WO2020241750A1 - Base material with water repellent oil repellent layer - Google Patents

Abstract

The present invention provides a base material with a water repellent oil repellent layer, which comprises a water repellent oil repellent layer having excellent fingerprint removal properties.　A base material with a water repellent oil repellent layer according to the present invention comprises a base material and a water repellent oil repellent layer that is arranged on the main surface of the base material and contains a condensation product of a fluorine-containing compound; the amount of excess fluorine in the water repellent oil repellent layer as calculated by a predetermined method is 2 or more.

Description

Base material with water and oil repellent layer

The present invention relates to a base material with a water- and oil-repellent layer.

Fluorine-containing compounds are preferably used as surface treatment agents because they exhibit high lubricity, water and oil repellency, and the like. When water and oil repellency is imparted to the surface of the base material by the surface treatment agent, it becomes easy to wipe off the dirt on the surface of the base material, and the dirt removal property is improved. Among the above-mentioned fluorine-containing compounds, the fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain in which an ether bond (—O—) is present in the middle of the fluoroalkylene chain is a compound having excellent flexibility, and particularly, such as fats and oils. Excellent in removing dirt.
For example, Patent Document 1 describes a fluorine-containing compound that is excessively adhered to a base material after forming a water-repellent oil-repellent layer using a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain, or derived from the fluorine-containing compound. It is disclosed that the water- and oil-repellent layer is wiped off with an organic solvent in order to remove the components.

JP-A-2018-193548

In recent years, the required performance for a water-repellent oil-repellent layer formed by using a fluorine-containing compound has been increased. For example, when the water-repellent oil-repellent layer is applied to a member constituting a surface to be touched by a finger, it adheres to the surface. A water- and oil-repellent layer having excellent performance (fingerprint removal property) that can be easily removed by wiping off the fingerprints is required.
When the present inventors evaluated the water-repellent and oil-repellent layer described in Patent Document 1, they found that there was room for improvement in fingerprint removability.

Therefore, an object of the present invention is to provide a base material with a water-repellent oil-repellent layer having a water-repellent oil-repellent layer having excellent fingerprint removing properties.

As a result of diligent studies on the above problems, the present inventors have made a base material with a water-repellent oil-repellent layer having a base material and a water-repellent oil-repellent layer containing a condensate of a fluorine-containing compound arranged on the main surface of the base material. In the present invention, it has been found that if a water-repellent oil-repellent layer having a surplus fluorine amount of 2 or more calculated according to a predetermined method is used, the water-repellent oil-repellent layer is excellent in fingerprint removal property, and the present invention has been made.

That is, the inventors have found that the above problem can be solved by the following configuration.
[1] A base material with a water-repellent oil-repellent layer having a base material and a water-repellent oil-repellent layer containing a condensate of a fluorine-containing compound arranged on the main surface of the base material, which is calculated by the following method. A base material with a water-repellent oil-repellent layer, characterized in that the excess amount of fluorine in the water-repellent oil-repellent layer is 2 or more.
(Calculation method for excess fluorine)
Using a fluorescent X-ray analyzer (Rigaku, ZSX100e), measurement diameter: 30 mm, measurement line: FKα, filter: OUT, slit: standard, spectroscopic crystal: RX35 (Rigaku), detector: PC, PHA: 100-300, peak angle: 38.794 deg. (20 sec), B.I. G. Angle: 43.000 deg. The fluorine atomic strength F1 in the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer and the surface of the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer measured under the condition of (10 sec). Fluorine atomic strength F2 in the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer after wiping 100 times with Kimwipe (registered trademark) moistened with Asahiclean (registered trademark) AE-3000 (manufactured by AGC). Therefore, the excess fluorine amount is calculated by the following formula (I).
Fluorine surplus = (F1-F2) / F2 × 100 (I)

[2] The base material with a water-repellent oil-repellent layer according to [1], wherein the excess amount of fluorine is 5 or more.
[3] The base material with a water-repellent oil-repellent layer according to [1] or [2], wherein the excess amount of fluorine is 400 or less.
[4] The base material with a water-repellent oil-repellent layer according to [1] or [2], wherein the excess amount of fluorine is 200 or less.
[5] The substrate with a water-repellent oil-repellent layer according to any one of [1] to [4], wherein the fluorine-containing compound has a poly (oxyfluoroalkylene) chain and a reactive silyl group.
[6] The base material with a water- and oil-repellent layer according to [5], wherein the fluorine-containing compound has two or more reactive silyl groups.
[7] The base material with a water-repellent oil-repellent layer according to [6], wherein the fluorine-containing compound has the reactive silyl groups on both terminal sides of the poly (oxyfluoroalkylene) chain.

[8] The water- and oil-repellent layer of [7], wherein the compound in which the reactive silyl group is located on both terminal sides of the poly (oxyfluoroalkylene) chain is a compound represented by the formula (3-2). With base material.
^{_{[L 3-n (R)}} n Si-] k2 Y 12 - (OX) m -Y 11 [-Si (R) n L 3-n] g2 (3-2)
However, in equation (3-2),
X is a fluoroalkylene group having one or more fluorine atoms.
m is an integer greater than or equal to 2
Y ¹¹ is a linking group of (g2 + 1) valence,
Y ¹² is a linking group of (k2 + 1) valence,
R is a monovalent hydrocarbon group and
L is a hydrolyzable group or a hydroxyl group,
n is an integer of 0 to 2 and
g2 is an integer greater than or equal to 1 and
k2 is an integer of 1 or more.

[9] The base material with a water-repellent oil-repellent layer according to [6], wherein the fluorine-containing compound has two or more reactive silyl groups on one end side of the poly (oxyfluoroalkylene) chain.
[10] The base material with a water-repellent oil-repellent layer according to any one of [1] to [9], wherein the number average molecular weight (Mn) of the fluorine-containing compound is 1,000 to 20,000.
[11] The condensate of the fluorine-containing compound has a compound having a reactive silyl group on both terminal sides of the poly (oxyfluoroalkylene) chain and a reactive silyl group on only one terminal side of the poly (oxyfluoroalkylene) chain. The base material with a water-repellent and oil-repellent layer according to [5], which is a condensate of a mixture containing a fluorine-containing compound having.
[12] The water-repellent repellency of [11], wherein the fluorine-containing compound having a reactive silyl group only on one terminal side of the poly (oxyfluoroalkylene) chain is a fluorine-containing compound having two or more reactive silyl groups. Base material with oil layer.

According to the present invention, it is possible to provide a base material with a water-repellent oil-repellent layer having a water-repellent oil-repellent layer having excellent fingerprint removing properties.

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

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

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

[Base material with water and oil repellent layer]
The base material with a water-repellent oil-repellent layer of the present invention is a base material with a water-repellent oil-repellent layer having a base material and a water-repellent oil-repellent layer containing a condensate of a fluorine-containing compound arranged on the main surface of the base material. Therefore, the excess amount of fluorine in the water-repellent oil-repellent layer calculated by the method described later is 2 or more.
In the following description, a water- and oil-repellent layer that is the main surface of the base material that may be used in contact with other articles or human fingers and / or may be held by human fingers during operation. The surface on which is placed is called the "main surface". The main surface is not limited to a flat surface.

The base material with a water- and oil-repellent layer of the present invention is excellent in fingerprint removal of the water- and oil-repellent layer. The details of this reason have not been clarified, but it is presumed to be due to the following reasons.
When a water- and oil-repellent layer is formed using a fluorine-containing compound, a component that is not bonded to a substrate derived from the fluorine-containing compound (for example, an unreacted fluorine-containing compound or a condensate of a fluorine-containing compound. Hereinafter, " (Also referred to as "surplus component") and the like may be present in the water- and oil-repellent layer. Conventionally, it has been considered that the surplus component deteriorates the performance of the water-repellent oil-repellent layer. Therefore, the water-repellent oil-repellent layer is sufficiently washed with an organic solvent or the like to remove the surplus component.
However, the present inventors have found that the fingerprint removability of the water-repellent oil-repellent layer is further improved if the surplus component is present to some extent (that is, the fluorine amount surplus is 2 or more).

(Base material)
The substrate may be another article (eg, a stylus) or a substrate that may be used in contact with a human finger, a substrate that may be held by a human finger during operation, and / or another article (eg, a stylus). , A base material that may be placed on a mounting table) and is not particularly limited as long as it is a base material that is required to be provided with water and oil repellency. Specific examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened.
As the base material, a touch panel base material and a display base material are preferable, and a touch panel base material is particularly preferable. The base material for the touch panel preferably has translucency. “Having translucency” means that the vertically incident visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. Glass and transparent resin are preferable as the material of the base material for the touch panel.
The base materials include building materials, decorative building materials, interiors, transportation equipment (for example, automobiles), signs / notices, drinkers / tableware, water tanks, ornamental equipment (for example, forehead, boxes), laboratory equipment, furniture, art / Glass or resin film used for sports games, and glass sheet or resin used for exterior parts (excluding display parts) of devices such as mobile phones (for example, smartphones), mobile information terminals, game machines, and remote controls. Films are also preferred.

The water- and oil-repellent layer may be formed directly on the main surface of the base material, or may be formed on the base material via another film formed on the main surface of the base material. As a specific example of the above other film, a base film formed on the main surface of the base material by subjecting the base material with the compound described in paragraphs 0008 to 0905 of International Publication No. 2011/016458, SiO ₂ or the like. Can be mentioned.

(Water and oil repellent layer)
The excess fluorine content of the water-repellent oil-repellent layer calculated by the following method is 2 or more, and is preferably 10 or more, preferably 20 or more, in that the fingerprint-removing property of the water-repellent oil-repellent layer is more excellent. Especially preferable.
The upper limit of the excess amount of fluorine in the water- and oil-repellent layer is preferably 400 or less, more preferably 300 or less, further preferably 200 or less, and particularly preferably 150 or less. When the upper limit of the excess fluorine amount is 400 or less, the transparency of the water-repellent oil-repellent layer becomes high, so that the appearance of the water-repellent oil-repellent layer is excellent.
The excess amount of fluorine in the water-repellent oil-repellent layer is determined by the film forming conditions (for example, drying conditions in the wet coating method, vapor deposition conditions in the dry coating method, heating in the wet coating method and the dry coating method) when forming the water-repellent oil-repellent layer. Post-treatment conditions such as humidification and light irradiation, application amount of fluorine-containing compound), cleaning conditions of water- and oil-repellent layer (for example, type of organic solvent used for cleaning, number of wipes with cloth moistened with organic solvent, cloth It can be adjusted by the pressure when wiping with.

The method for calculating the excess amount of fluorine in the water- and oil-repellent layer is as follows.
Using a fluorescent X-ray analyzer (Rigaku, ZSX100e), measurement diameter: 30 mm, measurement line: FKα, filter: OUT, slit: standard, spectroscopic crystal: RX35 (Rigaku), detector: PC, PHA: 100-300, peak angle: 38.794 deg. (20 sec), B.I. G. Angle: 43.000 deg. The fluorine atomic strength F1 in the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer and the surface of the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer measured under the condition of (10 sec) are registered with Asahiclean. From the fluorine atomic strength F2 in the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer after wiping 100 times with Kimwipe (registered trademark) moistened with AE-3000 (manufactured by AGC), the following formula (I) ) To calculate the excess fluorine amount.
Fluorine surplus = (F1-F2) / F2 × 100 (I)

Asahiclean (registered trademark) AE-3000 (manufactured by AGC) is 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF ₃ CH ₂ OCF ₂ CF ₂ H, fluorine). System organic solvent).
Kimwipe (registered trademark) is pulp paper, and it is preferable to use Kimwipe (registered trademark) S-200 (manufactured by Nippon Paper Crecia).

Specific examples of the procedure for swelling the Kimwipe with a solvent include a method in which the Kimwipe is immersed in AE-3000 for 3 minutes and then the Kimwipe is taken out.
In the method for calculating the excess fluorine amount, the operation of wiping the water-repellent oil-repellent layer is preferably carried out by applying a load in the range of 0.98 to 490N to the Kimwipe, and applying a load in the range of 9.8 to 98N to the Kimwipe. It is more preferable to carry out by applying a load in the range of 20 to 98N to the Kimwipe.
In the method for calculating the excess fluorine amount, the operation of wiping the water-repellent oil-repellent layer is preferably performed in an environment of a humidity of 60% RH and a room temperature (23 ° C.).

In the method for calculating the excess amount of fluorine, after wiping the water- and oil-repellent layer, the water- and oil-repellent layer is sufficiently dried, and the base material with the water- and oil-repellent layer is returned to room temperature (23 ° C.), and then the fluorine atom strength It is preferable to measure F2.
The water- and oil-repellent layer may be dried under the condition that the fluorine-based organic solvent adhering to the water- and oil-repellent layer is sufficiently evaporated. Specifically, the drying temperature is preferably 60 to 200 ° C. (preferably 150 ° C.), and the drying time is preferably 20 to 120 minutes (preferably 45 minutes).

The fluorine atomic strength F1 and the fluorine atomic strength F2 are preferably measured in an environment with a humidity of 60% RH and a room temperature (23 ° C.).

<Fluorine-containing compound>
The water- and oil-repellent layer contains a condensate of a fluorine-containing compound. Two or more kinds of fluorine-containing compounds may be used in combination.
The fluorine-containing compound is not particularly limited as long as it has a condensable group, but the poly (oxyfluoroalkylene) chain and the reactive silyl in that the water-repellent oil-repellent layer has better fingerprint-removing property and water-repellent oil-repellent property. It is preferably a compound having a group.
Among them, in the formation of the water-repellent oil-repellent layer, the water-repellent oil-repellent layer has a plurality of reactive silyl groups in that the fingerprint-removing property of the water-repellent oil-repellent layer is more excellent. It is preferable to use a fluorine-containing compound in which is located (for example, a compound represented by the formula (3-2) described later), and a compound in which reactive silyl groups are located on both terminal sides of a poly (oxyfluoroalkylene) chain (for example, For example, a compound represented by the formula (3-2) described later) and a fluorine-containing compound in which a reactive silyl group is located only on one terminal side of the poly (oxyfluoroalkylene) chain (for example, the compound represented by the formula (3-2) described later). It is particularly preferable to use a mixture of the compound represented by 1) and the fluorine-containing compound containing.

The reactive silyl group means a hydrolyzable silyl group and a silanol group (Si—OH). Specific examples of the hydrolyzable silyl group include a group in which L of the group represented by the formula (2) described later is a hydrolyzable group.
The hydrolyzable silyl group becomes a silanol group represented by Si-OH by the hydrolysis reaction. The silanol groups further undergo a dehydration condensation reaction between the silanol groups to form a Si—O—Si bond. Further, the silanol group can form a Si—O—Si bond by a dehydration condensation reaction with a silanol group that can be contained in the base material or the base layer. That is, when a fluorine-containing compound having a reactive silyl group is used for forming a water-repellent oil-repellent layer, a part or all of the reactive silyl group of the fluorine-containing compound is hydrolyzed and dehydrated and condensed in the water-repellent oil-repellent layer. Contains the condensate.

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

X is a fluoroalkylene group having one or more fluorine atoms.
The number of carbon atoms of the fluoroalkylene group is preferably 1 to 6 and particularly preferably 2 to 4 from the viewpoint of more excellent weather resistance and corrosion resistance of the water- and oil-repellent layer.
The fluoroalkylene group may be linear, branched or cyclic.
The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times the number of carbon atoms, and particularly preferably 1.7 to 2 times, from the viewpoint of more excellent corrosion resistance of the water- and oil-repellent layer.
As the fluoroalkylene group, a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group) is preferable.

Specific examples of the (OX) _{is, -OCHF -, - OCF 2 CHF} -, - OCHFCF 2 -, - OCF 2 CH 2 -, - OCH 2 CF 2 -, - OCF 2 CF 2 CHF -, - OCHFCF 2 CF _2- , -OCF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -,- OCF _2- , -OCF ₂ CF _2- , -OCF ₂ CF ₂ CF _2- , -OCF (CF ₃ ) CF _2- , -OCF ₂ CF ₂ CF ₂ CF _2- , -OCF (CF ₃ ) CF ₂ CF _{2 -, - OCF 2 CF 2} CF 2 CF 2 CF 2 -, - OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -, - O-cycloC 4 F 6 -, - O-cycloC 5 F 8 -, - O-cycloC ₆ F _10- can be mentioned.
Here, -cycloC ₄ F _6- means a perfluorocyclobutane diyl group, and specific examples thereof include a perfluorocyclobutane-1,2-diyl group. -CycloC ₅ F ₈ - means a perfluoro cyclopentane-diyl group, and specific examples thereof include perfluoro cyclopentane-1,3-diyl group. -CycloC ₆ F _10- means a perfluorocyclohexanediyl group, and specific examples thereof include a perfluorocyclohexane-1,4-diyl group.

The number of repetitions m of (OX) is an integer of 2 or more, an integer of 2 to 200 is more preferable, an integer of 5 to 150 is further preferable, an integer of 5 to 100 is particularly preferable, and an integer of 10 to 50 is the most preferable. preferable.
(OX) _m may contain two or more kinds of (OX).
The binding order of two or more types of (OX) is not limited, and may be arranged randomly, alternately, or in blocks.
Including two or more kinds of (OX) means that two or more kinds of (OX) having different carbon atoms are present in the fluorine-containing compound, and two or more kinds of (OX) having different hydrogen atom numbers are present. , There are two or more types of (OX) with different hydrogen atom positions, and even if the number of carbon atoms is the same, the presence or absence of side chains and the type of side chains (number of side chains, number of carbons in side chains, etc.) ) Is different, which means that there are two or more types of (OX).
The arrangement of two or more (OX), for _{example, {(OCF 2) m21 (} OCF 2 CF 2) m22} structure represented by the, m21 amino (OCF ₂₎ and m22 amino _(OCF 2 CF ₂ ) and means that they are randomly arranged. _Further, the structure represented by _{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2) m25 is a m25 amino _{(OCF 2} CF 2) and m25 amino _{(OCF 2 CF 2 CF 2 CF} 2) Indicates that they are arranged alternately.

(OX) _m is [(OCH _ma F _(2-ma) ) _m11・ (OC ₂ H _mb F _(4-mb) ) _m12・ (OC ₃ H _mc F _(6-mc) ) _m13・ (OC) ₄ H _md F _(8-md) ) _m14・ (OC ₅ H _me F _(10-me) ) _m15・ (OC ₆ H _mf F _(12-mf) ) _m16・ (O-cycloC ₄ H _mg F _{(6) -Mg)} ) _m17 · (O-cycloC ₅ H _mh F _(8-mh) ) _m18 · (O-cycloC ₆ H _mi F _(10-mi) ) _m19 ] is preferable. Here, -cycloC ₄ H _mg F _{(6- mg)} represents a fluorocyclobutane-diyl group, and a fluorocyclobutane-1,2-diyl group is preferable. -CycloC ₅ H _mh F _(8-mh) represents a fluorocyclopentane diyl group, preferably a fluorocyclopentane-1,3-diyl group. -CycloC ₆ H _mi F _(10-mi) represents a fluorocyclohexanediyl group, preferably a fluorocyclohexane-1,4-diyl group.
ma is 0 or 1, mb is an integer of 0 to 3, mc is an integer of 0 to 5, md is an integer of 0 to 7, me is an integer of 0 to 9, and mf is an integer of 0 to 9. It is an integer of 0 to 11, mg is an integer of 0 to 5, mh is an integer of 0 to 7, and mi is an integer of 0 to 9.
m11, m12, m13, m14, m15, m16, m17, m18 and m19 are each independently an integer of 0 or more, preferably 100 or less.
m11 + m12 + m13 + m14 + m15 + m16 + m17 + m18 + m19 are integers of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, further preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.
Among them, m12 is preferably an integer of 2 or more, and particularly preferably an integer of 2 to 200.
In addition, C ₃ H _mc F _(6-mc) , C ₄ H _md F _(8-md) , C ₅ H _me F _(10-me) and C ₆ H _mf F _(12-mf) are linear. However, it may have a branched chain shape, and a linear shape is preferable from the viewpoint of more excellent friction resistance of the water-repellent oil-repellent layer.

The above equation represents the type of unit and its number, and does not represent an array of units. That is, m11 to m19 represent the number of units, for example, (OCH _ma F _(2-ma) ) _m11 represents a block in which (OCH _ma F _(2-ma) ) units are m11 consecutive. is not. Similarly, the description order of (OCH _ma F _(2-ma) ) to (O-cycloC ₆ H _mi F _(10-mi) ) does not indicate that they are arranged in the description order.
In the above equation, when 2 or more of m11 to m19 are not 0 (that is, when (OX) _m is composed of two or more units), the sequences of different units are random sequences, alternating sequences, block sequences and It may be any combination of these sequences.
Further, each of the above units may also be different if the unit includes two or more units. For example, when m11 is 2 or more, a plurality of (OCH _ma F _(2-ma) ) may be the same or different.

(OX) _m preferably has the following structure.
_{{(OCF 2) m21 (OCF} 2 CF 2) m22},
(OCF ₂ CF ₂ ) _m23 ,
(OCF ₂ CF ₂ CF ₂ ) _m24 ,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2) m25,
(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m26 (OCF ₂ ) _m27 ,
(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m26 (OCF ₂ CF ₂ ) _m27 ,
(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m26 (OCF ₂ ) _m27 ,
(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m26 (OCF ₂ CF ₂ ) _m27 ,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 -OCF 2) m28,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 -OCF 2 CF 2) m28,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 CF 2 -OCF 2) m28,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 CF 2 -OCF 2 CF 2) m28,
_{(OCF 2 -OCF 2 CF 2 CF} 2 CF 2 CF 2) m28,
_{(OCF 2 -OCF 2 CF 2 CF} 2 CF 2 CF 2 CF 2) m28,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2 CF 2) m28,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2 CF 2 CF 2) m28.
However, m21 is an integer of 1 or more, m22 is an integer of 1 or more, m21 + m22 is an integer of 2 to 500, m23 and m24 are independently integers of 2 to 500, and m25 is 1 It is an integer of ~ 250, m26 and m27 are each independently an integer of 1 or more, m26 + m27 is an integer of 2 to 500, and m28 is an integer of 1 to 250.

(OX) _m is more preferably having the following structure from the viewpoint that compound (1) can be easily produced.
_{{(OCF 2) m21 (OCF} 2 CF 2) m22},
(OCF ₂ CF ₂ CF ₂ ) _m24 ,
_{(OCF 2 CF 2) 2 {} (OCF 2) m21 (OCF 2 CF 2) m22-2},
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2) m25-1 OCF 2 CF 2,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 -OCF 2) m28,
_{(OCF 2 CF 2 CF 2 CF} 2 CF 2 CF 2 -OCF 2) m28,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2 CF 2) m28-1 OCF 2 CF 2,
_{(OCF 2 CF 2 -OCF 2 CF} 2 CF 2 CF 2 CF 2 CF 2) m28-1 OCF 2 CF 2.
However, for m22-2, m25-1 and m28-1, the numbers of m22, m25 and m28 are selected so as to be an integer of 1 or more.
Among these, from the viewpoint of abrasion resistance and fingerprint removal of water- and oil-repellent layer is more excellent, _(OX) m _{is, {(OCF 2) m21 (} OCF 2 CF 2) m22} a is preferably.
In _{{(OCF 2) m21 (OCF} 2 CF 2) m22}, m22 / m21 from that abrasion resistance and fingerprint removal of water- and oil-repellent layer is more excellent, preferably 0.1 to 10, 0.2 ~ 5.0 is more preferable, 0.2 to 2.0 is further preferable, 0.2 to 1.5 is particularly preferable, and 0.2 to 0.85 is most preferable.

The number average molecular weight (Mn) of (OX) _m is preferably 1,000 to 20,000, more preferably 1,500 to 18,000, and particularly preferably 2,000 to 14,000.
When Mn is 1,000 or more, the fluidity of the molecular chain of the fluorine-containing compound and the fluorine content are high, so that the fingerprint removing property of the water- and oil-repellent layer is more excellent.

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

When the fluorine-containing compound has a reactive silyl group (preferably group (2)), the number of reactive silyl groups is preferably one or more, and the water- and oil-repellent layer has more excellent abrasion resistance. More preferably, 4 or more are more preferable, and 6 or more are particularly preferable.
When the fluorine-containing compound has a reactive silyl group (preferably group (2)), the upper limit of the number of reactive silyl groups is that the fluorine content of the fluorine-containing compound is high and the fingerprint removability is more excellent. Therefore, 25 pieces are preferable, 18 pieces are more preferable, and 12 pieces are particularly preferable.
When there are a plurality of reactive silyl groups in one molecule, the plurality of reactive silyl groups may be the same or different. From the viewpoint of easy availability of raw materials and easy production of fluorine-containing compounds, they are preferably the same.

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

L is a hydrolyzable group or a hydroxyl group.
The hydrolyzable group of L is a group that becomes a hydroxyl group by a hydrolyzing reaction. That is, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH by the hydrolysis reaction. The silanol groups further react between the silanol groups to form a Si—O—Si bond. Further, the silanol group can form a Si—O—Si bond by undergoing a dehydration condensation reaction with a silanol group derived from an oxide contained in the underlying layer.

Specific examples of L include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable. As the acyl group, an acyl group having 1 to 6 carbon atoms is preferable. As the acyloxy group, an acyloxy group having 1 to 6 carbon atoms is preferable.
As L, an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferable from the viewpoint that the fluorine-containing compound can be more easily produced. As L, an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgassing during coating and the storage stability of the fluorine-containing compound is more excellent, and when long-term storage stability of the fluorine-containing compound is required, The ethoxy group is particularly preferable, and the methoxy group is particularly preferable when the reaction time after coating is short.

n is an integer of 0 to 2.
n is preferably 0 or 1, and particularly preferably 0. The presence of a plurality of L makes the adhesion of the water-repellent oil-repellent layer to the base material stronger.
When n is 1 or less, the plurality of Ls present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of fluorine-containing compounds, it is preferable that a plurality of L's are the same. When n is 2, the plurality of Rs present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and easy production of fluorine-containing compounds, it is preferable that a plurality of R's are the same.

The fluorine-containing compound is preferably a compound represented by the following formula (3) in that it is more excellent in water and oil repellency and fingerprint removing property of the water and oil repellent layer.
[A- (OX) _m- ] _j Y ¹ [-Si (R) _n L _3-n ] _g (3)

A is a perfluoroalkyl group or -Y ² [-Si (R) _n L _3-n ] _k .
The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, particularly preferably 1 to 3, from the viewpoint of more excellent abrasion resistance of the water- and oil-repellent layer.
The perfluoroalkyl group may be linear, branched or cyclic.
However, when A is −Y ² [−Si (R) _n L _3-n ] _k , j is 1.

Perfluoroalkyl groups include CF _3- , CF ₃ CF _2- , CF ₃ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF (CF ₃ )-etc.
As the perfluoroalkyl group, CF _3- , CF ₃ CF _2- , and CF ₃ CF ₂ CF ₂ --are preferable because the water- and oil-repellent layer has more excellent water- and oil-repellent properties.

Y ² is a (k + 1) valence linking group.
Y ² may be a group that does not impair the effects of the present invention. For example, an alkylene group, a carbon atom, a nitrogen atom, or silicon which may have an ethereal oxygen atom or a divalent organopolysiloxane residue. Atomic, 2- to 8-valent organopolysiloxane residues, and formulas (3-1A), formulas (3-1B), formulas (3-1A-1) to (3-1A-6) described later to Si ( R) Groups excluding _n L _3-n can be mentioned.
Further, Y ² may be a group (g2-1) to a group (g2-14) described later.

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

Y ¹ is a (j + g) valence linking group.
Y ¹ may be a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, or a silicon atom which may have an ethereal oxygen atom or a divalent organopolysiloxane residue. 2,8-valent organopolysiloxane residues, and Si (R) from formulas (3-1A), formulas (3-1B), formulas (3-1A-1) to (3-1A-6) described later. ) Groups excluding _n L _3-n can be mentioned.
Further, Y ¹ may be a group (g2-1) to a group (g2-14) described later.

j is an integer of 1 or more. The j is preferably 1 to 6 from the viewpoint of more excellent water and oil repellency of the water and oil repellent layer, and is particularly preferably 1 from the viewpoint of easily producing the compound (1).
g is an integer of 1 or more. From the viewpoint of more excellent abrasion resistance of the water- and oil-repellent layer, g is preferably 1 to 15, more preferably 1 to 6, further preferably 2 to 4, and particularly preferably 2 or 3. On the other hand, from the viewpoint of more excellent fingerprint removing property of the water-repellent and oil-repellent layer, g is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
k is an integer of 1 or more. From the viewpoint of more excellent abrasion resistance of the water- and oil-repellent layer, k is preferably 1 to 15, more preferably 1 to 6, further preferably 2 to 4, and particularly preferably 2 or 3. On the other hand, from the viewpoint of more excellent fingerprint removing property of the water-repellent and oil-repellent layer, k is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
From the viewpoint of more excellent abrasion resistance of the water- and oil-repellent layer, k + g is preferably 2 to 25, more preferably 4 to 18, and particularly preferably 6 to 12. On the other hand, k + g is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 2 from the viewpoint of more excellent fingerprint removing property of the water and oil repellent layer.

When the compound (3) has a plurality of _{[-Si (R) n L 3} -n], a plurality of _{[-Si (R) n L 3} -n] may or may not be the same.

The compound (3) includes a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2) from the viewpoint of being more excellent in abrasion resistance and fingerprint removing property of the water- and oil-repellent layer. Is preferable, and the compound represented by the following formula (3-2) is particularly preferable.
[R ^f1- (OX) _m- ] _j1 Y ¹⁰ [-Si (R) _n L _3-n ] _g1 (3-1)
^{_{[L 3-n (R)}} n Si-] k2 Y 12 - (OX) m -Y 11 [-Si (R) n L 3-n] g2 (3-2)
The definitions of X, L, R, m, and n in the formula (3-1) are synonymous with the definitions of each group in the formula (3). Y ¹⁰ is a linking group having a (j1 + g1) valence, and a specific example thereof is the same as Y ¹ in the formula (3). R ^f1 is a perfluoroalkyl group, and preferred embodiments and specific examples of the perfluoroalkyl group are as described above. j1 and g1 are synonymous with the definitions of j and g in equation (3), respectively.
The definitions of X, L, R, m, and n in the formula (3-2) are synonymous with the definitions of each group in the formula (3). Y ¹¹ is a linking group having a (g2 + 1) valence, and a specific example thereof is the same as that of Y ^{1 in} (3). Y ¹² is a linking group having a (k2 + 1) valence, and a specific example thereof is the same as Y ² in the formula (3). k2 and g2 are synonymous with the definitions of k and g in equation (3), respectively.
If having a plurality of a plurality of compound (3-1) is _{^{[R f1 - - (OX)}} m] [R f1 - (OX) m -] may or may not be the same. When the compounds (3-1) and the compound (3-2) has a plurality of _{[-Si (R) n L 3} -n], a plurality of _{[-Si (R) n L 3} -n] are the same May be different.

-Y ¹⁰ [-Si (R) _n L _3-n ] in the formula (3-1) The group represented by _g1 and -Y ¹¹ [-Si (R) _n L ₃ ) in the formula (3-2). _-N ] The group represented by _g2 and the group represented by -Y ¹² [-Si (R) _n L _3-n ] _k2 are preferably groups (3-1A) or groups (3-1B), respectively.
-Q ^a -X ³¹ (-Q ^b -Si (R) _n L _3-n ) _h (-R ³¹ ) _i (3-1A)
-Q ^c- [CH ₂ C (R ³² ) (-Q ^d _- Si (R) _n L _3-n )] _y- R ³³ (3-1B)
The definitions of R, L, and n in the formulas (3-1A) and (3-1B) are as described above.

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

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

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

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

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

Q ^c is a single bond or divalent linking group.
Definition of the divalent linking group are the same as those defined as described in the above-described Q ^a.
The carbon number of the alkylene group which may have an etheric oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.

R ³² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.
As the alkyl group, a methyl group is preferable.

Q ^d is a single bond or an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. From the viewpoint of easy production of a compound, Q ^d is preferably a single bond or -CH _2- .

R ³³ is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.

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

As the group (3-1A), the groups (3-1A-1) to (3-1A-6) are preferable.
-(X ³² ) _s1- Q ^b1 _- SiR _n L _3-n (3-1A-1)
-(X ³³ ) _s2- Q ^a2- N [-Q ^b2 _- Si (R) _n3 L _3-n ] ₂ (3-1A-2)
-Q ^a3 -G (R ^g ) [-Q ^b3 _- Si (R) _n L _3-n ] ₂ (3-1A-3)
-[Q ^e ] _s4- Q ^a4- (O) _t4- C [-(O) _u4- Q ^b4- Si (R) _n L _3-n ] _3-w1 (-R ³¹ ) _w1 (3-1A-) 4)
-Q ^a5- Si [-Q ^b5 _- Si (R) _n L _3-n ] ₃ (3-1A-5)
-[Q ^e ] _v -Q ^a6- Z ^a [-Q ^b6 _- Si (R) _n L _3-n ] _w2 (3-1A-6)
The definitions of R, L, and n in the formulas (3-1A-1) to (3-1A-6) are as described above.

In the group (3-1A-1), X ³² is -O-, -C (O) O-, -SO ₂ N (R ^d )-, -N (R ^d ) SO _2- , -N (R). ^d ) C (O)-or-C (O) N (R ^d )-(where N in the equation binds to Q ^b1 ).
The definition of R ^d is as described above.
s1 is 0 or 1.

Q ^b1 is an alkylene group. The alkylene group may have an —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.
When the alkylene group has an —O—, silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is preferable to have these groups between carbon atoms.
The carbon number of the alkylene group represented by Q ^b1 is preferably 1 to 10, and particularly preferably 2 to 6.

As for Q ^b1 , when s1 is 0, -CH ₂ OCH ₂ CH ₂ CH _2- , -CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH _2- , -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ --is preferable. (X ³² ) When _s1 is −O−, −CH ₂ CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable. (X ³² ) When _s1 is −C (O) N (R ^d ) −, an alkylene group having 2 to 6 carbon atoms is preferable (however, N in the formula is bonded to Q ^b1 ). If Q ^b1 is these groups, the compound can be easily produced.

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

In the group ^{(3-1A-2), X} 33 is, -O -, - NH -, - C (O) O -, - SO 2 N (R d) -, - N (R d) SO 2 -, -N (R ^d ) C (O)-or-C (O) N (R ^d )-.
The definition of R ^d is as described above.

Q ^a2 is a single bond, an alkylene group, -C (O)-, or an ethereal oxygen atom between carbon atoms of an alkylene group having 2 or more carbon atoms, -C (O)-, and -C (O). ) A group having O-, -OC (O)-, or -NH-.
The carbon number of the alkylene group represented by Q ^a2 is preferably 1 to 10, and particularly preferably 1 to 6.
^Ethereal oxygen atom, -C (O)-, -C (O) O-, -OC (O)-, -C between carbon atom and carbon atom of alkylene group having 2 or more carbon atoms represented by ^Qa2 (O) N (R ^d )-, -N (R ^d ) C (O)-, -N (R ^d ) C (O) N (R ^d )-, -N (R ^d ) C (O) O -, -OC (O) N (R ^d )-, -SO ₂ N (R ^d )-, -N (R ^d ) SO _2- , -C (O) N (R ^d )-, or -NH- The number of carbon atoms of the group having is preferably 2 to 10, and particularly preferably 2 to 6.

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

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

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

As Q ^b2 , -CH ₂ CH ₂ CH _2- and -CH ₂ CH ₂ OCH ₂ CH ₂ CH _2- are preferable from the viewpoint of easy production of a compound (however, the right side binds to Si).

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

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

In the group (3-1A-3), Q ^a3 is a single bond or an alkylene group which may have an ethereal oxygen atom, and a single bond is preferable from the viewpoint of easy production of a compound.
The number of carbon atoms of the alkylene group which may have an etheric oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.

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

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

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

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

In the group (3-1A-4), Q ^e is -C (O) O-, -SO ₂ N (R ^d )-, -N (R ^d ) SO _2- , -N (R ^d ) C ( O)-or-C (O) N (R ^d )-.
The definition of R ³¹ is as described above.
s4 is 0 or 1.
Q ^a4 is an alkylene group which may have a single bond or an ethereal oxygen atom.
The carbon number of the alkylene group which may have an etheric oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.
t4 is 0 or 1 (where Q ^a4 is 0 when it is a single bond).
As for -Q ^a4- (O) _t4- , when s4 is 0, it is a single bond, -CH ₂ O-, -CH ₂ OCH _2- , -CH ₂ OCH ₂ CH _{2 because} it is easy to produce a compound. O-, -CH ₂ OCH ₂ CH ₂ OCH _2- , -CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH _2- is preferable (however, the left side is bonded to (OX) _m ), and s4 is 1. Is preferably a single bond, -CH _2- , -CH ₂ CH _2- .

Q ^b4 is an alkylene group, and the alkylene group is -O-, -C (O) N (R ^d )-(the definition of R ^d is as described above), a silphenylene skeleton group, and a divalent group. It may have an organopolysiloxane residue or a dialkylsilylene group.
When the alkylene group has an —O— or silphenylene skeleton group, it is preferable to have an —O— or silphenylene skeleton group between carbon atoms. When the alkylene group has a -C (O) N (R ^d )-, dialkylsilylene group or a divalent organopolysiloxane residue, it is between carbon atoms or the end on the side that binds to (O) _u4. It is preferable to have these groups in.
The carbon number of the alkylene group represented by Q ^b4 is preferably 1 to 10, and particularly preferably 2 to 6.

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

w1 is an integer of 0 to 2, preferably 0 or 1, and particularly preferably 0.
^{_{[- (O) u4 -Q b4}} -Si (R) n L 3-n] if there are two or more, two or more ^{_{[- (O) u4 -Q b4}} -Si (R) n L 3- _n ] may be the same or different.
If R ³¹ is two or more, two or more ^{(-R 31)} may be be the same or different.

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

In the group ^{(3-1A-5), Q a5} is an alkylene group which may have an etheric oxygen atom.
The carbon number of the alkylene group which may have an etheric oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6.
The Q ^a5, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH _2- is preferable (however, the right side is bonded to Si).

Q ^b5 is an alkylene group or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ^b5 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^b5 is preferably 2 to 10, and 2 to 10 is preferable. 6 is particularly preferable.
As Q ^b5 , -CH ₂ CH ₂ CH _2- and -CH ₂ CH ₂ OCH ₂ CH ₂ CH _2- are preferable from the viewpoint of easy production of a compound (however, the right side is Si (R) _n L _3-n. Combine with.).

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

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

The definition of Q ^{e in} the group (3-1A-6) is as defined in the group (3-1A-4) described above.
v is 0 or 1.

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

Z ^a is a (w + 1) -valent organopolysiloxane residue.
w2 is an integer of 2 to 7.
Examples of the (w2 + 1) -valent organopolysiloxane residue include the following groups. However, ^Ra in the following equation is as described above.

Q ^b6 is an alkylene group or a group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ^b6 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of the group having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^b6 is preferably 2 to 10 and 2 to 10 6 is particularly preferable.
As Q ^b6 , -CH ₂ CH _2- and -CH ₂ CH ₂ CH _2- are preferable from the viewpoint of easy production of a compound.
The w2 [-Q ^b6- Si (R) _n3 L _3-n ] may be the same or different.

Y ¹⁰ in the formula (3-1) is a group (g2-1) (where j1 = d1 + d3, g1 = d2 + d4), a group (g2-2) (where j1 = e1, g1 = e2). ), Group (g2-3) (where j1 = 1, g1 = 2), group (g2-4) (where j1 = h1, g1 = h2), group (g2-5) ) (However, j1 = i1, g1 = i2), group (g2-6) (where j1 = 1, g1 = 1), or group (g2-7) (where j1 = 1, g1 = i3).
Further, Y ¹¹ and Y ¹² in the formula (3-2) are independently groups (g2-1) (where g2 = d2 + d4, k2 = d2 + d4) and groups (g2-2) (where g2). = E2, k2 = e2), group (g2-3) (where g2 = 2, k2 = 2), group (g2-4) (where g2 = h2, k2 = h2). ), Group (g2-5) (where g2 = i2, k2 = i2), group (g2-6 (where g2 = 1, k2 = 1), or group (g2-) 7) (However, g2 = i3 and k2 = i3) may be used.

_{^{(-A 1 -Q 12 -) e1}} C (R e2) 4-e1-e2 (-Q 22 -) e2 (g2-2)
_{^{-A 1 -Q 13 -N (-Q 23}} -) 2 (g2-3)
_{^{(-A 1 -Q 14 -) h1}} Z 1 (-Q 24 -) h2 (g2-4)
_{^{(-A 1 -Q 15 -) i1}} Si (R e3) 4-i1-i2 (-Q 25 -) i2 (g2-5)
-A ¹ -Q ²⁶ - (g2-6)
^{-A 1 -Q 12 -CH (-Q 22} -) - Si (R e3) 3-i3 (-Q 25 -) i3 (g2-7)

However, in the formula (g2-1) ~ (g2-7), connected to the ^{A 1} side is _{^{(OX) m, Q 22,}} Q 23, Q 24, Q 25 or ^{Q 26} side is [-Si _{(R) n} Connect to [L _3-n ].
A ¹ is a single bond, -C (O) NR ^6- , -C (O)-, -OC (O) O-, -NHC (O) O-, -NHC (O) NR ^6- , -O -Or-SO ₂ NR ^6- .
Q ¹¹ represents a single bond, -O-, carbon of an alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or It is a group having —O—.
Q ¹² represents a single bond, the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- and a group ^having, Y ^{10, if Y 11} or ^{Y 12} has a ^{Q 12} 2 or more, two or more ^{Q 12} may be different even in the same.
Q ¹³ represents a single bond (provided that, ^{A 1} is -C (O) -.), The carbon of the alkylene group, having two or more alkylene groups having a carbon - -C between carbon atoms (O) ^NR 6 -, - A group having C (O)-, -NR ^6- or -O-, or a group having -C (O)-at the N-side end of an alkylene group.
Q ¹⁴ is Q ¹² if the atom in Z ¹ to which Q ¹⁴ is bonded is a carbon atom, and Q ¹³ if the atom in Z ¹ to which Q ¹⁴ is bonded is a nitrogen atom, Y ¹⁰ , Y ¹¹ or When Y ¹² has two or more Q ^14s , the two or more Q ^14s may be the same or different.
Q ^15, the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- a group having a ^There, Y ^{10, if Y 11} or ^{Y 12} has a ^{Q 15} 2 or more, two or more ^{Q 15} may be different even in the same.
Q ²² represents an alkylene group, a carbon number of 2 or more alkylene group having a carbon - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or a group having -O-, alkylene A group having -C (O) NR ^6- , -C (O)-, -NR ^6- or -O- at the end of the group not connected to Si, or a carbon-carbon of an alkylene group having 2 or more carbon atoms. -C between atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- and having and -C to the end on the side not connected to the ^{Si (O) NR 6 -,} - C ^{(O) -, - NR 6} - or a group having ^-O-, if Y ^{10, Y 11} or ^{Y 12} has a ^{Q 22} 2 or more, two or more ^{Q 22} is optionally substituted by one or more identical May be good.
Q ^23, the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- a group having a There, the two of Q ²³ may be the same or different.
Q ²⁴ is Q ²² if the atom in Z ¹ to which Q ²⁴ is bonded is a carbon atom, and Q ²³ if the atom in Z ¹ to which Q ²⁴ is bonded is a nitrogen atom, Y ¹⁰ , Y ¹¹ or When Y ¹² has two or more Q ^24s , the two or more Q ^24s may be the same or different.
Q ^25, the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- a group having a ^There, Y ^{10, if Y 11} or ^{Y 12} has a ^{Q 25} 2 or more, two or more ^{Q 25} may be different even in the same.
Q ^26, the carbon of the alkylene group or an alkylene group having 2 or more carbon, - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or -O- a group having a is there.
Z ¹ is a group having an h1 + h2 valent ring structure having a carbon atom or nitrogen atom to which Q ¹⁴ is directly bonded and a carbon atom or nitrogen atom to which Q ²⁴ is directly bonded.
R ^e1 is a hydrogen atom or an alkyl group, and when Y ¹⁰ , Y ¹¹ or Y ¹² has two or more ^{Re 1} , the two or more R ^{e 1s} may be the same or different.
^Re2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.
^Re3 is an alkyl group. R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

d1 is an integer of 0 to 3, preferably 1 or 2. d2 is an integer of 0 to 3, preferably 1 or 2. d1 + d2 is an integer of 1 to 3.
d3 is an integer of 0 to 3, preferably 0 or 1. d4 is an integer of 0 to 3, preferably 2 or 3. d3 + d4 is an integer of 1 to 3.
d1 + ^d3, in ^{Y 10} represents an integer of 1 to 5, preferably 1 or ^2, is 1 in the ^{Y 11} and ^{Y 12.}
d2 + ^d4, in ^{Y 10} represents an integer of 1 to 5, is preferably 4 or ^5, in ^{Y 11} and ^{Y 12} represents an integer of 3-5, is preferably 4 or 5.
e1 + e2 is 3 or 4. ^e1, in ^{Y 10} represents an integer of 1 to 3, 1 or and even preferably at ^2, is a 1 in the ^{Y 11} and ^{Y 12. e2,} in ^{Y 10} represents an integer of 1 to 3, is preferably 2 or ^3, in ^{Y 11} and ^{Y 12} is 2 or 3.
^h1, in ^{Y 10} represents an integer of 1 or more, 1 or and even preferably at ^2, it is a 1 in the ^{Y 11} and ^{Y 12.} h2 is an integer of 1 or more, preferably 2 or 3.
i1 + i2 is 3 or 4. ^i1, in ^{Y 10} represents an integer of 1 to 3, 1 or and even preferably at ^2, is a 1 in the ^{Y 11} and ^{Y 12. i2,} in ^{Y 10} represents an integer of 1 to 3, is preferably 2 or ^3, in ^{Y 11} and ^{Y 12} is 2 or 3.
i3 is 2 or 3.

^{Q 11, Q 12, Q 13} , Q 14, Q 15, Q 22, Q 23, Q 24, carbon atoms in the alkylene group of ^{Q 25} and ^{Q 26,} the compound (3-1) and the compound (3-2) 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is particularly preferable, because it is easy to manufacture the compound and the water and oil repellent layer is further excellent in abrasion resistance, light resistance and chemical resistance. However, the lower limit of the number of carbon atoms of the alkylene group when a specific bond is formed between carbon atoms is 2.

Examples of the ring structure in Z ¹ include the above-mentioned ring structure, and the preferred form is also the same. Since Q ¹⁴ and Q ²⁴ are directly bonded to the ring structure in Z ¹ , for example, an alkylene group is linked to the ring structure, and Q ¹⁴ and Q ²⁴ are not linked to the alkylene group.

The number of carbon atoms of the alkyl group of R ^e1 , ^{Re 2} or ^Re 3 is preferably 1 to 6 and more preferably 1 to 3 from the viewpoint of easy production of compound (3-1) and compound (3-2). ~ 2 is particularly preferable.
The number of carbon atoms in the alkyl group portion of the acyloxy group of Re ² is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of the compound (1).
h1 is preferably 1 to 6 and more preferably 1 to 4 because it is easy to produce the compound (3-1) and the compound (3-2) and the abrasion resistance of the water- and oil-repellent layer is further excellent. 1 or 2 is more preferable, and 1 is particularly preferable.
As h2, 2 to 6 are preferable, and 2 to 4 are more preferable because the compound (3-1) and the compound (3-2) can be easily produced and the friction resistance of the water- and oil-repellent layer is further excellent. Preferably, 2 or 3 is particularly preferred.

Other forms of Y ^10, group (g2-8) (provided that j1 = d1 + d3, g1 = d2 × k3 + d4 × k3.), Group (g2-9) (however, j1 = e1, g1 = e2 × k3), group (g2-10) (where j1 = 1, g1 = 2 × k3), group (g2-11) (where j1 = h1, g1 = h2 × k3). ), Group (g2-12) (where j1 = i1, g1 = i2 × k3), group (g2-13) (where j1 = 1, g1 = k3), or group (. g2-14) (where j1 = 1, g1 = i3 × k3) can be mentioned.
Other forms of Y ¹¹ and Y ¹² include groups (g2-8) (where k2 = d2 × k3, g2 = d4 × k3), groups (g2-9) (where k2 = e2 ×). k3, g2 = e2 × k3), group (g2-10) (where k2 = 2 × k3, g2 = 2 × k3), group (g2-11) (where k2 = h2 × k3, g2 = h2 × k3), group (g2-12) (where k2 = i2 × k3, g2 = i2 × k3), group (g2-13) (where k2 = k3, g2 = k3), or a group (g2-14) (where k2 = i3 × k3, g2 = i3 × k3).

_{^{(-A 1 -Q 12 -) e1}} C (R e2) 4-e1-e2 (-Q 22 -G 1) e2 (g2-9)
-A ^1- Q ^13- N (-Q ^23- G ¹ ) ₂ (g2-10)
_{^{(-A 1 -Q 14 -) h1}} Z 1 (-Q 24 -G 1) h2 (g2-11)
_{^{(-A 1 -Q 15 -) i1}} Si (R e3) 4-i1-i2 (-Q 25 -G 1) i2 (g2-12)
-A ^1- Q ^26- G ¹ (g2-13)
-A ^1- Q ^12- CH (-Q ^22- G ¹ ) -Si (R ^e3 ) _3-i3 (-Q ^25- G ¹ ) _i3 (g2-14)

However, in the formula (g2-8) ~ (g2-14), connected to the ^{A 1} side is _{(OX) m,} connected to the ^{G 1} side is _{[-Si (R) n L 3} -n]. G ¹ is a group ^{(g3), Y 10, Y} 11 or ^{Y 12} 2 or more in ^{G 1} with the can may be the same or different. The codes other than G ¹ are the same as the codes in the formulas (g2-1) to (g2-7).
-Si (R ⁸ ) _3-k3 (-Q ^3- ) _k3 (g3)
However, in the equation (g3), the Si side is connected to Q ²² , Q ²³ , Q ²⁴ , Q ²⁵ and Q ²⁶ , and the Q ³ side is connected to [-Si (R) _n L _3-n ]. R ⁸ is an alkyl group. Q ³ are carbon atoms in the alkylene group, having two or more alkylene groups having a carbon - -C between carbon atoms ^{(O) NR 6 -, -} C (O) -, - NR 6 - or a group having -O- or, _{^{- (OSi (R 9) 2}} ) is a p -O-, 2 or more ^{Q 3} are may be the same or different. k3 is 2 or 3. R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ⁹ is an alkyl group, a phenyl group or an alkoxy group, and the two R ^9s may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSI (R ⁹ ) ₂ ) may be the same or different.

The alkylene group of Q ³ are the compounds (3-1) and the compound (3-2) prepared easily point a, as well as abrasion resistance of the water-repellent oil-repellent layer, further excellent point light resistance and chemical resistance Therefore, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is particularly preferable. However, the lower limit of the number of carbon atoms of the alkylene group when a specific bond is formed between carbon atoms is 2.
The number of carbon atoms of the alkyl group of R ⁸ is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint that the compound (3-1) and the compound (3-2) can be easily produced.
The number of carbon atoms of the alkyl group of R ⁹ is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint that the compound (3-1) and the compound (3-2) can be easily produced.
The number of carbon atoms of the alkoxy group of R ⁹ is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2, from the viewpoint of excellent storage stability of the compound (3-1) and the compound (3-2). preferable.
p is preferably 0 or 1.

Examples of the compound (3-1) and the compound (3-2) include the compounds of the following formulas. The compound of the following formula is industrially easy to manufacture and handle, and the water and oil repellent layer has further excellent water and oil repellency, abrasion resistance, fingerprint removal, lubricity, chemical resistance, light resistance and chemical resistance. Of these, it is preferable because it has particularly excellent light resistance. Each ^{R f} and ^{Q f} in the formula of the compound, in the formula (3-1) described above _{^{[R f1 - (OX) m}} -] and in the formula (3-2) - _{(OX) m} - is the same as The same applies to the preferred form.

Examples of the compound (3-1) in which Y ¹⁰ is a group (g2-1) include the compound of the following formula.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-2) include the compounds of the following formulas.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-3) include the compounds of the following formulas.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-4) include the compounds of the following formulas.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-5) include the compounds of the following formulas.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-6) include the compounds of the following formulas.

Examples of the compound (3-1) in which Y ¹⁰ is a group (g2-7) include the compound of the following formula.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-8) include the compounds of the following formulas.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-9) include the compounds of the following formulas.

Examples of the compound (3-1) in which Y ¹⁰ is a group (g2-10) include the compound of the following formula.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-11) include the compounds of the following formulas.

Examples of the compound (3-1) in which Y ¹⁰ is a group (g2-12) include the compound of the following formula.

Examples of the compound (3-1) having Y ¹⁰ as a group (g2-13) include the compounds of the following formulas.

Examples of the compound (3-1) in which Y ¹⁰ is a group (g2-14) include the compounds of the following formulas.

Examples of the compound (3-2) having Y ¹¹ and Y ¹² as a group (g2-1) include the compounds of the following formulas.

Examples of the compound (3-2) having Y ¹¹ and Y ¹² as a group (g2-2) include the compounds of the following formulas.

Examples of the compound (3-2) having Y ¹¹ and Y ¹² as a group (g2-3) include the compounds of the following formulas.

Examples of the compound (3-2) having Y ¹¹ and Y ¹² as a group (g2-4) include the compounds of the following formulas.

Examples of the compound (3-2) having Y ¹¹ and Y ¹² as a group (g2-5) include the compounds of the following formulas.

Examples of the compound (3-2) having Y ¹¹ and Y ¹² as a group (g2-6) include the compounds of the following formulas.

Examples of the compound (3-2) having Y ¹¹ and Y ¹² as a group (g2-7) include the compounds of the following formulas.

Examples of the compound (3-2) having Y ¹¹ and Y ¹² as a group (g2-9) include the compounds of the following formulas.

Specific examples of the fluorine-containing compound include those described in the following documents. Perfluoropolyether-modified aminosilane described in JP-A-11-209585.
The silicon-containing organic fluoropolymer described in Japanese Patent No. 2874715.
The organosilicon compound described in JP-A-2000-144097.
Perfluoropolyether-modified aminosilane described in JP-A-2000-327772.
Fluorinated siloxane described in JP-A-2002-506887.
The organic silicone compound described in JP-A-2008-534696.
The fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936.
Compounds described in US Patent Application Publication No. 2010/0129672, International Publication No. 2014/1260664, and JP-A-2014-0701163.
The organosilicon compound according to International Publication No. 2011/060047 and International Publication No. 2011/059430.
Fluorine-containing organosilane compound according to International Publication No. 2012/0646949.
Fluoroxyalkylene group-containing polymer described in JP-A-2012-722272.
International Publication No. 2013/042732, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, Japanese Patent Application Laid-Open No. 2014-080473, International Publication No. Fluorine-containing ether compounds according to No. 2015/087902, International Publication No. 2017/038830, International Publication No. 2017/038832, International Publication No. 2017/187775.
Perfluoro (poly) ether-containing silane compounds according to JP-A-2014-218369, International Publication No. 2017/022437, International Publication No. 2018/079743, International Publication No. 2018/143433.
Fluoropolyether group-containing polymer-modified silanes described in JP-A-2015-199906, JP-A-2016-204656, JP-A-2016-210854, and JP-A-2016-222859.
International Publication No. 2018/216630, International Publication No. 2019/039226, International Publication No. 2019/039341, International Publication No. 2019/039186, International Publication No. 2019/0444479, Japanese Patent Application Laid-Open No. 2019-44158, Japanese Patent Application No. Fluorine-containing ether compound according to 2017-251611.

The number average molecular weight (Mn) of the fluorine-containing compound is preferably 1,000 to 20,000, more preferably 2,000 to 18,000, and particularly preferably 3,000 to 1,5,000. ..
When Mn is 1,000 or more, the fluidity and fluorine content of the molecular chain of the fluorine-containing compound are high, so that the fingerprint-removing property of the fluorine-containing compound is more excellent. When Mn is 20,000 or less, the viscosity can be easily adjusted within an appropriate range and the solubility is improved, so that the handleability at the time of film formation is excellent.

[Manufacturing method of base material with water- and oil-repellent layer]
The base material with a water- and oil-repellent layer of the present invention may be formed by using the above-mentioned fluorine-containing compound, or may be formed by using a composition containing the above-mentioned fluorine-containing compound and a liquid medium.
In the following, as an example of the method for producing a base material with a water-repellent oil-repellent layer of the present invention, a fluorine-containing compound or a composition containing a fluorine-containing compound and a liquid medium is used on the main surface of the base material. The method of forming the above will be described. The water- and oil-repellent layer can be formed under any of the production conditions of a dry coating using a fluorine-containing compound and a wet coating using a composition containing the fluorine-containing compound and a liquid medium.

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

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

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

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

The base material with a water- and oil-repellent layer of the present invention can be produced, for example, by the following method.
-A method of treating the main surface of a base material by a dry coating method using a fluorine-containing compound to obtain a base material with a water-repellent oil-repellent layer having a water-repellent oil-repellent layer formed on the main surface of the base material.
-A method in which a composition is applied to the main surface of a base material by a wet coating method and dried to obtain a base material having a water-repellent oil-repellent layer on the main surface of the base material.

Specific examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method. Among these, the vacuum vapor deposition method is preferable from the viewpoint of suppressing the decomposition of the fluorine-containing compound and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance in which a fluorine-containing compound is supported on a metal porous body such as iron or steel, or a pellet-like substance obtained by impregnating a composition and drying it may be used.

Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget. The method and the gravure coat method can be mentioned.

The drying temperature after wet coating the composition is preferably 20 to 200 ° C, particularly preferably 80 to 160 ° C.

In the method for producing a base material with a water / oil repellent layer of the present invention, the surface of the water / oil repellent layer may be washed with a solvent after the water / oil repellent layer is formed. However, the cleaning needs to be carried out under the condition that the excess fluorine amount of the water-repellent oil-repellent layer is 2 or more, and is preferably carried out under the condition that the excess fluorine amount of the water-repellent oil-repellent layer is 400 or less.
Specific examples of the above-mentioned cleaning method include a method of pouring a solvent on the surface of the water-repellent oil-repellent layer and a method of wiping the surface of the water-repellent oil-repellent layer with a fiber structure such as paper or cloth moistened with the solvent. Be done. Among them, a method of wiping the surface of the water-repellent oil-repellent layer with a fiber structure moistened with a solvent is preferable in that the excess fluorine amount of the water-repellent oil-repellent layer can be easily adjusted to the above range.
In wiping the surface of the water-repellent oil-repellent layer with a fiber structure moistened with a solvent, for example, if conditions such as the number of wiping times, the load applied to the fiber structure at the time of wiping, and the type of solvent are adjusted, the fluorine of the water-repellent oil-repellent layer The amount surplus can be set in the above range.

As the solvent used for cleaning, an organic solvent is preferable because the amount of excess components removed can be easily adjusted.

In order to improve the friction resistance of the water- and oil-repellent layer, an operation for promoting the reaction between the fluorine-containing compound and the base material or the base layer may be performed, if necessary. Examples of the operation include heating, humidification, and light irradiation. For example, by heating a base material with a water-repellent oil-repellent layer on which a water-repellent oil-repellent layer is formed in a moist atmosphere, a hydrolysis reaction of a reactive silyl group to a silanol group and a siloxane bond by a condensation reaction of a silanol group are formed. Reactions such as formation, condensation reaction of silanol groups on the surface of the base material or the base layer and silanol groups of the fluorine-containing compound can be promoted.

The water- and oil-repellent layer formed by the above procedure contains a compound obtained through a hydrolysis reaction and a condensation reaction of a fluorine-containing compound.

Hereinafter, the present invention will be described in detail with reference to an example. Example 1-2 to Example 1-4, Example 1-6 to Example 1-8, Example 1-10 to Example 1-15, Example 2-2 to Example 2-4, Example 2-6 to Example 2-9, Examples 2-11 to 2-13 and 2-15 are examples, and Examples 1-1, 1-5, 1-9, 2-1 and 2-5, 2-10 and Example 2-14 is a comparative example. However, the present invention is not limited to these examples.

[Physical properties and evaluation]
(Number average molecular weight)
The number average molecular weight of the fluorine-containing compound was calculated by determining the number (mean value) of oxyperfluoroalkylene groups with reference to the terminal groups by ¹ H-NMR and ¹⁹ F-NMR. The terminal group is, for example, A or Si (R) _n L _3-n in the formula (3).

(Excess fluorine amount)
The fluorine amount surplus of the water-repellent oil-repellent layer was calculated according to the above-mentioned method for calculating the fluorine amount surplus.
The fluorine atomic strength F1 was measured in an environment with a humidity of 60% RH and a room temperature of 23 ° C.
For the operation of wiping the base material with a water-repellent oil-repellent layer, a Kimwipe moistened by immersing Kimwipe S-200 (manufactured by Nippon Paper Crecia) in Asahi Clean AE-3000 (manufactured by AGC) for 3 minutes. Using. To wipe the water- and oil-repellent layer, use a reciprocating traverse tester (manufactured by KNT) equipped with a moistened Kimwipe, and reciprocate 50 times at a pressure of 29 N and a speed of 320 cm / min (that is, wipe 100 times). And carried out. The moistened Kimwipe was replaced with a new one every 10 round trips.

(Fingerprint removal)
After adhering an artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) to the flat surface of a silicone rubber stopper, wipe off excess oil with a non-woven fabric (Bencot (registered trademark) M-3 manufactured by Asahi Kasei Corporation). Prepared a fingerprint stamp. The fingerprint stamp was placed on a water-repellent and oil-repellent layer and pressed at a load of 9.8 N for 10 seconds. The haze at the place where the fingerprint was attached was measured with a haze meter and used as the initial value. The fingerprints were wiped off at a load of 2.0 N using a reciprocating traverse tester (manufactured by KNT) equipped with Bencot M-3. The value of haze was measured for each round trip of wiping, and the number of times of wiping that haze became 10% or less from the initial value was measured. The smaller the number of wipes, the easier it is to remove fingerprint stains, and the better the fingerprint removal property. The evaluation criteria are as follows, and any evaluation of D or higher can be used practically.
A: The number of wipes is 3 or less.
B: The number of wipes is 4 to 5 times.
C: The number of wipes is 6 to 7 times.
D: The number of wipes is 8 to 10 times.
E: The number of wipes is 11 or more.

(appearance)
The haze of the water- and oil-repellent layer was measured with a haze meter (manufactured by Toyo Seiki Co., Ltd.). The smaller the haze, the more uniformly the fluorine-containing compound can be applied, and the better the appearance. The evaluation criteria are as follows.
◎ (excellent): Haze is less than 0.1%.
○ (Good): Haze is 0.1% or more and less than 0.5%.
Δ (possible): Haze is 0.5% or more and less than 1.0%.
× (impossible): Haze is 1.0% or more.

[Compound (3-2A)]
Fluorolink® S10 (manufactured by Solvay) was used as compound (3-2A). (CH ₃ CH ₂ O) ₃ Si-C ₃ H _6- NHC (O) -CF ₂ -{(OCF ₂ ) _q (OC ₄ F ₈ ) _p } -OCF ₂ C (O) NH-C ₃ H ₆ -Si (OCH ₂ CH ₃ ) ₃ (3-2A)
Number average molecular weight (Mn): 1,600, p = 5.5, q = 5.5

[Compound (3-2B)]
Compound (3-2B) was obtained according to Example 4 of JP-A-2015-199906. In the following chemical formula,-[OCF ₂ ] _p1- [OC ₄ F ₈ ] _q1- represents a random sequence chain having p1 (OCF ₂ ) and q1 (OC ₄ F ₈ ).

In the above formula (3-2B), p1: q1 ≈ 47: 53, p1 + q1 ≈ 43, and the number average molecular weight (Mn) of the compound (3-2B) is 4,800.

[Compound (3-2C)]
The compound described in paragraph 0048 of JP-A-2015-037541 was used as the compound (3-2C).

In the above formula (3-2C), p1 / q1 = 1.0, p1 + q1≈45, and the number average molecular weight (Mn) of the compound (3-2C) is 5,400.

[Mixture (M1): (Mixture of compound (3-1A) and compound (3-2D))]
A mixture (M1) containing the following compound (3-1A) and the following compound (3-2D) was synthesized by the following procedure.

(Synthesis Example D-1)
Compound (D-1) was obtained according to the method described in Example 1-1 of Examples of WO 2013-121984.
CF ₂ = CFO-CF ₂ CF ₂ CF ₂ CH ₂ OH (D-1)

(Synthesis Example D-2)
In a 200 mL eggplant flask, 16.2 g of HO-CH ₂ CF ₂ CF ₂ CH _2- OH and 13.8 g of potassium carbonate were placed, stirred at 120 ° C., and 278 g of compound (D-1) was added to 120. The mixture was stirred at ° C. for 2 hours. The temperature was returned to 25 ° C., 50 g each of AC-2000 (product name, manufactured by AGC, C ₆ F ₁₃ H) and hydrochloric acid was added, and the liquid was separated to concentrate the organic phase. The obtained crude reaction solution was purified by column chromatography to obtain 117.7 g (yield 40%) of compound (D-2).

NMR spectrum of compound (D-2);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 6.0 (12H), 4.6 (20H), 4.2 (4H), 4 .1 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -85 (24F), -90 (24F), -120 (20F), -122 (4F), -123 (4F), -126 (24F), -144 (12F)
Average value of the number of units m + n: 10.

(Synthesis Example D-3)
In a 50 mL eggplant flask connected to a reflux condenser, 20 g of the compound (D-2) obtained in Synthesis Example D-2, 2.4 g of sodium fluoride powder, 20 g of AC-2000, CF ₃ CF ₂ CF ₂ 18.8 g of OCF (CF ₃ ) COF was added. The mixture was stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the sodium fluoride powder was removed with a pressure filter, and excess CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF and AC-2000 were distilled off under reduced pressure to compound (D-3). 24 g (yield 100%) was obtained.

NMR spectrum of compound (D-3);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 6.0 (12H), 5.0 (4H), 4.6 (20H), 4 .2 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -85 (24F), -90 (24F), -119 (4F), -120 (20F), -122 (4F), -126 (24F), -129 (4F), -131 (2F), -144 (12F).
Average value of the number of units m + n: 10.

(Synthesis Example D-4)
250 mL of ClCF ₂ CFClCF ₂ OCF ₂ CF ₂ Cl (hereinafter referred to as "CFE-419") was placed in a 500 mL nickel reactor, and nitrogen gas was bubbled. After the oxygen gas concentration was sufficiently lowered, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour. A CFE-419 solution (concentration: 10% by mass, compound D-3: 24 g) of the compound (D-3) obtained in Synthesis Example D-3 was added over 6 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in compound D-3 (mol / hour) was controlled to be 2: 1. After the addition of compound D-3 was completed, a CFE-419 solution of benzene (concentration: 0.1% by mass, benzene: 0.1 g) was added intermittently. After the addition of benzene was completed, the fluorine gas was bubbled for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 25.3 g (yield 90%) of compound (D-4).

NMR spectrum of compound (D-4);
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -79 (4F), -81 (6F), -82 (6F), -83 (48F), -87 (44F),-124 (48F), -129 (4F), -131 (2F).
Average value of the number of units l: 11.

(Synthesis Example D-5)
In a 50 mL eggplant flask, 25.3 g of the compound (D-4) obtained in Synthesis Example D-4, 2.2 g of sodium fluoride, and 25 mL of AC-2000 were placed and stirred in an ice bath. 1.7 g of methanol was added and stirred at 25 ° C. for 1 hour. After filtration, the filtrate was purified by column chromatography. 15 g (yield 80%) of compound (D-5) was obtained.

NMR spectrum of compound (D-5);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 4.2 (6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -83 (44F), -87 (44F), 119 (4F), -124 (44F).
Average value of the number of units l: 11.

(Synthesis Example D-6)
In a 50 mL eggplant flask, 15 g of the compound (D-5) obtained in Synthesis Example D-5, 3.2 g of H ₂ NCH ₂ C (CH ₂ CH = CH ₂ ) ₃ , and 15 mL of AC-2000 were placed. The mixture was stirred at 0 ° C. for 24 hours. The crude reaction solution was purified by column chromatography and separated into three fractions containing the desired product. A total of 11.2 g (yield 70%) of compound (D-6) was obtained. Fractions of each of the three types were obtained as (C4-6a), (C4-6b) and (C4-6c).
The fractions (C4-6a) to (C4-6c) contained compound (D-6) and compound (D-7). Then, the ratio (CF ₃ / CF ₂ ) was determined by ¹⁹ F-NMR using a fraction (C4-6a). Incidentally, CF ₃ in a ratio means the number of moles of the compound (D-7) While _a -CF ₃ group at the end of the _(a -CF ₃ group within the dotted line frame in the formula), the ¹⁹ F-NMR - It is observed at 85-87 ppm. Further, CF ₂ in a ratio, the compound (D-7) at one end near the -CF ₂ - group (-CF ₂ within the dotted line frame in the formula - group) and both compounds (D-6) -CF ₂ in the vicinity of the end - group (-CF ₂ within the dotted line frame in the formula - group) and means the total number of moles of, is observed -120ppm in ¹⁹ F-NMR.
CF ₃ / CF ₂ = 0.11 in the fraction (C4-6a)

NMR spectrum of compound (D-6);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 6.1 (6H), 5.2 (12H), 3.4 (4H), 2 .1 (12H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -83 (44F), -87 (44F), -120 (4F), -124 (44F).
Average value of the number of units l: 11.

(Synthesis Example D-7)
In a 50 mL eggplant flask, 1 g of the distillate (C4-6a) obtained in Synthesis Example D-6, 0.21 g of trimethoxysilane, 0.001 g of aniline, 1.0 g of AC-6000, platinum / 1, 0.0033 g of 3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added, and the mixture was stirred at 25 ° C. overnight. The solvent and the like were distilled off under reduced pressure to obtain 1.2 g (yield 100%) of the mixture (M1).
The mixture (M1) contained compound (3-1A) and compound (3-2D).
Using the mixture (M1), the ratio (CF ₃ / CF ₂ ) was determined by ¹⁹ F-NMR in the same manner as in Synthesis Example D-6. The groups in the dotted frame in the formula are the groups to be measured by ¹⁹ F-NMR.
CF ₃ / CF ₂ = 0.11 in the mixture (M1)

NMR spectrum of compound (3-2D);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 3.6 (54H), 3.4 (4H), 1.3 (24H), 0 .9 (12H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -83 (44F), -87 (44F), -120 (4F), -124 (44F).
Average value of the number of units m + n: 11.

[Compound (3-2D)]
The compound (3-2D) was obtained by separating the compound (3-1A) and the compound (3-2D) by molecular distillation in the mixture (M1) obtained as described above.

[Synthesis Example E1]
(Synthesis Example E1-1)
Compound (X1-1) was obtained according to the method described in Example 1-1 of Examples of WO 2013-121984.
CF ₂ = CFO-CF ₂ CF ₂ CF ₂ CH ₂ OH (X1-1)

(Synthesis Example E1-2)
10 g of the compound (X1-1) obtained in Synthesis Example E1-1 was placed in a 100 mL stainless steel reactor, and the mixture was stirred at 175 ° C. for 200 hours. The obtained organic phase was concentrated to give 6 g of compound (X1-2).

NMR spectrum of compound (X1-2);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 4.1 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -80 (2F), -85 (2F), -123 (4F), -126 (4F), -128 (2F), -131 (2F), -137 (1F), -139 (1F)

(Synthesis Example E1-3)
In a 200 mL eggplant flask, 5 g of the compound (X1-2) obtained in Synthesis Example E1-2 and 1.2 g of potassium carbonate were placed, stirred at 120 ° C., and 25 g of the compound (X1-1) was added to 120 ° C. Was stirred for 2 hours. Back to 25 ℃, AC-2000 (product name, AGC _Corp., C _{6 F 13} H) and hydrochloric acid were placed 30g each, were separated, the organic phase was concentrated. The obtained crude reaction solution was purified by column chromatography to obtain 21 g of compound (X1-3).

NMR spectrum of compound (X1-3);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 6.0 (10H), 4.6 (20H), 4.1 (4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -80 (2F), -85 (22F), -91 (20F), -120 (20F), -123 (4F), -126 (24F), -128 (2F), -131 (2F), -137 (1F), -139 (1F), -144 (10F)
Average value of the number of units m + n: 10.

(Synthesis Example E1-4)
In a 50 mL eggplant flask connected to a reflux condenser, 20 g of the compound (X1-3) obtained in Synthesis Example E1-3, 7.1 g of sodium fluoride powder, 20 g of AC-2000, CF ₃ CF ₂ CF ₂ 20 g of OFF (CF ₃ ) COF was added. The mixture was stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. After cooling to room temperature, sodium fluoride powder was removed with a pressure filter, and excess CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF and AC-2000 were distilled off under reduced pressure to compound (X1-4). 24 g of was obtained.

NMR spectrum of compound (X1-4);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 6.0 (10H), 5.0 (4H), 4.6 (20H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -79 (4F), -80 (2F), -81 (6F), -82 (6F), -85 (22F), -91 (20F), -119 (4F), -120 (20F), -126 (24F), -128 (2F), -129 (4F), -131 (2F), -131 (2F) ), -137 (1F), -139 (1F), -144 (10F).
Average value of the number of units m + n: 10.

(Synthesis Example E1-5)
250 mL of CFE-419 was placed in a 500 mL nickel reactor and nitrogen gas was bubbled. After the oxygen gas concentration was sufficiently lowered, 20% by volume of fluorine gas diluted with nitrogen gas was bubbled for 1 hour. A CFE-419 solution (concentration: 10%, compound (X1-4): 20 g) of the compound (X1-4) obtained in Synthesis Example E1-4 was added over 3 hours. The ratio of the introduction rate of fluorine gas (mol / hour) to the introduction rate of hydrogen atoms in the compound (X1-4) (mol / hour) was controlled to be 2: 1. After the addition of the compound (X1-4) was completed, a CFE-419 solution of benzene (concentration: 0.1%, benzene: 0.1 g) was added intermittently. After the addition of benzene was completed, the fluorine gas was bubbled for 1 hour, and finally the inside of the reactor was sufficiently replaced with nitrogen gas. The solvent was distilled off to obtain 21 g of a mixture containing the compound (X1-5) as a main component.

NMR spectrum of compound (X1-5);
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -79 (4F), -80 (2F), -81 (6F), -82 (6F), -83 (46F), -87 (40F), -124 (48F), -128 (2F), -129 (4F), -131 (2F), -131 (2F), -137 (1F), -139 (1F) ).
Average value of the number of units m + n: 10.

(Synthesis Example E1-6)
In a 50 mL eggplant flask, 20 g of a mixture containing the compound (X1-5) obtained in Synthesis Example E1-5 as a main component, 1.8 g of sodium fluoride, and 20 mL of AC-2000 were placed and stirred in an ice bath. did. 1.4 g of methanol was added, and the mixture was stirred at 25 ° C. for 1 hour. After filtration, the filtrate was purified by column chromatography. 14 g of a mixture containing the compound (X1-6) as a main component was obtained.

NMR spectrum of compound (X1-6);
^{1 1} H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: tetramethylsilane (TMS)) δ (ppm): 4.2 (6H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -80 (2F), -83 (42F), -87 (40F), -119 (4F), -124 (44F), -128 (2F), -131 (2F), -137 (1F), -139 (1F).
Average value of the number of units m + n: 10.

(Synthesis Example E1-7)
In a 50 mL eggplant flask, 12 g of a mixture containing the compound (X1-6) obtained in Synthesis Example E1-6 as a main component, 1.1 g of H ₂ NCH ₂ CH (CH ₂ CH = CH ₂ ) ₂ , AC- 12 mL of 2000 was added and stirred at 0 ° C. for 24 hours. The crude reaction solution was purified by column chromatography and separated into three fractions containing the desired product. A total of 9 g of the compound (X1-7) was obtained. Fractions of each of the three types were designated as (C1-7a), (C1-7b), and (C1-7c), and a part of the fraction of (C1-7c) was further purified by column chromatography (C1-7d). ) Was obtained.
The fractions (C1-7a) to (C1-7d) contained compound (X1-7) and compound (X1-8).

(Synthesis Example E1-8)
In a 50 mL eggplant flask, 1 g of the distillate (C1-7a) obtained in Synthesis Example E1-7, 0.21 g of trimethoxysilane, 0.001 g of aniline, AC-6000 (product name, manufactured by AGC, C). 1.0 g of ₆ F ₁₃ C ₂ H ₅ ) and 0.0033 g of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added, and the mixture was stirred at 25 ° C. overnight. The solvent and the like were distilled off under reduced pressure to obtain 1.2 g of a mixture (M2) containing the compound (2-B).
The mixture (M2) contained compound (1-B) and compound (2-B). Then, the ratio (CF ₃ / CF ₂ ) was determined by ¹⁹ F-NMR using each fraction. CF ₃ in a ratio means the number of moles of the compound (1-B) -CF ₃ group at one end of the (-CF ₃ group within the dotted line frame in the ^formula), the ¹⁹ F-NMR -85 ~ Observed at -87 ppm. Further, CF ₂ in the ratio, compound (1-B) one end vicinity in -CF ₂ the - group (-CF ₂ within the dotted line frame in the formula - group) and both compounds (2-B) -CF ₂ in the vicinity of the end - group (-CF ₂ within the dotted line frame in the formula - group) and means the total number of moles ^of, is observed -120ppm in ¹⁹ F-NMR.
CF ₃ / CF ₂ = 0.17 in the mixture (M2)
The average value of the number of units m + n in compound (2-B) is 10.

[Synthesis Example F]
Compound (3-1B) was obtained according to the method described in Example 2 of Examples of WO 2009-008380. Average value of the number of units n: 7.
CF ₃ O- [CF ₂ CF ₂ O] _n CF ₂ C (O) NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (3-1B)

[Synthesis Example G]
Compound (3-1C) was obtained according to the method described in Example 3-4 of Examples of WO 2017-038832. Average value of the number of units n: 13.
CF ₃ O- [CF ₂ CF ₂ O-CF ₂ CF ₂ CF ₂ CF ₂ O] _n CF ₂ CF _2- O-CF ₂ CF ₂ CF ₂ CH ₂ N [(CH ₂ ) ₃ Si (OCH ₃ ) ₃ ] ₂ (3-1C)

[Example 1-1]
Compound (3-2A) and Novec 7200 (product name, manufactured by 3M, C ₄ F ₉ OC ₂ H ₅ , boiling point 76 ° C.) as an organic solvent are mixed to prepare the composition (solid content) of Example 1-1. Concentration: 10% by mass) was obtained.
0.5 g of the obtained composition was filled in a molybdenum-based boat in a vacuum vapor deposition apparatus (VTR-350M, manufactured by ULVAC), and the inside of the vacuum vapor deposition apparatus was exhausted to 1 × 10 ^-3 Pa or less. The boat on which the composition is placed is heated at a heating rate of 10 ° C./min or less, and when the vapor deposition rate by the crystal oscillation type film thickness meter exceeds 1 nm / sec, the shutter is opened and the base material (chemically tempered glass) is opened. The film formation on the surface of the The shutter was set to close when the film thickness reached 50 nm, and the film formation on the surface of the substrate was completed.
The base material on which the compound in the composition was deposited was heat-treated at 200 ° C. for 30 minutes to obtain a base material with a film in which a film containing a condensate of a fluorine-containing compound was formed on the base material.
Then, the surface of the film containing the condensate of the fluorine-containing compound was wiped 50 times with Kim Wipe S-200 moistened with AE-3000 (manufactured by AGC), and then dried at 150 ° C. for 45 minutes. A substrate with a water- and oil-repellent layer of 1-1 was obtained.
Various physical properties were measured and evaluated using the obtained base material with a water- and oil-repellent layer. The results are shown in Table 1.

[Example 1-2 to Example 1-17]
The type of fluorine-containing compound, the organic solvent used for wetting Kim Wipe S-200 (indicated as wet in the table. IPA means isopropyl alcohol), and the film containing the condensate of the fluorine-containing compound. Substrate with water-repellent and oil-repellent layer of Examples 1-2 to 1-17 was obtained in the same manner as in Example 1-1 except that the number of wiping times was changed as shown in Table 1.
Various physical properties were measured and evaluated using the obtained base material with a water- and oil-repellent layer. The results are shown in Table 1.

[Example 2-1]
Compound (3-2A) and Novec 7200 as an organic solvent were mixed to obtain the composition of Example 2-1 (solid content concentration: 20% by mass).
A base material (chemically tempered glass) was dipped in the obtained composition, left for 30 minutes, and then the base material was pulled up (dip coating method). The coating film was dried at 200 ° C. for 30 minutes to obtain a substrate with a film in which a film containing a condensate of a fluorine-containing compound was formed on the substrate.
Then, the film containing the condensate of the fluorine-containing compound was wiped 50 times with Kim Wipe S-200 moistened with AE-3000 (manufactured by AGC), and then dried at 150 ° C. for 45 minutes. Example 2- A substrate with a water- and oil-repellent layer of 1 was obtained.
Various physical properties were measured and evaluated using the obtained base material with a water- and oil-repellent layer. The results are shown in Table 2.

[Example 2-2 to Example 2-20]
Other than changing the type of fluorine-containing compound, the organic solvent used to wipe the film containing the condensate of the fluorine-containing compound, and the number of times the film containing the condensate of the fluorine-containing compound was wiped as shown in Table 2. Obtained the base material with the water- and oil-repellent layer of Examples 2-2 to 2-20 in the same manner as in Example 2-1.
Various physical properties were measured and evaluated using the obtained base material with a water- and oil-repellent layer. The results are shown in Table 2.

As shown in Tables 1 and 2, it was confirmed that the fingerprint removing property was excellent when a base material with a water-repellent oil-repellent layer having a water-repellent oil-repellent layer having an excess fluorine amount of 2 or more was used (Examples 1-2 to 2). Example 1-4, Example 1-6 to Example 1-8, Example 1-10 to Example 1-15, Example 1-17, Example 2-2 to Example 2-4, Example 2-6 to Example 2-9, Examples 2-11 to 2-14, Examples 2-16 to 2-20).
In addition, in Example 1-1 to Example 1-17 and Example 2-1 to Example 2-20, the base material after determining the excess amount of fluorine was further wiped back and forth 10 times using AE-3000. However, there was no change in the value of F2.

The base material with a water-repellent oil-repellent layer of the present invention can be used for various applications in which water-repellent and oil-repellent properties are required. For example, display input devices such as touch panels; transparent glass or transparent plastic members, lenses for glasses, antifouling members for kitchens; water- and moisture-proof members and antifouling members for electronic devices, heat exchangers, batteries, etc. Antifouling member for toiletry; member that requires liquid repellency while conducting; water-repellent / waterproof / water-sliding member of heat exchanger; can be used for vibration sieve, surface low friction member such as inside a cylinder, and the like. More specific examples of use include a display front protective plate, an antireflection plate, a polarizing plate, an antiglare plate, or an antiglare coating on the surface thereof, a mobile phone (for example, a smartphone), or a personal digital assistant. , Game machines, devices such as remote controls, touch panel sheets, touch panel displays, and other devices that have display input devices that operate on the screen with human fingers or palms (for example, glass or film used for display units, etc., and Glass or film used for the exterior part other than the display part). In addition to the above, decorative building materials around water such as toilets, baths, washrooms, kitchens; waterproof members for wiring boards; water-repellent / waterproof / sliding members for heat exchangers; water-repellent members for solar cells; printed wiring boards Waterproof / water-repellent material; Waterproof / water-repellent material for electronic device housings and electronic parts; Waterproof / water-repellent material for power transmission lines; Waterproof / water-repellent material for various filters; Radio absorbers and sound absorbing materials Waterproofing members; Antifouling members for baths, kitchen equipment, toiletries; Surface low friction members such as vibrating sieves and cylinders; Mechanical parts, vacuum equipment parts, bearing parts, transportation equipment parts such as automobiles; Tools, etc. Examples include surface protection members.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2019-102320 filed on May 31, 2019 are cited here and incorporated as disclosure of the specification of the present invention. Is.

Claims (12)

1. A base material with a water- and oil-repellent layer having a base material and a water- and oil-repellent layer containing a condensate of a fluorine-containing compound arranged on the main surface of the base material.
   A base material with a water-repellent oil-repellent layer, wherein the excess fluorine amount of the water-repellent oil-repellent layer calculated by the following method is 2 or more.
   (Calculation method for excess fluorine)
   Using a fluorescent X-ray analyzer (Rigaku, ZSX100e), measurement diameter: 30 mm, measurement line: FKα, filter: OUT, slit: standard, spectroscopic crystal: RX35 (Rigaku), detector: PC, PHA: 100-300, peak angle: 38.794 deg. (20 sec), B.I. G. Angle: 43.000 deg. The fluorine atomic strength F1 in the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer and the surface of the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer measured under the condition of (10 sec). Fluorine atomic strength F2 in the water-repellent oil-repellent layer of the base material with the water-repellent oil-repellent layer after wiping 100 times with Kimwipe (registered trademark) moistened with Asahiclean (registered trademark) AE-3000 (manufactured by AGC). Therefore, the excess fluorine amount is calculated by the following formula (I).
   Fluorine surplus = (F1-F2) / F2 × 100 (I)
2. The base material with a water-repellent oil-repellent layer according to claim 1, wherein the excess amount of fluorine is 5 or more.
3. The base material with a water-repellent oil-repellent layer according to claim 1 or 2, wherein the excess amount of fluorine is 400 or less.
4. The base material with a water-repellent oil-repellent layer according to claim 1 or 2, wherein the excess amount of fluorine is 200 or less.
5. The base material with a water-repellent oil-repellent layer according to any one of claims 1 to 4, wherein the fluorine-containing compound has a poly (oxyfluoroalkylene) chain and a reactive silyl group.
6. The base material with a water-repellent oil-repellent layer according to claim 5, wherein the fluorine-containing compound has two or more reactive silyl groups.
7. The base material with a water-repellent oil-repellent layer according to claim 6, wherein the fluorine-containing compound has the reactive silyl groups on both terminal sides of the poly (oxyfluoroalkylene) chain.
8. The water- and oil-repellent layer according to claim 7, wherein the compound in which the reactive silyl group is located on both end sides of the poly (oxyfluoroalkylene) chain is a compound represented by the formula (3-2). Base material.
   ^{_{[L 3-n (R)}} n Si-] k2 Y 12 - (OX) m -Y 11 [-Si (R) n L 3-n] g2 (3-2)
   However, in equation (3-2),
   X is a fluoroalkylene group having one or more fluorine atoms.
   m is an integer greater than or equal to 2
   Y ¹¹ is a (g2 + 1) valence linking group.
   Y ¹² is a linking group of (k2 + 1) valence,
   R is a monovalent hydrocarbon group and
   L is a hydrolyzable group or a hydroxyl group,
   n is an integer of 0 to 2 and
   g2 is an integer greater than or equal to 1 and
   k2 is an integer of 1 or more.
9. The base material with a water-repellent oil-repellent layer according to claim 6, wherein the fluorine-containing compound has two or more reactive silyl groups on one end side of the poly (oxyfluoroalkylene) chain.
10. The base material with a water-repellent oil-repellent layer according to any one of claims 1 to 9, wherein the number average molecular weight (Mn) of the fluorine-containing compound is 1,000 to 20,000.
11. The condensate of the fluorine-containing compound has a compound having a reactive silyl group on both terminal sides of the poly (oxyfluoroalkylene) chain and a fluorine-containing compound having a reactive silyl group on only one terminal side of the poly (oxyfluoroalkylene) chain. The base material with a water- and oil-repellent layer according to claim 5, which is a condensate of a mixture containing a compound.
12. The water- and oil-repellent layer according to claim 11, wherein the fluorine-containing compound having a reactive silyl group only on one terminal side of the poly (oxyfluoroalkylene) chain is a fluorine-containing compound having two or more reactive silyl groups. With base material.