—R ^f —CH═CHCH ₃ (6-2)
In the case of the body (5-2), it can be considered that one of two allyl groups is transferred or both are transferred, and two types of by-products generated by this transfer and hydrosilylation reaction are considered.
Furthermore, in the production of compound (1) by hydrosilylation reaction, unreacted substances may remain. For example, when the compound (1) is produced from the precursor (5-1) and the unreacted precursor (5-1) remains in the obtained compound (1), the precursor (5-1) Becomes an impurity. When the compound (1) is produced from the precursor (5-2), if one allyl group is unreacted, it also becomes an impurity. Further, the compound (6-2) and the like generated by the transfer of the allyl group also becomes an impurity if left without undergoing a hydrosilylation reaction. Hereinafter, the by-product is used in the meaning including the remaining unreacted product.

In the present invention, identification and quantification of by-products in the fluorine-containing ether compound are performed by ¹ H-NMR (300.4 MHz) and ¹⁹ F-NMR (282.7 MHz). In addition, when producing the target compound (1) by hydrosilylating the precursor (5-1) or (5-2), a compound that may be generated by hydrosilylation (in the case of the precursor (5-1) In the case where no spectral peak derived from the compound (6-1) or the compound (6-2)) is detected, the by-product content is defined as zero. Moreover, when the spectrum peak originating in these impurities is observed, content of this by-product is calculated | required by determination by an internal standard.
Identification and quantification of components mixed in the production process of compound (1) are performed by ¹ H-NMR (300.4 MHz) and ¹⁹ F-NMR (282.7 MHz).

The compound (1) obtained by hydrosilylating the precursor (5-1) or (5-2) yields a fluorine-containing ether compound with few by-products and less impurities. Although the reason why a fluorine-containing ether compound with few impurities is obtained has not been clarified, the present inventors consider as follows.
In general, it is known that a high reaction selectivity can be obtained in a hydrosilylation reaction to a terminal vinyl group (—CH═CH ₂ ) by using a transition metal catalyst such as Pt. However, according to the knowledge of the present inventors, in the case of allyl ether (—CH ₂ —O—CH ₂ CH═CH ₂ ) in which —CH ₂ — is bonded to the allyl group via an ether bond, the reaction is performed. The selectivity is low. According to Patent Document 3, since the reaction selectivity is low, it contains a by-product of less than 15 mol%. The cause is considered to be that a by-product is generated by some interaction between the lone pair of etheric oxygen atoms and the transition metal catalyst.
Since the precursor (5-1) or (5-2) is an allyl ether in which —CF ₂ — is bonded to an allyl group via an ether bond, non-determination on the etheric oxygen is caused by the electron withdrawing property of fluorine. The charge density of the shared electron pair is reduced. It is presumed that the interaction between the etheric oxygen atom and the transition metal catalyst described above is weakened or eliminated, whereby the formation of by-products is suppressed and the reaction selectivity of the hydrosilylation reaction is high.

Furthermore, in order to increase the reaction rate of the hydrosilylation reaction, the hydrosilane compound (7) is preferably HSiX _m R _n (X represents a halogen atom). X is particularly preferably a chlorine atom. Compared with the case where L ^{1 of the} hydrosilane compound (7) is a hydrolyzable group other than X, the reactivity of HSiX _m R _n is higher, so that allyl group transfer is relatively less likely to occur. Remaining is also reduced. Thereby, a fluorine-containing ether with fewer impurities is obtained.
As described above, the hydrolyzable group L is preferably an alkoxy group having 1 to 4 carbon atoms. In that case, it is preferable to react HSiX _m R _n to produce a compound (1) in which L is X, and then convert X to an alkoxy group to obtain a compound (1) in which L is an alkoxy group. . Thereby, the fluorine-containing ether which is high in purity and whose hydrolyzable group is an alkoxy group can be obtained.
As a method of substituting X with an alkoxy group, a known method can be used. For example, when X is a chlorine atom, a method in which a trialkyl ester of orthoformate such as methyl orthoformate is reacted to convert the chlorine atom to an alkoxy group, an alkali metal alkoxide such as sodium methoxide is reacted to convert the chlorine atom into an alkoxy group The chlorine atom can be substituted with an alkoxy group by a method of converting into an alkoxy group.

In general, fluorinated ethers having a main chain composed of a perfluoropolyether chain and a terminal group having a hydrolyzable silyl group are produced by adding a hydrosilane compound to an unsaturated group such as an allyl group by a hydrosilylation reaction. In this case, impurities having a structure with the same main chain and different ends are likely to be generated, and it is difficult to remove the generated impurities. Therefore, fluorine-containing ethers containing such impurities are used as they are without being generated. However, the fluorine-containing ethers having a large amount of impurities may deteriorate the properties required for their use.
As described above, the compound (1) produced by the method of forming B by adding a hydrosilane compound to an allyl group by a hydrosilylation reaction often contains a small amount of impurities. It is difficult to separate and purify the impurity from the target product because the target product and the impurity are compounds having R ^f in common and the difference in the terminal structure having a hydrolyzable silyl group is slight. It is. However, when the compound (1) having the specific structure described above is produced by a hydrosilylation reaction from the precursor having the specific structure described above, conventional fluorine-containing ethers having a similar hydrolyzable silyl group can be obtained. Compared to the case, the compound (1) having a small amount of impurities can be obtained.
Since the production of the compound (1) produces less impurities, the compound (1) with high purity can be easily obtained. Most of the impurities after removing the easily removed can components of the solvent and catalyst and the like used in the reaction is believed to be unreacted having a by-product or R ^f have the above R ^f, these impurities It is an impurity that is difficult to remove by purification.

The fluorine-containing ether compound represented by the formula (1) in the present invention also means a high-purity fluorine-containing ether compound having a small content of impurities that are difficult to separate. That is, the fluorine-containing ether compound represented by the formula (1) and an impurity having R ^f generated during the production thereof, and the content of the impurity with respect to the total of the fluorine-containing ether compound and the impurity is The composition of the fluorine-containing ether compound which is 95 mass% or more is also meant.
The purity of the fluorine-containing ether compound represented by the formula (1) is particularly preferably 98% by mass or more. That is, the content of impurities is particularly preferably 2% by mass or less. When the purity is not less than the above lower limit, the water / oil repellency and friction resistance when used for the surface treatment of the substrate are improved. When the impurity content is not more than the upper limit of the above range, the water and oil repellency and friction resistance when used for the surface treatment of the substrate are improved.
In applications that require a high-purity fluorine-containing ether compound such as dry coating, it is preferable to use a fluorine-containing ether compound having a purity of 95% by mass or more. Moreover, although it is preferable to use such a fluorine-containing ether compound with a high purity also in another use, depending on a use, a fluorine ether compound with a somewhat lower purity can also be used. In any case, since the fluorine-containing ether compound of the present invention has a high purity, a surface treatment layer having excellent properties as described above can be obtained.

(Method for producing precursor (5-1))
<Preparation method (i) of precursor (5-1-1)>
An example in which a1 = 1 and b1 = x in formula (4-1) is used as the method for producing the precursor (5-1-1) when A-O- ^Rf- is the (4-1) group. Will be described.
The compound (11) represented by the following formula (11) is heated in the presence of a metal fluoride catalyst (for example, NaF, CsF, KF, AgF, etc.) to thermally decompose the ester, and then allyl bromide ( The precursor (5-1-1) is obtained by reacting Br—CH ₂ CH═CH ₂ ).

<Preparation method (ii) of precursor (5-1-1)>
The precursor (5-1-1) can also be produced by the following method.
Compound represented by the following formula (12) to (12), the metal fluoride catalyst (e.g. NaF, CsF, KF, AgF, etc.) is reacted with allyl bromide _{(Br-CH 2 CH = CH} 2) in the presence of Thereby, a precursor (5-1-1) is obtained.

<Precursor (5-1-2) Production Method (iii)>
^{A-O-R f} - is the manufacturing method of (4-1) precursor is a group (5-1-2), it is a1 = 3, c1 = x in the formula (4-1) Example Will be described.
The compound (21) (hexafluoropropylene oxide) represented by the following formula (21) is subjected to ring-opening polymerization using an alkali metal fluorination catalyst (for example, CsF) in an ether solvent such as glyme. A compound (22) represented by (22) is obtained.
Like the manufacturing method to the compound (22) (ii), a metal fluoride catalyst (e.g. NaF, CsF, KF, AgF, etc.) is reacted with allyl bromide in the presence of _{(Br-CH 2 CH = CH} 2) Thereby, a precursor (5-1-2) is obtained.

<Preparation method (iv) of precursor (5-1-3)>
^{A-O-R f} - precursor when it is the (4-3) based on the manufacturing method of (5-1-3), it is a1 = 3, e1 = x in the formula (4-3) Example Will be described.
First, tetrafluoroethylene and paraformaldehyde are reacted to obtain 2,2,3,3-tetrafluorooxetane (the following formula (31)). This step can be carried out, for example, in a method of reacting in anhydrous hydrogen fluoride at 30 to 60 ° C., preferably 50 ° C. for 24 hours.

Next, the obtained 2,2,3,3-tetrafluorooxetane is subjected to ring-opening polymerization in an ether solvent such as diglyme using an alkali metal fluorination catalyst (for example, CsF) to obtain the following formula (32 ) Is obtained.
Further, the compound (33) represented by the following formula (33) is obtained by substituting the fluorine atom for the hydrogen atom remaining in the intermediate (32) using fluorine gas. This step can be performed, for example, by a method of fluorinating residual hydrogen in the molecule with fluorine gas diluted with nitrogen for 70 hours while gradually raising the temperature of the intermediate (32) to 70 to 100 ° C.

Next, allyl bromide (Br—CH ₂ CH═CH ₂ ) is added to the compound (33) in the presence of a metal fluoride catalyst (eg, NaF, CsF, KF, AgF, etc.) in the same manner as in the production method (ii). Is reacted to obtain the precursor (5-1-3).

<Preparation method (v) of precursor (5-1-4)>
The production method of the precursor (5-1-4) when A—O—R ^f — is the (4-4) group is defined as a1 = 1, b2 = x ¹ , d1 in the formula (4-4). = with an example a x ² will be described.
First, tetrafluoroethylene is reacted with oxygen to obtain a compound (41) represented by the following formula (41). This step can be performed, for example, by the following method.
That is, a photochemical reactor cooled to −60 ° C. is charged with hydrofluorocarbon as a solvent and irradiated with ultraviolet rays while oxygen is added to the reactor at a certain rate. When tetrafluoroethylene is added thereto at a specific rate, tetrafluoroethylene reacts with oxygen to obtain compound (41). Compound (41) is an intermediate in which an unstable peroxide skeleton remains in the molecule.
Next, the unstable peroxide site in the compound (41) is decomposed to obtain the compound (42) represented by the following formula (42). This step can be performed, for example, by treating the compound (41) with nitrogen-diluted fluorine gas at 200 ° C. or higher.

Thereafter, allyl bromide (Br—CH ₂ CH═CH ₂ ) is added to the compound (42) in the presence of a metal fluoride catalyst (eg, NaF, CsF, KF, AgF, etc.) in the same manner as in the production method (ii). Is reacted to obtain the precursor (5-1-4).

[Method for producing substrate having surface treatment layer]
Since the fluorine-containing ether compound of the present invention has high purity, it can be used as it is in a method for producing a substrate having a surface treatment layer by treating the surface of the substrate by a dry coating method. The purity of the fluorine-containing ether compound is preferably 95% by mass or more, particularly preferably 98% by mass or more. The fluorine-containing ether compound of the present invention is suitable for forming a surface treatment layer having excellent adhesion by a dry coating method. Examples of the dry coating method include vacuum deposition, CVD, sputtering, and the like. From the viewpoint of suppressing the decomposition of the fluorinated ether compound and the simplicity of the apparatus, the vacuum deposition method can be suitably used. The vacuum deposition method can be subdivided into resistance heating method, electron beam heating method, high frequency induction heating method, reactive deposition, molecular beam epitaxy method, hot wall deposition method, ion plating method, cluster ion beam method, etc. Any method can be applied. The resistance heating method can be suitably used from the viewpoint of suppressing the decomposition of the fluorinated ether compound and the simplicity of the apparatus. The vacuum deposition apparatus is not particularly limited, and a known apparatus can be used.

The film forming conditions in the case of using the vacuum vapor deposition method vary depending on the type of the vacuum vapor deposition method to be applied. In the case of the resistance heating method, the vacuum degree before vapor deposition is preferably 1 × 10 ⁻² Pa or less, and preferably 1 × 10 ⁻³ Pa. The following are particularly preferred: The heating temperature of the vapor deposition source is not particularly limited as long as the fluorine-containing ether compound vapor deposition source has a sufficient vapor pressure. Specifically, 30 to 400 ° C is preferable, and 50 to 300 ° C is particularly preferable. When the heating temperature is equal to or higher than the lower limit of the above range, the film formation rate is good. When the amount is not more than the upper limit of the above range, water and oil repellency and friction resistance can be imparted to the surface of the substrate without causing decomposition of the fluorine-containing ether compound.
At the time of vacuum deposition, the substrate temperature is preferably in the range from room temperature (20 to 25 ° C.) to 200 ° C. When the substrate temperature is 200 ° C. or lower, the film formation rate becomes good. The upper limit of the substrate temperature is more preferably 150 ° C. or less, and particularly preferably 100 ° C. or less.
When the surface of the substrate is treated by a dry coating method using a fluorine-containing ether compound, the surface treatment layer formed on the surface of the substrate by the treatment preferably has a thickness of 1 to 100 nm, preferably 1 to 50 nm. Particularly preferred. When the film thickness of the surface treatment layer is not less than the lower limit of the above range, the effect of the surface treatment can be sufficiently obtained. Use efficiency is high as it is below the upper limit of the said range. The film thickness is measured by, for example, using an X-ray diffractometer ATX-G for thin film analysis (manufactured by Rigaku) to obtain an interference pattern of reflected X-rays by the X-ray reflectivity method, and the vibration period of the interference pattern. It can be calculated from

  In particular, in the vacuum deposition method, since the purity of the fluorine-containing ether compound is high and the content of impurities is small, the effect of improving water and oil repellency and friction resistance is great. This is because by-products and unreacted raw materials having a low molecular weight such as the compound (6-2) which is an impurity are vapor-deposited on the surface of the base material before the compound (1). It is thought that the chemical bond between the supporting compound (1) and the surface of the base material is hindered from being suppressed.

The fluorine-containing ether compound of the present invention forms a coating film by coating a coating liquid containing the compound on the surface of the substrate, and removes the liquid medium from the coating film to thereby form a substrate having a surface treatment layer. Can be manufactured.
As a method for applying the coating liquid, a known method can be appropriately used.
Application methods include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, ink jet method, flow coating method, roll coating method, casting method, Langmuir-Blodgett method or gravure coating. The method is preferred.
The method for removing the liquid medium may be any method capable of evaporating and removing the liquid medium from the coating film of the coating liquid, and known methods can be appropriately used. The temperature at which the liquid medium is removed by evaporation may be at least the boiling point of the liquid medium, and is appropriately selected depending on the type of the liquid medium. In some cases, the liquid medium can be removed under reduced pressure, so that the liquid medium can be removed by evaporation at a temperature lower than the boiling point of the liquid medium. The specific temperature at which the liquid medium is removed by evaporation depends on the type of the liquid medium, but is preferably 10 to 300 ° C, particularly preferably 20 to 200 ° C.
After the liquid medium is removed by evaporation, the surface treatment layer formed on the surface of the substrate is preferably 1 to 100 nm, particularly preferably 1 to 50 nm, as a film thickness. When the film thickness of the surface treatment layer is not less than the lower limit of the above range, the effect of the surface treatment can be sufficiently obtained. Use efficiency is high as it is below the upper limit of the said range. The film thickness can be measured in the same manner as the method for measuring the film thickness of the surface treatment layer formed by the dry coating method.

In order to improve the durability against friction of the surface treatment layer after forming the surface treatment layer on the surface of the substrate by the dry coating method or the method using a coating liquid, the fluorine-containing ether compound and the substrate are used as necessary. You may perform operation for promoting reaction with. Examples of such operations include heating, humidification, and light irradiation. For example, by heating a substrate on which a surface treatment layer is formed in an atmosphere having moisture, hydrolysis reaction of hydrolyzable silyl groups to silanol groups, reaction of hydroxyl groups on the substrate surface with silanol groups, silanols, Reactions such as formation of siloxane bonds by group condensation reactions can be promoted.
After the surface treatment, compounds in the surface treatment layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific methods include, for example, a method of pouring a solvent over the surface treatment layer and a method of wiping with a cloth soaked with a solvent.

(Coating solution)
The coating liquid of the present invention contains compound (1) and a liquid medium. The coating solution may be liquid, may be a solution, or may be a dispersion.
The coating liquid should just contain the compound (1), and may contain the impurity containing the by-product produced | generated at the manufacturing process of the compound (1). Preferably, the coating liquid contains the fluorine-containing ether compound having a purity of 95% by mass or more and a liquid medium.
The compound (1) of the present invention is preferably contained in the coating solution in an amount of 0.001 to 10% by mass, particularly preferably 0.1 to 1% by mass.

<Liquid medium>
The boiling point of the liquid medium in the present invention is preferably from 30 to 200 ° C, particularly preferably from 40 to 150 ° C. As the liquid medium, an organic solvent is preferable. The organic solvent may be a fluorinated organic solvent or a non-fluorinated organic solvent.
Examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferable. The ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms in the fluorinated alkane is preferably 70% or more and a compound having at least one hydrogen atom. Examples of commercially available products include 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, manufactured by Asahi Glass Co., Ltd.), C ₂ F ₅ CHFCHFCCF. ₃ (Bertrel: product name, manufactured by DuPont).
Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.
As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. In the present invention, fluoroalkyl ether means difluoroalkyl ether and alkylfluoroalkyl ether. The fluoroalkyl group in these two ethers is preferably a polyfluoroalkyl group, and the polyfluoroalkyl group may be a perfluoroalkyl group. As the alkyl fluoroalkyl ether, alkyl perfluoroalkyl ether is preferable. The ratio of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms in the fluoroalkyl ether is preferably 60% or more and a compound having at least one hydrogen atom. As commercially available products, 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 0CH 3} ( Novec -7100: product name, 3M _{Co.), C} 4 F ₉ 0C ₂ H ₅ (Novec -7200: product name, manufactured by 3M _{Co.), C 6 F 13 0CH 3} ( Novec -7300: product name, 3M Co., Ltd.).
Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
As the fluorine-based organic solvent, a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether are preferable from the viewpoint of solubility of the compound (1), and among them, a fluoroalkyl ether is particularly preferable.

As the non-fluorine-based organic solvent, a compound consisting of only hydrogen atoms and carbon atoms and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferable. Hydrocarbon organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ethers System organic solvents and ester organic solvents.
As the hydrocarbon organic solvent, hexane, heptane, cyclohexane and the like are preferable.
As the alcohol organic solvent, methanol, ethanol, propanol, isopropanol and the like are preferable.
As the ketone organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferable.
As the ether organic solvent, diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether and the like are preferable.
As the ester organic solvent, ethyl acetate, butyl acetate and the like are preferable.
As the non-fluorine organic solvent, a ketone organic solvent is particularly preferable from the viewpoint of the solubility of the compound (1).

The liquid medium in the present invention includes a fluorinated alkane, a fluorinated aromatic compound, a fluoroalkyl ether, a compound consisting only of hydrogen atoms and carbon atoms, and a group consisting of a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms. At least one organic solvent selected is preferred. In particular, a fluorine-based organic solvent selected from a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether is preferable.
The liquid medium may be a mixture of two or more of the above organic solvents, or a mixture of the above organic solvent and another liquid medium (an organic solvent other than the above). In the case of a mixture, it is preferable that at least one organic solvent selected from the above organic solvents is contained in a total amount of 90% by mass or more of the whole liquid medium from the viewpoint of improving the solubility of the fluorinated ether compound.
The coating liquid of the present invention preferably contains 90 to 90.999% by mass of a liquid medium, particularly preferably 99 to 99.99% by mass.

The coating liquid may contain other components in addition to the compound (1) and the liquid medium as long as the effects of the present invention are not impaired.
In the coating liquid, a part of the fluorine-containing ether compound may be a partially hydrolyzed condensate. The partially hydrolyzed condensate refers to a compound in which two or more molecules of a fluorine-containing ether compound are polymerized by a hydrolytic condensation reaction. That is, it refers to a compound in which a hydrolyzable group of a fluorine-containing ether compound is hydrolyzed and a siloxane bond is generated by a dehydration condensation reaction between the generated silanol groups, and the fluorine-containing ether compound is multimerized. A partially hydrolyzed condensate that has been multimerized to such an extent that the solubility in a liquid medium does not decrease can impart good water and oil repellency to the substrate surface, like the fluorinated ether compound.
Examples of other components that may be contained in the coating liquid include known additives such as an acid catalyst and a basic catalyst that promote hydrolysis and condensation reaction of the hydrolyzable silyl group.
Examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, and the like.
Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, ammonia and the like.
The content of other components in the coating liquid is preferably 10% by mass or less, and particularly preferably 1% by mass or less.

The solid content concentration of the coating liquid is preferably 0.001 to 10% by mass, particularly preferably 0.01 to 1% by mass.
The solid content concentration of the coating liquid in the present invention is calculated from the mass of the coating liquid before heating and the mass after evaporating and removing the liquid medium by heating in a convection dryer at 120 ° C. for 4 hours. Value.

(Base material)
In the present invention, the base material to be surface-treated is not particularly limited as long as it is a base material to which water and oil repellency is required. Examples of the material for the surface of the substrate include metals, resins, glasses, ceramics, and composite materials thereof.
By treating the surface of the substrate with the fluorine-containing ether compound (compound (1)) or the coating liquid containing the compound of the present invention to form a surface treatment layer, good water and oil repellency is imparted. In addition, even if the surface is repeatedly rubbed, excellent friction resistance is obtained in which the water and oil repellency is hardly lowered. Therefore, the substrate having the surface treatment layer obtained in this way has good water and oil repellency, and excellent friction resistance that is unlikely to decrease the water and oil repellency even when the surface is repeatedly rubbed. Since it has, it is suitable as a member which comprises a touch panel. 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 making the surface having the surface treatment layer of the base material 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. In this specification, “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 a transparent resin base material is preferable. As the glass, soda lime glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, and chemically tempered glass is particularly preferable. As the transparent resin substrate, polycarbonate is preferable.
Further, as the substrate in the present invention, a display substrate 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, and the fluorine-containing ether compound of the present invention or By forming the surface treatment layer by the surface treatment using the coating liquid, good dirt removal property can be obtained.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the following, “%” is “% by mass” unless otherwise specified.

[Example 1: Production of fluorinated ether compound (15A)]
In this example, the precursor production method (i) was used.
First, 19.0 g of the compound (11A) represented by the above formula (11) and having an average x value of 11.2 in the formula (11) in a 50 mL eggplant flask connected to a simple distillation apparatus, and 0.02 of CsF. 352 g was added and the temperature was raised to 80 ° C. to thermally decompose the ester. In order to remove the hexafluoropropylene oxide derivative, which is a by-product generated by decomposition, out of the system, the pressure was reduced to 10 mmHg while maintaining the temperature at 80 ° C. and maintained for 1 hour. Thereafter, 12 mL of tetraglyme and 4.39 g of CsF were added to the eggplant flask and then stirred at 50 ° C. for 1 hour in a nitrogen atmosphere. 2.49g of allyl bromide was dripped with the dropping funnel, keeping at 50 degreeC. The temperature was raised to 80 ° C. and reacted for 12 hours in a nitrogen atmosphere. After completion of the reaction, the fluorine-based solvent CT-Solv. Extraction and washing were performed with 100E (product name, manufactured by Asahi Glass Co., Ltd.) and water, and the organic phase after two-layer separation was recovered. A 5% aqueous sodium hydroxide solution was added to the organic phase and stirred for 30 minutes, and then the organic phase after separation of the two layers was recovered. The solvent of the recovered organic phase was distilled off under reduced pressure, and after purification by column chromatography, fine dust was removed by passing through a membrane filter having a pore size of 0.5 μm, and expressed by the above formula (5-1-1), 14.2 g (yield 70.1%) of a precursor (5-1-1A) having an average x value of 11.2 in 5-1-1) was obtained. The precursor (5-1-1A) is liquid at room temperature (20-25 ° C.).

NMR spectrum of the obtained precursor (5-1-1A);
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS, internal standard: bis (trifluoromethyl) benzene δ (ppm): 5.9, 5.3, 4.6.
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ , internal standard: bis (trifluoromethyl) benzene δ (ppm): −55.9, −88.3, −89.0, − 90.8 to -91.0.

Next, the precursor (5-1-1A) was hydrosilylated.
That is, 2.56 g of the precursor (5-1-1A) obtained above, 3.77 g of bis (trifluoromethyl) benzene, platinum (0) -1 in a 25 mL two-necked flask connected with a reflux condenser. , 3-Divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene solution (platinum content: 2% by mass), 0.0424 g and 0.959 g of trichlorosilane were added in the stated order, , Reacted at 60 ° C. for 4 hours. After completion of the reaction, bis (trifluoromethyl) benzene and trichlorosilane were distilled off under reduced pressure to quantitatively obtain a compound (13A) represented by the following formula (13) and having an average value of x of 11.2. . Compound (13A) is a liquid at room temperature. Further, a compound (14A) represented by the following formula (14) and having an average value of x of 11.2 was produced as a by-product.
The content of the compound (13A) in the product obtained in this step was 98% by mass, and the content of the compound (14A) was 2% by mass.

NMR spectrum of the obtained compound (13A);
¹ H-NMR (300.4 MHz, solvent: mixed solvent of deuterated chloroform and R-113, standard: TMS, internal standard: 1,3-bis (trifluoromethyl) benzene δ (ppm): 4.1, 2. 0, 1.4.
¹⁹ F-NMR (282.7 MHz, solvent: mixed solvent of deuterated chloroform and R-113, standard: CFCl ₃ , internal standard: 1,3-bis (trifluoromethyl) benzene δ (ppm): −56.2, -88.6, -89.4, -91.3, -91.8.

Next, the chlorine atom of compound (13A) was substituted with a methoxy group.
That is, 2.73 g of the compound (13A) obtained above was placed in a 25 mL two-necked flask connected with a reflux condenser and a dropping funnel, and 1.49 g of a mixed solution of trimethyl orthoformate and methanol (trimethyl orthoformate: Methanol = 26.7: 1 [mol: mol]) was added dropwise using a dropping funnel. After dripping, it was made to react at 60 degreeC by nitrogen atmosphere for 3 hours. Thereafter, 0.424 g of methanol was again dropped with a dropping funnel, and the mixture was reacted at 60 ° C. for 3 hours in a nitrogen atmosphere. After completion of the reaction, trimethyl orthoformate and methanol were distilled off under reduced pressure. In order to remove the platinum catalyst remaining in the system, activated carbon was added to the residue, stirred for 10 minutes, and then passed through a membrane filter having a pore size of 0.5 μm, and expressed by the following formula (15), the average value of x As a result, 1.72 g (yield 63.8%) of a fluorine-containing ether compound (15A) having a molecular weight of 12.2. The fluorine-containing ether compound (15A) is liquid at room temperature. From the NMR analysis, the number average molecular weight of the fluorine-containing ether compound (15A) was 1,550.
The content of the fluorinated ether compound (15A) in the product obtained in this step (described as “content of target compound” in the table; the same shall apply hereinafter) was 98% by mass, and was detected as an impurity. The amount was 2% by mass of the compound (14A).

NMR spectrum of the resulting fluorine-containing ether compound (15A);
¹ H-NMR (300.4 MHz, solvent: mixed solvent of deuterated chloroform and R-113, standard: TMS, internal standard: 1,3-bis (trifluoromethyl) benzene δ (ppm): 4.0, 1. 8, 0.7.
¹⁹ F-NMR (282.7 MHz, solvent: mixed solvent of deuterated chloroform and R-113, standard: CFCl 3, internal standard: 1,3-bis (trifluoromethyl) benzene δ (ppm): −56.2, − 88.6, -89.3, -91.3, -91.4.

[Comparative Example 1: Production of fluorinated ether compound (15B)]
In this example, the precursor production method (ii) was used.
First, 120 mL of tetraglyme and 15.4 g of CsF were added to a 300 mL three-necked flask connected with a dropping funnel and a reflux condenser, represented by the above formula (12), and the average value of x in formula (12) was 8 48.7 g of the compound (12B) of No. 4 was added dropwise using a dropping funnel, followed by stirring for 1 hour. Thereafter, 11.9 g of allyl bromide was added dropwise with a dropping funnel and reacted at 80 ° C. for 1 day in a nitrogen atmosphere. After completion of the reaction, CTsolv. Extraction and washing were performed with 100E (product name, manufactured by Asahi Glass Co., Ltd.) and water, and the organic phase after separation into two layers was recovered using a separatory funnel. A 5% aqueous sodium hydroxide solution was added to the organic phase and stirred for 30 minutes. After stirring, the organic phase after two-layer separation was recovered using a separatory funnel. The collected organic phase solvent was distilled off under reduced pressure, and the residue was washed with a mixed solvent of methanol and water. After washing, the organic phase after separation into two layers was recovered using a separatory funnel. The recovered organic phase was purified by column chromatography, represented by the above formula (5-1-1), and a precursor (5-1 that has an average x value of 8.5 in formula (5-1-1) -1B) was obtained 15.0 g (yield 29.1%). The precursor (5-1-1B) is a liquid at room temperature.

NMR spectrum of the obtained precursor (5-1-1B);
¹ H-NMR (300.4 MHz, solvent: heavy acetone, standard: TMS, internal standard: bis (trifluoromethyl) benzene δ (ppm): 6.0, 5.4, 4.7.
¹⁹ F-NMR (282.7 MHz, solvent: heavy acetone, standard: CFCl ₃ , internal standard: bis (trifluoromethyl) benzene δ (ppm): −55.2, −87.8, −88.5, − 89.4--90.4.

Next, the precursor (5-1-1B) was hydrosilylated.
That is, in a 50 mL two-necked flask connected with a reflux condenser, 15.0 g of the precursor (5-1-1B) obtained above, 15.0 g of bis (trifluoromethyl) benzene, platinum (0)- 0.0373 g of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (platinum content: 2% by mass) and 7.57 g of trichlorosilane were added in the order described, and a nitrogen atmosphere The reaction was carried out at 60 ° C. for 4 hours. After completion of the reaction, bis (trifluoromethyl) benzene and trichlorosilane were distilled off under reduced pressure to quantitatively obtain a compound (13B) represented by the above formula (13) and having an average x value of 8.5. . Compound (13B) is a liquid at room temperature.
In the measurement of impurities in the product obtained in this step, a peak that appeared to be a condensate was slightly observed, but quantification was difficult. Therefore, the content of the compound (13B) in the product obtained in this step was about 99. It is considered that the content of impurities is about 1% by mass.

NMR spectrum of the obtained compound (13B);
¹ H-NMR (300.4 MHz, solvent: mixed solvent of deuterated chloroform and R-113, standard: TMS, internal standard: 1,3-bis (trifluoromethyl) benzene δ (ppm): 4.0, 2. 0, 1.5.
¹⁹ F-NMR (282.7 MHz, solvent: mixed solvent of deuterated chloroform and R-113, standard: CFCl ₃ , internal standard: 1,3-bis (trifluoromethyl) benzene δ (ppm): −56.1, -88.7, -89.5, -90.9, -91.4, -91.7.

Next, the chlorine atom of compound (13B) was substituted with a methoxy group.
That is, 16.4 g of the compound (13B) obtained above was placed in a 50 mL two-necked flask connected with a reflux condenser and a dropping funnel, and 11.8 g of a mixed solution of trimethyl orthoformate and methanol (trimethyl orthoformate: Methanol = 26.7: 1 [mol: mol]) was added dropwise using a dropping funnel. After dripping, it was made to react at 60 degreeC by nitrogen atmosphere for 3 hours. Thereafter, 0.424 g of methanol was again dropped with a dropping funnel, and the mixture was reacted at 60 ° C. for 3 hours in a nitrogen atmosphere. After completion of the reaction, trimethyl orthoformate and methanol were distilled off under reduced pressure. In order to remove the platinum catalyst remaining in the system, activated carbon was added to the residue, stirred for 10 minutes, and then passed through a membrane filter having a pore size of 0.5 μm, and expressed by the above formula (15), the average value of x As a result, 14.6 g (yield 90.3%) of a fluorine-containing ether compound (15B) having a ratio of 8.5 was obtained. The fluorine-containing ether compound (15B) is liquid at room temperature. From the NMR analysis, the number average molecular weight of the fluorine-containing ether compound (15B) was 1,240.
In the measurement of impurities in the product obtained in this step, no impurity peak was observed. The content of the fluorine-containing ether compound (15B) in the product obtained in this step is considered to be about 99% by mass and the content of impurities is about 1% by mass.

NMR spectrum of the resulting fluorine-containing ether compound (15B);
¹ H-NMR (300.4 MHz, solvent: mixed solvent of deuterated chloroform and R-113, standard: TMS, internal standard: 1,3-bis (trifluoromethyl) benzene δ (ppm): 4.0, 1. 8, 0.7.
¹⁹ F-NMR (282.7 MHz, solvent: mixed solvent of deuterated chloroform and R-113, standard: CFCl 3, internal standard: 1,3-bis (trifluoromethyl) benzene δ (ppm): −56.1, − 88.8, -89.5, -91.0, -91.4.

(Manufacture of a substrate having a surface treatment layer)
Using the fluorine-containing ether compound (including impurities) obtained in Example 1 and Comparative Example 1, the substrate was surface treated. For each example, a substrate having a surface treatment layer was produced using the following dry coating method and coating method, respectively. Chemically tempered glass was used as the substrate. About the base material which has the obtained surface treatment layer, it evaluated by the following method. The results are shown in Table 1.
<Dry coating method>
Dry coating was performed using a vacuum evaporation apparatus (VTR-350M, manufactured by ULVAC) (vacuum evaporation method). 0.5 g of each fluorine-containing ether compound was filled in a molybdenum boat in a vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was evacuated to 1 × 10 ⁻³ Pa or less. The boat in which the fluorine-containing ether compound is arranged is heated at a rate of temperature increase of 10 ° C./min or less, and when the deposition rate by the crystal oscillation type film thickness meter exceeds 1 nm / second, the shutter is opened and the surface of the substrate is exposed. Film formation was started. When the film thickness reached about 50 nm, the shutter was closed to finish the film formation on the substrate surface. The substrate on which the fluorine-containing ether compound is deposited is heat-treated at 200 ° C. for 30 minutes, and then washed with C ₃ HF ₅ Cl ₂ (AK-225: product name, manufactured by Asahi Glass Co., Ltd.), which is a fluorine-containing solvent. Thereby, the base material which has a surface treatment layer was obtained.
<Coating method>
The fluorine-containing ether compound obtained in each example was mixed with C ₄ F ₉₀ C ₂ H ₅ (Novec-7200: product name, manufactured by 3M) as a solvent, and a coating having a solid content concentration of 0.05% by mass A liquid was prepared. The substrate was dipped in the coating solution (dip coating method), allowed to stand for 30 minutes, and then lifted. The substrate was dried at 200 ° C. for 30 minutes and washed with AK-225 (product name, manufactured by Asahi Glass Co., Ltd.), which is a fluorine-containing solvent, to obtain a substrate having a surface treatment layer.

(Evaluation method)
<Initial water contact angle>
About the base material (base material which has a surface treatment layer) which each surface-treated by the dry coating method and the apply | coating method, the water contact angle (initial stage) was measured with the following measuring method.
<Initial water drop angle>
About the base material (base material which has a surface treatment layer) each surface-treated by the apply | coating method, the water fall angle (initial stage) was measured with the following measuring method.

<Abrasion resistance>
About the base material which has a surface treatment layer, the friction test was done on the following test conditions using the following testing machine based on JISL0849. The smaller the decrease in water repellency (water contact angle) when the number of frictions is increased, the smaller the decrease in performance due to friction and the better the friction resistance.
Testing machine: Reciprocating traverse testing machine (manufactured by KT Corporation),
Test conditions: A cellulose non-woven fabric (Bencot M-3: manufactured by Asahi Kasei Co., Ltd.) was used to reciprocate a predetermined number of friction times with a load of 1 kg, and then the water contact angle was measured by the following method.
For example, in the case of a base material for a touch panel, it is desirable that the water contact angle with a friction frequency of 100,000 is 100 ° or more.

<Measurement method of water contact angle>
The contact angle of 2 μL of distilled water placed on the surface-treated surface of the substrate having the surface treatment layer was measured using a contact angle measuring device DM-500 (manufactured by Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface-treated surface of the substrate, and the average value was calculated. The 2θ method was used to calculate the contact angle.
<Measurement method of water drop angle>
The surface of the substrate having the surface treatment layer is maintained when the surface-treated surface is held horizontally, and after dropping 50 μL of water droplets on the surface, the substrate is gradually tilted and the substrate surface when the water droplets start to fall down And the horizontal plane (fall angle) were measured using a fall angle measuring device SA-11 (manufactured by Kyowa Interface Science Co., Ltd.).

As shown in the results of Table 1, in Example 1 and Comparative Example 1, the initial water contact angle and water falling angle are good and good regardless of whether it is a dry coating method or a coating method. It was confirmed to have water repellency.
In particular, Example 1 in which the number average molecular weight of the fluorine-containing ether compound is within the scope of the present invention is higher than that of Comparative Example 1 in which the number average molecular weight is small. It was confirmed that the decrease was small and the film had excellent friction resistance.

The fluorine-containing ether compound of the present invention is used as a surface treatment agent capable of imparting good water / oil repellency to the substrate surface. The surface treatment layer formed by this surface treatment agent is easy to wipe off dirt on the surface treatment layer, and has high dirt removability. For example, in a touch panel having this surface treatment layer, the water and oil repellency is not easily lowered even when repeatedly rubbed with a finger, and the performance of easily removing a fingerprint by wiping is maintained for a long time.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-206032 filed on September 21, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (11)

Represented by the following formula (1), a number average molecular weight of Ri der 1,500 to 10,000, a purity not less than 98 wt%, the fluorine-containing ether compound.
A-O-R ^f -B (1)
Symbols in the formula (1) indicate the following.
A: C1-C6 perfluoroalkyl group, or B.
R ^f : a linking group represented by the following formula (2).
_{- (CF 2 CF 2 O)} b (CF (CF 3) CF 2 O) c (CF 2 O) d (CF 2 CF 2 CF 2 O) e - ··· (2)
Symbols in the formula (2) indicate the following.
b, c, d and e are each independently an integer of 0 or more, and b + c + d + e is 6 to 147. However, in the formula (2), the bonding order of repeating units of (CF ₂ CF ₂ O), (CF (CF ₃ ) CF ₂ O), (CF ₂ O), and (CF ₂ CF ₂ CF ₂ O) is It is not limited, You may couple | bond with a block at random or a block mutually.
B: Group represented by the following formula (3).
_{- (CH 2) 3 SiL m} R n ··· (3)
The symbol in Formula (3) shows the following.
L: C1-C4 alkoxy group .
R: a hydrogen atom or a monovalent hydrocarbon group.
m and n: m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n = 3. Represented by the following formula (1-2), the number-average molecular weight of Ri der 1,500 to 10,000, a purity not less than 98 wt%, the fluorine-containing ether compound of claim 1.
_{F (CF 2) a11 -O- (} CF 2 CF 2 O) b11 - (CH 2) 3 SiL m R n ··· (1-2)
The symbol in Formula (1-2) shows the following.
L: C1-C4 alkoxy group .
R: a hydrogen atom or a monovalent hydrocarbon group.
a11: An integer of 1 to 6.
b11: An integer of 8 to 84.
m and n: m is an integer of 1 to 3, n is an integer of 0 to 2, and m + n = 3. The fluorine-containing ether compound according to claim 1 or 2 , wherein m is 3 and n is 0. The coating liquid containing the fluorine-containing ether compound as described in any one of Claims 1-3 , and a liquid medium. The coating liquid according to claim 4 , wherein the liquid medium contains at least one fluorine-based organic solvent selected from the group consisting of a fluorinated alkane, a fluorinated aromatic compound, and a fluoroalkyl ether. The manufacturing method of the base material which has a surface treatment layer which vacuum-deposits the fluorine-containing ether compound as described in any one of Claims 1-3 on the surface of a base material. The manufacturing method of the base material which has a surface treatment layer which removes the said liquid medium after apply | coating the coating liquid of Claim 4 or 5 to the surface of a base material. The method of applying the coating liquid 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, a flow coating method, a roll coating method, The manufacturing method of the base material which has a surface treatment layer of Claim 7 which is a casting method, a Langmuir-Blodgett method, or a gravure coat method. The material of said substrate, metal, resin, glass, ceramic or a composite material thereof, process for producing a substrate having a surface treatment layer according to any one of claims 6-8. The base material which has a surface treatment layer processed with the fluorine-containing ether compound as described in any one of Claims 1-3 . The touch panel which has the surface treatment layer processed by the fluorine-containing ether compound as described in any one of Claims 1-3 in an input surface.