WO2016190047A1 - Method for manufacturing article having surface treatment layer - Google Patents

Abstract

The present invention relates to a method for manufacturing an article having a substrate, a silicon oxide layer positioned on the substrate, and a surface treatment layer formed on the silicon oxide layer, the manufacturing method including the steps of forming the silicon oxide layer using a chemical vapor deposition method, and forming the surface treatment layer on the resultant silicon oxide layer using a surface treatment agent including a fluorine-containing silane compound.

Description

Method for producing article having surface treatment layer

The present invention relates to a method for producing an article having a surface treatment layer, particularly an article having a surface treatment layer obtained from a surface treatment agent containing a fluorine-containing silane compound.

It is known that certain fluorine-containing compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. ing.

As such a fluorine-containing silane compound, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is known. It has been. For example, Patent Document 1 describes a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part. In Patent Document 1, on the outermost surface of the substrate, forming a SiO ₂ layer, by applying a surface treatment agent comprising a fluorine-containing silane compound in the SiO ₂ layer on, to form a surface treatment layer.

JP 2013-1117012 A

The surface treatment layer is required to have high durability so as to provide a desired function to the base material over a long period of time. Since the layer obtained from the surface treatment agent containing a perfluoropolyether group-containing silane compound can exhibit the above-described functions even in a thin film, it is suitable for optical members such as glasses and touch panels that require optical transparency or transparency. In particular, these applications are required to further improve the friction durability.

As described in Patent Document 1, as a pretreatment when forming a surface treatment layer, a method of forming a SiO ₂ layer on the outermost surface of a substrate and then applying a surface treatment agent thereon is known. However, when the above-mentioned SiO ₂ layer is formed by a physical vapor deposition method (PVD method: Physical Vapor Deposition), the present inventors may not have sufficient friction durability and sweat durability. I noticed.

Therefore, an object of the present invention is to provide a method capable of producing an article having a surface treatment layer having more excellent friction durability and sweat durability (that is, acid and alkali resistance).

As a result of intensive studies, the inventors of the present invention used a chemical vapor deposition method (CVD: Chemical Vapor Deposition) instead of a PVD method such as vacuum deposition for the silicon oxide layer formed on the outermost layer of the substrate. It was found that an article having a surface-treated layer with more excellent friction durability and sweat durability can be provided.

According to a first aspect of the present invention, a substrate;
A silicon oxide layer located on the substrate;
A method for producing an article comprising a surface treatment layer formed on the silicon oxide layer,
Forming a silicon oxide layer using a chemical vapor deposition method, and forming a surface treatment layer on the obtained silicon oxide layer using a surface treatment agent containing a fluorine-containing silane compound; A manufacturing method is provided.

According to the second aspect of the present invention, an article obtained by the above manufacturing method is provided.

According to the present invention, by using a CVD method, a silicon oxide layer is formed, and a surface treatment layer is formed thereon, thereby having water repellency, oil repellency, antifouling properties, and excellent An article comprising a surface treatment layer having friction resistance and sweat resistance can be produced.

Hereinafter, the production method of the present invention will be described.

The article manufactured by the manufacturing method of the present invention comprises a base material, a silicon oxide layer located on the base material, and a surface treatment layer formed on the silicon oxide layer.

First, prepare the base material. Substrates that can be used in the present invention include, for example, glass, sapphire glass, resin (natural or synthetic resin, such as a general plastic material, and may be a plate, film, or other form), metal ( It may be a single metal such as aluminum, copper, iron or a composite of an alloy, etc.), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. It can be composed of any suitable material, such as a building member. Preferably, the substrate is glass.

As the glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemical bond Particularly preferred is borosilicate glass.

The shape of the substrate is not particularly limited. Further, the surface region of the substrate on which the silicon oxide layer and the surface treatment layer are to be formed may be at least part of the substrate surface, and is appropriately determined according to the use and specific specifications of the article to be manufactured. obtain.

Some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface of the substrate. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic materials that can be used for the antireflection layer include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO. , Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be. In addition, the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, And a liquid crystal display module or the like.

In one embodiment, the substrate may be pretreated before forming the silicon oxide layer on the substrate. By performing the pretreatment, the adhesion between the base material and the silicon oxide layer is improved, and higher friction durability can be obtained.

The pretreatment is not particularly limited, and examples thereof include washing with an oxidant solution such as H ₂ O ₂ and H ₂ SO ₄ or an alcohol such as ethanol. Washing with a mixed solution of H ₂ O ₂ / H ₂ SO ₄ / H ₂ O (1 to 5: 1 to 5: 1 to 20) or ethanol is preferable, and a mixture of H ₂ O ₂ / H ₂ SO ₄ / H ₂ O is preferable. More preferred is washing with a solution.

Next, a silicon oxide (SiO _x ) layer is formed on the surface of the substrate.

The silicon oxide layer is formed by a CVD method. The CVD method is a method of forming a non-volatile film by supplying a raw material in a gaseous state and reacting it on the surface of a substrate. Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD, and similar methods. Preferably, plasma CVD is used.

A silicon compound is used as the silicon source in the CVD method. Examples of the silicon compound include silane compounds such as SiH ₄ and Si ₂ H ₆ , and organosilicon compounds such as triethoxysilane and tetraethoxysilane. Preferably, SiH ₄ is used.

As the oxygen source in the CVD method, oxygen gas is preferably used.

The carrier gas in the CVD method is appropriately selected according to the type of the CVD method, and for example, an inert gas such as nitrogen gas, argon gas, helium gas, or hydrogen gas is used.

The conditions for forming the silicon oxide layer by the CVD method are appropriately set according to the type of CVD method used, the thickness of the silicon oxide layer, and the like. For example, when the silicon oxide layer is formed by plasma CVD, it is preferably performed under the following conditions.
RF (Radio Frequency) power density: 0.5 to 2.0 W / cm ² , preferably 0.7 to 1.5 W / cm ² , for example 1.0 W / cm ² ;
Substrate temperature: 100-400 ° C., preferably 150-300 ° C., for example 200 ° C .;
Process pressure: 50 to 500 Pa, preferably 100 to 300 Pa, for example 150 to 200 Pa;
Material gas flow ratio (volume ratio):
SiH ₄ : N ₂ O = 1: 10 to 1: 100, preferably 1:20 to 1:50, for example 1:25 to 1:35;
SiH ₄ : H ₂ = 1: 50 to 1: 500, preferably 1:80 to 1: 300, for example 1: 100 to 1: 200.

The thickness of the silicon oxide layer formed by the CVD method is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 70 nm, further preferably 10 to 40 nm, and still more preferably 10 to 20 nm. By setting the film thickness of the silicon oxide layer within the above range, a surface treatment layer having higher friction durability can be formed on the silicon oxide layer. In the present specification, the film thickness of the silicon cyclized layer is a value measured by an ellipsometer.

The silicon oxide layer formed by the above CVD method may have a surface roughness (Ra: centerline average roughness) of preferably 0.2 nm or less, more preferably 0.15 nm or less. The Ra is defined in JIS B0601: 1982.

The silicon oxide layer formed by the CVD method is preferably at least partly, more preferably 50% or more of the whole silicon oxide layer, and still more preferably 80% or more of the whole silicon oxide layer. The amorphous state in the silicon oxide layer can be confirmed by measuring the intensity of a diffraction peak caused by a crystal by an X-ray diffraction method (XRD).

The silicon oxide layer formed by the CVD method, preferably has a density of ^{2.25g / cm 3 ~ 2.60g / cm} 3, more preferably ^{2.30g / cm 3 ~ 2.50g / cm} 3 , even more preferably a density of ^{2.35g / cm 3 ~ 2.45g / cm} 3, for example a density of ^{2.38g / cm 3 ~ 2.42g / cm} 3. The density of the silicon oxide layer can be measured by an X-ray reflectometry (XRR) method.

The silicon oxide layer formed by the CVD method has a hydrogen concentration in the film of preferably 1 at% or more, for example, 2 at% or more, 3 at% or more, 4 at% or more, or 5 at% or more, preferably 10 at% or less, For example, it is 9 at% or less, 8 at% or less, 7 at% or less, or 6 at% or less. For example, the hydrogen concentration in the film is 1 to 10 at%, 2 to 10 at%, 3 to 10 at%, 4 to 10 at%, or 5 to 10 at%, or 1 to 9 at%, 1 to 8 at%, 1 to 7 at%, or 1 It can be ˜6 at%, alternatively 2-9 at%, 3-8 at%, 4-7 at%, or 5-6 at%. The hydrogen concentration in the silicon oxide layer can be measured by Rutherford Backscattering Spectrometry (RBS).

The Si / O composition ratio (mol ratio) in the silicon oxide layer formed by the CVD method can be 1.5 or less, and preferably is greater than 0.5. The Si / O composition ratio is preferably 0.6 to 1.5, more preferably 0.7 to 1.3, such as 0.7 to 1.2, 0.8 to 1.3 or 0.8 to 1. .2. The Si / O composition ratio in the silicon oxide layer can be measured by a Rutherford Backscattering Spectrometry (RBS) method.

In one embodiment, the silicon oxide layer may be pretreated before forming the surface treatment layer on the obtained silicon oxide layer. By performing the pretreatment, the adhesion between the silicon oxide layer and the surface treatment layer is improved, and higher friction durability can be obtained.

Examples of the pretreatment include ion cleaning. The ion cleaning is not particularly limited, but oxygen ion cleaning and argon ion cleaning are preferable, and oxygen ion cleaning is more preferable.

Ion cleaning conditions may vary depending on the type of gas used, but oxygen ion cleaning is performed under the following conditions. However, the ion cleaning is not limited to the following conditions as long as impurities on the silicon oxide layer can be removed.
(Oxygen ion cleaning conditions)
Accelerating voltage: 500 to 1500V, preferably 800 to 1200V, typically 1000V
Acceleration current: 100 to 1000 mA, preferably 300 to 700 mA, typically 500 mA
Gas amount: 10 to 100 sccm, preferably 30 to 70 sccm, typically 50 sccm
Pressure: 1 × 10 ⁻³ Pa to 1 × 10 ⁻¹ Pa, preferably 1 × 10 ⁻² Pa to 5 × 10 ⁻² Pa, typically 2 × 10 ⁻² Pa

Next, a surface treatment layer is formed on the silicon oxide layer obtained above using a surface treatment agent containing a fluorine-containing silane compound.

［式中：
　ＰＦＰＥは、各出現においてそれぞれ独立して、式：
　　　－（ＯＣ_４Ｆ_８）_ａ－（ＯＣ_３Ｆ_６）_ｂ－（ＯＣ_２Ｆ_４）_ｃ－（ＯＣＦ_２）_ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ^１は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　Ｒ^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ^１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
　Ｒ^１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎは、（－ＳｉＲ^１ _ｎＲ^２ _３－ｎ）単位毎に独立して、０～３の整数であり；
　ただし、式（Ａ１）、（Ａ２）、（Ｂ１）および（Ｂ２）において、少なくとも１つのＲ^２が存在し； 
　Ｘ^１は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　Ｘ^２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表し；
　ｔは、各出現においてそれぞれ独立して、１～１０の整数であり；
　αは、それぞれ独立して、１～９の整数であり；
　α’は、それぞれ独立して、１～９の整数であり；
　Ｘ^５は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　βは、それぞれ独立して、１～９の整数であり；
　β’は、それぞれ独立して、１～９の整数であり；
　Ｘ^７は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　γは、それぞれ独立して、１～９の整数であり；
　γ’は、それぞれ独立して、１～９の整数であり；
　Ｒ^ａは、各出現においてそれぞれ独立して、－Ｚ－ＳｉＲ^７１ _ｐＲ^７２ _ｑＲ^７３ _ｒを表し；
　Ｚは、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
　Ｒ^７１は、各出現においてそれぞれ独立して、Ｒ^ａ’を表し；
　Ｒ^ａ’は、Ｒ^ａと同意義であり；
　Ｒ^ａ中、Ｚ基を介して直鎖状に連結されるＳｉは最大で５個であり；
　Ｒ^７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ^７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｐは、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑは、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒは、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、（Ｚ－ＳｉＲ^７１ _ｐＲ^７２ _ｑＲ^７３ _ｒ）単位において、ｐ、ｑおよびｒの和は３であり、式（Ｃ１）および（Ｃ２）において、少なくとも１つのＲ^７２が存在し；
　Ｒ^ｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ^ｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｋは、各出現においてそれぞれ独立して、１～３の整数であり；
　ｌは、各出現においてそれぞれ独立して、０～２の整数であり；
　ｍは、各出現においてそれぞれ独立して、０～２の整数であり；
　ただし、γを付して括弧でくくられた単位において、ｋ、ｌおよびｍの和は３であり；
　Ｘ^９は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　δは、それぞれ独立して、１～９の整数であり；
　δ’は、それぞれ独立して、１～９の整数であり；
　Ｒ^ｄは、各出現においてそれぞれ独立して、－Ｚ^２－ＣＲ^８１ _ｐ２Ｒ^８２ _ｑ２Ｒ^８３ _ｒ２を表し；
　Ｚ^２は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
　Ｒ^８１は、各出現においてそれぞれ独立して、Ｒ^ｄ’を表し；
　Ｒ^ｄ’は、Ｒ^ｄと同意義であり；
　Ｒ^ｄ中、Ｚ^２基を介して直鎖状に連結されるＣは最大で５個であり；
　Ｒ^８２は、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ^８５ _ｎ２Ｒ^８６ _３－ｎ２を表し；
　Ｙは、各出現においてそれぞれ独立して、２価の有機基を表し；
　Ｒ^８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ^８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎ２は、（－Ｙ－ＳｉＲ^８５ _ｎ２Ｒ^８６ _３－ｎ２）単位毎に独立して、０～３の整数を表し；
　Ｒ^８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｐ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　Ｒ^ｅは、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ^８５ _ｎ２Ｒ^８６ _３－ｎ２を表し；
　Ｒ^ｆは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｋ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｌ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｍ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、式（Ｄ１）および（Ｄ２）において、少なくとも１つのＲ^８５が存在する。］
で表される１種またはそれ以上の化合物である。 The fluorine-containing silane compound preferably contains a perfluoropolyether group. For example, the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) And (D2):

[Where:
PFPE has the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n is an integer of 0 to 3, independently for each (-SiR ¹ _n R ² _3-n ) unit;
Provided that in formulas (A1), (A2), (B1) and (B2), at least one R ² is present;
Each X ¹ independently represents a single bond or a divalent to 10-valent organic group;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
each α is independently an integer from 1 to 9;
α ′ is each independently an integer of 1 to 9;
Each X ⁵ independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
X ⁷ each independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer from 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence;
Z represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R ⁷¹ independently represents R ^{a ′} at each occurrence;
R ^{a ′} is synonymous with R ^a ;
In R ^a , the maximum number of Si linearly linked via the Z group is 5;
R ⁷² independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁷³ independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p is independently an integer from 0 to 3 at each occurrence;
q is independently an integer from 0 to 3 at each occurrence;
r is independently an integer from 0 to 3 at each occurrence;
Provided that in the (Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r ) unit, the sum of p, q and r is 3, and in formulas (C1) and (C2), at least one R ⁷² is present;
R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k is an integer of 1 to 3 independently at each occurrence;
l is an integer from 0 to 2 independently at each occurrence;
m is an integer from 0 to 2 independently at each occurrence;
Provided that the sum of k, l and m is 3 in the unit enclosed in parentheses with γ;
X ⁹ each independently represents a single bond or a divalent to 10-valent organic group;
each δ is independently an integer from 1 to 9;
each δ ′ is independently an integer from 1 to 9;
R ^d independently represents at each occurrence —Z ² —CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 ;
Z ² independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁸¹ independently represents R ^{d ′} at each occurrence;
R ^{d ′} is synonymous with R ^d ;
In R ^d , the maximum number of C linked in a straight chain via the Z ² group is 5;
R ⁸² independently represents at each occurrence —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ;
Y represents a divalent organic group independently at each occurrence;
R ⁸⁵ independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁸⁶ independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n2 independently represents an integer of 0 to 3 for each (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) unit;
R ⁸³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p2 is independently an integer from 0 to 3 at each occurrence;
q2 is independently an integer from 0 to 3 at each occurrence;
r2 is independently an integer from 0 to 3 at each occurrence;
R ^e independently represents at each occurrence —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ;
R ^f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k2 is independently an integer from 0 to 3 at each occurrence;
l2 is independently an integer from 0 to 3 at each occurrence;
m2 is an integer from 0 to 3 independently at each occurrence;
However, in formulas (D1) and (D2), at least one R ⁸⁵ is present. ]
Or one or more compounds represented by:

As used herein, “hydrocarbon group” means a group containing carbon and hydrogen, and a group in which one hydrogen atom has been eliminated from a hydrocarbon. Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.

As used herein, the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C _1-6 alkyl optionally substituted by one or more halogen atoms Group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C _6-10 aryl group and a 5-10 membered heteroaryl group.

As used herein, “divalent to decavalent organic group” means a divalent to decavalent group containing carbon. Such a divalent to decavalent organic group is not particularly limited, and examples thereof include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group. For example, the divalent organic group is not particularly limited, and examples thereof include a divalent group in which one hydrogen atom is further eliminated from a hydrocarbon group.

The perfluoropolyether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) will be described below. .

Formulas (A1) and (A2):

In the above formula, PFPE is — (OC ₄ F ₈ ) _a — (OC ₃ F ₆ ) _b — (OC ₂ F ₄ ) _c — (OCF ₂ ) _d —, which corresponds to a perfluoropolyether group. Here, a, b, c and d are each independently 0 or an integer of 1 or more, and the sum of a, b, c and d is at least 1. Preferably, a, b, c and d are each independently an integer of 0 to 200, for example, an integer of 1 to 200, more preferably an integer of 0 to 100. Preferably, the sum of a, b, c and d is 5 or more, more preferably 10 or more, for example 10 or more and 100 or less. Further, the order of presence of each repeating unit with a, b, c or d in parentheses is arbitrary in the formula. Among these repeating units, — (OC ₄ F ₈ ) — represents — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —, — (OCF (CF ₃ ) CF ₂ CF ₂ ) —, — (OCF ₂ CF (CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ))-,-(OC (CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C (CF ₃ ) ₂ )-,-(OCF (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-may be used, but preferably — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —. -(OC ₃ F ₆ )-is any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))- Preferably, it is — (OCF ₂ CF ₂ CF ₂ ) —. In addition, — (OC ₂ F ₄ ) — may be any of — (OCF ₂ CF ₂ ) — and — (OCF (CF ₃ )) —, preferably — (OCF ₂ CF ₂ ) —. is there.

In one embodiment, PFPE is — (OC ₃ F ₆ ) _b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200), Preferably, — (OCF ₂ CF ₂ CF ₂ ) _b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF ₃ ) CF ₂ ) _b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200), more preferably — (OCF ₂ CF ₂ CF ₂ ) _b- (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).

In another embodiment, PFPE has the following structure:-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d- (wherein a and b are each independently And c and d are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, and the subscripts a, b, c Or the order of presence of each repeating unit in parentheses with d attached is arbitrary in the formula), preferably — (OCF ₂ CF ₂ CF ₂ CF ₂ ) _a — (OCF ₂ CF ₂ CF ₂ ) _b- (OCF ₂ CF ₂ ) _c- (OCF ₂ ) _d- . In one embodiment, PFPE is — (OC ₂ F ₄ ) _c — (OCF ₂ ) _d — (wherein c and d are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the subscript c or d is arbitrary in the formula).

In yet another embodiment, PFPE is a group represented by — (OC ₂ F ₄ —R ¹⁵ ) _{n ″} —. In the formula, R ¹⁵ represents OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F. ₈ is a group selected from, or independent of _{.OC 2 F 4, OC 3 F} 6 and _OC 4 _{F 8} is a combination of two or three groups independently selected from these groups The combination of 2 or 3 groups selected is not particularly limited. For example, —OC ₂ F ₄ OC ₃ F ₆ —, —OC ₂ F ₄ OC ₄ F ₈ —, —OC ₃ F ₆ OC ₂ F _{4 -, - OC 3 F 6 OC} 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F 8 -, - OC 4 F 8 OC 3 F 6 -, - OC 4 F _{8 OC 2 F 4 -, -} OC 2 F 4 OC 2 F 4 _{C 3 F 6 -, - OC} 2 F 4 OC 2 F 4 OC 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 - _{, -OC 2 F 4 OC 4 F} 8 OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 -, - OC 3 F ₆ OC ₃ F ₆ OC ₂ F ₄ —, and —OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ — and the like. The above n ″ is an integer of 2 to 100, preferably an integer of 2 to 50 is there. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either linear or branched, preferably linear. In this embodiment, the PFPE is preferably — (OC ₂ F ₄ —OC ₃ F ₆ ) _{n ″} — or — (OC ₂ F ₄ —OC ₄ F ₈ ) _{n ″} —.

In the above formula, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

The “alkyl group having 1 to 16 carbon atoms” in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.

Rf is preferably an alkyl group having 1 to 16 carbon atoms, which is substituted with one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 fluoroalkylene group, still more preferably Is a perfluoroalkyl group having 1 to 16 carbon atoms.

The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF ₃ , —CF ₂ CF ₃ , or —CF ₂ CF ₂ CF ₃ . .

In the above formula, R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, at each occurrence.

In the above formula, R ² independently represents a hydroxyl group or a hydrolyzable group at each occurrence.

The “hydrolyzable group” as used herein means a group capable of leaving from the main skeleton of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include —OR, —OCOR, —O—N═CR ₂ , —NR ₂ , —NHR, halogen (in these formulas, R is a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms). And the like, and —OR (that is, an alkoxy group) is preferable. Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.

In the above formulas, R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.

In the above formula, R ¹² each independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.

In the above formula, n is independently an integer of 0 to 3, preferably 0 to 2, more preferably 0 for each (-SiR ¹ _n R ² _3-n ) unit. However, in the formula, all n are not 0 simultaneously. In other words, at least one R ² is present in the formula.

In the above formula, each X ¹ independently represents a single bond or a divalent to 10-valent organic group. The X ¹ is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (A1) and (A2). And a silane moiety (that is, a group parenthesized with α) that provides the binding ability to the base material. Therefore, X ¹ may be any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.

In the above formula, α is an integer of 1 to 9, and α ′ is an integer of 1 to 9. These α and α ′ can vary depending on the valence of X ¹ . In the formula (A1), the sum of α and α ′ is the same as the valence of X ¹ . For example, when X ¹ is a 10-valent organic group, the sum of α and α ′ is 10, for example, α is 9 and α ′ is 1, α is 5 and α ′ is 5, or α is 1 and α 'Can be nine. Further, when X ¹ is a divalent organic group, α and α ′ are 1. In formula (A2), alpha is a value obtained by subtracting 1 from the valence of X ^1.

X ¹ is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.

In one embodiment, X ¹ is a divalent to tetravalent organic group, α is 1 to 3, and α ′ is 1.

In another embodiment, X ¹ is a divalent organic group, α is 1 and α ′ is 1. In this case, the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).

Examples of X ¹ are not particularly limited, but for example, the following formula:
-(R ³¹ ) _{p '} -(X ^a ) _q'-
[Where:
R ³¹ represents a single bond, — (CH ₂ ) _{s ′} — or o-, m- or p-phenylene group, preferably — (CH ₂ ) _{s ′} —
s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
X ^a represents-(X ^b ) _{l '} -
X ^b is independently at each occurrence —O—, —S—, o—, m- or p-phenylene, —C (O) O—, —Si (R ³³ ) ₂ —, — ( Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ —, —CONR ³⁴ —, —O—CONR ³⁴ —, —NR ³⁴ — and — (CH ₂ ) _{n ′} — Represents a group,
R ³³ each independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a phenyl group or a C _1-6 alkyl group, and more preferably a methyl group. And
R ³⁴ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group) at each occurrence;
m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,
n ′ is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
l ′ is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p ′ is 0 or 1;
q ′ is 0 or 1,
Here, at least one of p ′ and q ′ is 1, and the order of presence of each repeating unit in parentheses attached with p ′ or q ′ is arbitrary]
The bivalent group represented by these is mentioned. Here, R ³¹ and X ^a (typically ^a hydrogen atom of R ³¹ and X ^a ) are one or more selected from a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group It may be substituted with a substituent.

Preferably, X ¹ is — (R ³¹ ) _{p ′} — (X ^a ) _{q ′} —R ³² —. R ³² represents a single bond, — (CH ₂ ) _{t ′} — or o-, m- or p-phenylene group, and preferably — (CH ₂ ) _{t ′} —. t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R ³² (typically a hydrogen atom of R ³² ) is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. It may be.

Preferably, X ¹ is
A C _1-20 alkylene group,
-R ³¹ -X ^c -R ^32- , or -X ^d -R ^32-
[Wherein, R ³¹ and R ³² are as defined above. ]
It can be.

More preferably, said X ¹ is
A C _1-20 alkylene group,
-(CH ₂ ) _s' -X ^c- ,
-(CH ₂ ) _{s '} -X ^c- (CH ₂ ) _t'-
-X ^d- , or -X ^d- (CH ₂ ) _{t '} -
[Wherein, s ′ and t ′ are as defined above]. ]
It is.

In the above formula, X ^c is
-O-,
-S-,
-C (O) O-,
-CONR ³⁴ -,
-O-CONR ³⁴ -,
-Si (R ³³ ) _2- ,
-(Si (R ³³ ) ₂ O) _{m '} -Si (R ³³ ) _2- ,
—O— (CH ₂ ) _{u ′} — (Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ —,
—O— (CH ₂ ) _{u ′} —Si (R ³³ ) ₂ —O—Si (R ³³ ) ₂ —CH ₂ CH ₂ —Si (R ³³ ) ₂ —O—Si (R ³³ ) ₂ —,
—O— (CH ₂ ) _{u ′} —Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ —,
—CONR ³⁴ — (CH ₂ ) _{u ′} — (Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ —,
—CONR ³⁴ — (CH ₂ ) _{u ′} —N (R ³⁴ ) —, or —CONR ³⁴ — (o-, m- or p-phenylene) -Si (R ³³ ) ₂ —
[Wherein, R ³³ , R ³⁴ and m ′ are as defined above;
u ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ]. X ^c is preferably —O—.

In the above formula, X ^d is
-S-,
-C (O) O-,
-CONR ³⁴ -,
—CONR ³⁴ — (CH ₂ ) _{u ′} — (Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ —,
—CONR ³⁴ — (CH ₂ ) _{u ′} —N (R ³⁴ ) —, or —CONR ³⁴ — (o-, m- or p-phenylene) -Si (R ³³ ) ₂ —
[Wherein each symbol is as defined above. ]
Represents.

More preferably, said X ¹ is
A C _1-20 alkylene group,
— (CH ₂ ) _{s ′} —X ^c — (CH ₂ ) _{t ′} —, or —X ^d — (CH ₂ ) _{t ′} —
[Wherein each symbol is as defined above. ]
It can be.

Even more preferably, said X ¹ is
A C _1-20 alkylene group,
— (CH ₂ ) _{s ′} —O— (CH ₂ ) _{t ′} —,
_{- (CH 2) s' -} (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -,
— (CH ₂ ) _{s ′} —O— (CH ₂ ) _{u ′} — (Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ — (CH ₂ ) _{t ′} —, or — (CH ₂ ) _s′— O— (CH ₂ ) _{t ′} —Si (R ³³ ) ₂ — (CH ₂ ) _{u ′} —Si (R ³³ ) ₂ — (C _v H _2v ) —
Wherein R ³³ , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3. It is an integer. ]
It is.

In the above formula, — (C _v H _2v ) — may be linear or branched. For example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH It may be (CH ₃ ) —, —CH (CH ₃ ) CH ₂ —.

The X ¹ group is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group (preferably a C _1-3 perfluoroalkyl group). May be.

In one embodiment, the X ¹ group can be other than an —O—C _1-6 alkylene group.

［式中、Ｒ^４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ_１－６アルコキシ基、好ましくはメチル基であり；
　Ｄは、
－ＣＨ_２Ｏ（ＣＨ_２）_２－、
－ＣＨ_２Ｏ（ＣＨ_２）_３－、
－ＣＦ_２Ｏ（ＣＨ_２）_３－、
－（ＣＨ_２）_２－、
－（ＣＨ_２）_３－、
－（ＣＨ_２）₄－、
－ＣＯＮＨ－（ＣＨ_２）_３－、
－ＣＯＮ（ＣＨ_３）－（ＣＨ_２）_３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ_２）_３－（式中、Ｐｈはフェニルを意味する）、および

（式中、Ｒ^４２は、それぞれ独立して、水素原子、Ｃ_１－６のアルキル基またはＣ_１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。）
から選択される基であり、
　Ｅは、－（ＣＨ_２）_ｎ－（ｎは２～６の整数）であり、
　Ｄは、分子主鎖のＰＦＰＥに結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ In another embodiment, examples of X ¹ groups include the following groups:

[Wherein, each R ⁴¹ independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
D is
—CH ₂ O (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ —,
—CF ₂ O (CH ₂ ) ₃ —,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _(CH 2) ₄ -,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
—CON (Ph) — (CH ₂ ) ₃ — (wherein Ph represents phenyl), and

(In the formula, each R ⁴² independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.)
A group selected from
E is — (CH ₂ ) _n — (n is an integer of 2 to 6);
D binds to PFPE of the molecular backbone, and E binds to the opposite group of PFPE. ]

などが挙げられる。 Specific examples of X ¹ include, for example:
—CH ₂ O (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ —,
—CH ₂ O (CH ₂ ) ₆ —,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _2- ,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CF 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 OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —
—CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₃ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _3- ,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _2- ,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
-(CH ₂ ) _6- ,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
—CON (Ph) — (CH ₂ ) ₃ — (wherein Ph represents phenyl),
-CONH- (CH ₂ ) _6- ,
-CON (CH ₃ )-(CH ₂ ) _6- ,
—CON (Ph) — (CH ₂ ) ₆ — (wherein Ph represents phenyl),
—CONH— (CH ₂ ) ₂ NH (CH ₂ ) ₃ —,
—CONH— (CH ₂ ) ₆ NH (CH ₂ ) ₃ —,
—CH ₂ O—CONH— (CH ₂ ) ₃ —,
—CH ₂ O—CONH— (CH ₂ ) ₆ —,
-S- (CH ₂ ) _3- ,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂ (CH ₂ ) _2- ,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂₀ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —
-C (O) O- (CH ₂ ) _3- ,
-C (O) O- (CH ₂ ) _6- ,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ —CH (CH ₃ ) —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₃ —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ —CH (CH ₃ ) —CH ₂ —,
-OCH _2- ,
—O (CH ₂ ) ₃ —,
-OCHFCF _2- ,

Etc.

In still another embodiment, X ¹ is a group represented by the formula: — (R ¹⁶ ) _x — (CFR ¹⁷ ) _y — (CH ₂ ) _z —. In the formula, x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order in which each repeating unit enclosed in parentheses is in the formula Is optional.

In the above formula, R ¹⁶ is independently an oxygen atom, phenylene, carbazolylene, —NR ²⁶ — (wherein R ²⁶ represents a hydrogen atom or an organic group) or a divalent organic group at each occurrence. is there. Preferably, R ¹⁶ is an oxygen atom or a divalent polar group.

The “divalent polar group” is not particularly limited, but —C (O) —, —C (═NR ²⁷ ) —, and —C (O) NR ²⁷ — (in these formulas, R ²⁷ is Represents a hydrogen atom or a lower alkyl group). The “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.

In the above formula, R ¹⁷ is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom, at each occurrence. The “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, more preferably a trifluoromethyl group.

In this embodiment, X ¹ is preferably of the formula: — (O) _x — (CF ₂ ) _y — (CH ₂ ) _z —, wherein x, y and z are as defined above The order in which each repeating unit is included is arbitrary in the formula).

Examples of the group represented by the above formula: — (O) _x — (CF ₂ ) _y — (CH ₂ ) _z — include, for example, — (O) _{x ′} — (CH ₂ ) _{z ″} —O — [(CH _{2) z '''-O-]} z "", and _{- (O) x' - (} CF 2) y "- (CH 2) z" -O - [(CH 2) z '''-O- _{Z ″ ″} (wherein x ′ is 0 or 1, y ″, z ″ and z ′ ″ are each independently an integer of 1 to 10, and z ″ ″ is 0 or 1) These groups are bonded at the left end to the PFPE side.

In another preferred embodiment, X ¹ is —O—CFR ¹³ — (CF ₂ ) _e —.

Each R ¹³ independently represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. It is.

The above e is 0 or 1 independently.

In one embodiment, R ¹³ is a fluorine atom and e is 1.

［式中、
　Ｒ^４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ_１－６アルコキシ基好ましくはメチル基であり；
　各Ｘ^１基において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥに結合する以下の基：
－ＣＨ_２Ｏ（ＣＨ_２）_２－、
－ＣＨ_２Ｏ（ＣＨ_２）_３－、
－ＣＦ_２Ｏ（ＣＨ_２）_３－、
－（ＣＨ_２）_２－、
－（ＣＨ_２）_３－、
－（ＣＨ_２）₄－、
－ＣＯＮＨ－（ＣＨ_２）_３－、
－ＣＯＮ（ＣＨ_３）－（ＣＨ_２）_３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ_２）_３－（式中、Ｐｈはフェニルを意味する）、または

［式中、Ｒ^４２は、それぞれ独立して、水素原子、Ｃ_１－６のアルキル基またはＣ_１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥと反対の基（即ち、式（Ａ１）、（Ａ２）、（Ｄ１）および（Ｄ２）においては炭素原子、また、下記する式（Ｂ１）、（Ｂ２）、（Ｃ１）および（Ｃ２）においてはＳｉ原子）に結合する－（ＣＨ_２）_ｎ”－（ｎ”は２～６の整数）であり、存在する場合、残りは、それぞれ独立して、メチル基、フェニル基またはＣ_１－６アルコキシ基である。 In yet another embodiment, examples of X ¹ groups include the following groups:

[Where:
Each of R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
In each X ¹ group, any some of T are attached to the PFPE of the molecular backbone:
—CH ₂ O (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ —,
—CF ₂ O (CH ₂ ) ₃ —,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _(CH 2) ₄ -,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
—CON (Ph) — (CH ₂ ) ₃ — (wherein Ph represents phenyl), or

[Wherein, each R ⁴² independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
And some of the other T is a group opposite to PFPE of the molecular main chain (that is, a carbon atom in the formulas (A1), (A2), (D1) and (D2)), and a formula ( B1), (B2), (C1) and (C2) are bonded to Si atoms)-(CH ₂ ) _{n "} -(n" is an integer of 2 to 6). Each independently represents a methyl group, a phenyl group or a C _1-6 alkoxy group.

In this embodiment, X ¹ , X ⁵ , X ⁷ and X ⁹ can each independently be a trivalent to 10 valent organic group.

In the above formula, t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2 to 10, preferably an integer from 2 to 6.

In the above formula, X ² independently represents a single bond or a divalent organic group at each occurrence. X ² is preferably an alkylene group having 1 to 20 carbon atoms, more preferably — (CH ₂ ) _u — (wherein u is an integer of 0 to 2).

［式中：
　ＰＦＰＥは、それぞれ独立して、式：
　　　－（ＯＣ_４Ｆ_８）_ａ－（ＯＣ_３Ｆ_６）_ｂ－（ＯＣ_２Ｆ_４）_ｃ－（ＯＣＦ_２）_ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり； 
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ^１は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　Ｒ^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ^１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
　Ｒ^１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎは、０～２の整数であり、好ましくは０であり；
　Ｘ^１は、－Ｏ－ＣＦＲ^１３－（ＣＦ_２）_ｅ－であり； 
　Ｒ^１３は、フッ素原子または低級フルオロアルキル基であり；
　ｅは、０または１であり；
　Ｘ^２は、－（ＣＨ_２）_ｕ－であり；
　ｕは、０～２の整数であり；
　ｔは、１～１０の整数である。］
で表される化合物である。 Preferred compounds represented by formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′):

[Where:
Each PFPE is independently of the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n is an integer from 0 to 2, preferably 0;
X ¹ is —O—CFR ¹³ — (CF ₂ ) _e —;
R ¹³ is a fluorine atom or a lower fluoroalkyl group;
e is 0 or 1;
X ² is — (CH ₂ ) _u —;
u is an integer from 0 to 2;
t is an integer of 1 to 10. ]
It is a compound represented by these.

The compounds represented by the above formulas (A1) and (A2) are obtained by introducing, for example, —CH ₂ CR ¹² (X It can be obtained by reacting a vinyl monomer corresponding to ^2- SiR ¹ _n R ² _3-n ) —.

Formulas (B1) and (B2):

In the above formulas (B1) and (B2), Rf, PFPE, R ¹ , R ² and n are as defined in the above formulas (A1) and (A2).

In the above formulas, X ⁵ each independently represents a single bond or a divalent to 10-valent organic group. The X ⁵ is a perfluoropolyether part (Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (B1) and (B2); It is understood as a linker that connects a silane moiety (specifically, —SiR ¹ _n R ² _3-n ) that provides a binding ability with a substrate. Therefore, X ⁵ may be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.

In the above formula, β is an integer of 1 to 9, and β ′ is an integer of 1 to 9. These β and β ′ are determined according to the valence of X ³ , and in the formula (B1), the sum of β and β ′ is the same as the valence of X ⁵ . For example, when X ⁵ is a 10-valent organic group, the sum of β and β ′ is 10, for example, β is 9 and β ′ is 1, β is 5 and β ′ is 5, or β is 1 and β 'Can be nine. When X ⁵ is a divalent organic group, β and β ′ are 1. In formula (B2), beta is a value obtained by subtracting 1 from the valence of the value of X ^5.

X ⁵ is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.

In one embodiment, X ⁵ is a divalent to tetravalent organic group, β is 1 to 3, and β ′ is 1.

In another embodiment, X ⁵ is a divalent organic group, β is 1 and β ′ is 1. In this case, the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).

Examples of X ⁵ are not particularly limited, and examples thereof include those similar to those described for X ¹ .

などが挙げられる。 Among these, preferable specific X ⁵ is
—CH ₂ O (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ —,
—CH ₂ O (CH ₂ ) ₆ —,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _2- ,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CF 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 OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —
—CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₃ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _3- ,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _2- ,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
-(CH ₂ ) _6- ,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
—CON (Ph) — (CH ₂ ) ₃ — (wherein Ph represents phenyl),
-CONH- (CH ₂ ) _6- ,
-CON (CH ₃ )-(CH ₂ ) _6- ,
—CON (Ph) — (CH ₂ ) ₆ — (wherein Ph represents phenyl),
—CONH— (CH ₂ ) ₂ NH (CH ₂ ) ₃ —,
—CONH— (CH ₂ ) ₆ NH (CH ₂ ) ₃ —,
—CH ₂ O—CONH— (CH ₂ ) ₃ —,
—CH ₂ O—CONH— (CH ₂ ) ₆ —,
-S- (CH ₂ ) _3- ,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂ (CH ₂ ) _2- ,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂₀ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —
-C (O) O- (CH ₂ ) _3- ,
-C (O) O- (CH ₂ ) _6- ,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ —CH (CH ₃ ) —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₃ —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ —CH (CH ₃ ) —CH ₂ —,
-OCH _2- ,
—O (CH ₂ ) ₃ —,
-OCHFCF _2- ,

Etc.

［式中：
　ＰＦＰＥは、それぞれ独立して、式：
　　　－（ＯＣ_４Ｆ_８）_ａ－（ＯＣ_３Ｆ_６）_ｂ－（ＯＣ_２Ｆ_４）_ｃ－（ＯＣＦ_２）_ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ^１は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　Ｒ^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　ｎは、０～２の整数であり、好ましくは０であり；
　Ｘ^５は、－ＣＨ_２Ｏ（ＣＨ_２）_２－、－ＣＨ_２Ｏ（ＣＨ_２）_３－または－ＣＨ_２Ｏ（ＣＨ_２）_６－である］
で表される化合物である。 Preferred compounds represented by formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′):

[Where:
Each PFPE is independently of the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
n is an integer from 0 to 2, preferably 0;
X ⁵ is —CH ₂ O (CH ₂ ) ₂ —, —CH ₂ O (CH ₂ ) ₃ — or —CH ₂ O (CH ₂ ) ₆ —
It is a compound represented by these.

［式中：
　ＰＦＰＥは、それぞれ独立して、式：
　　　－（ＯＣ_４Ｆ_８）_ａ－（ＯＣ_３Ｆ_６）_ｂ－（ＯＣ_２Ｆ_４）_ｃ－（ＯＣＦ_２）_ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｘ^５’は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　βは、それぞれ独立して、１～９の整数であり；
　β’は、それぞれ独立して、１～９の整数であり；
　Ｒ^８２は、単結合または２価の有機基である。］
で表される化合物を、ＨＳｉＭ_３（式中、Ｍは、それぞれ独立して、ハロゲン原子、Ｒ^１またはＲ^２であり、Ｒ^１は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基であり、Ｒ^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基である）と反応させて、必要に応じて、上記ハロゲン原子を、Ｒ^１またはＲ^２に変換して、式（Ｂ１”）または（Ｂ２”）：

［式中、ＰＦＰＥ、Ｒｆ、Ｘ^５’、β、β’およびＲ^８２は、上記と同意義であり；
　ｎは、０～３の整数である。］
で表される化合物として得ることができる。 The compounds represented by the above formulas (B1) and (B2) can be produced by a known method, for example, the method described in Patent Document 1 or an improved method thereof. For example, the compounds represented by the formulas (B1) and (B2) are represented by the following formulas (B1-4) or (B2-4):

[Where:
Each PFPE is independently of the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
Each X ^{5 ′} independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
R ⁸² is a single bond or a divalent organic group. ]
HSiM ₃ (wherein, M is each independently a halogen atom, R ¹ or R ² , and R ¹ is independently a hydrogen atom or a carbon number of 1 at each occurrence) And each R ² is independently a hydroxyl group or a hydrolyzable group at each occurrence, and the halogen atom is optionally substituted with R ¹ or R ^2. Into the formula (B1 ″) or (B2 ″):

[Wherein, PFPE, Rf, X ^{5 ′} , β, β ′ and R ⁸² are as defined above;
n is an integer of 0 to 3. ]
It can obtain as a compound represented by these.

In the formula (B1 ″) or (B2 ″), the portion from X ^{5 ′} to R ⁸² —CH ₂ CH ₂ — corresponds to X ⁵ in the formula (B1) or (B2).

Formulas (C1) and (C2):

In the above formulas (C1) and (C2), Rf and PFPE are the same as those described for the above formulas (A1) and (A2).

In the above formulae, X ⁷ each independently represents a single bond or a divalent to 10-valent organic group. The ^{X 7} is a formula (C1) and in the compounds represented by (C2), mainly perfluoropolyether unit for providing water repellency and surface slipperiness, etc. (Rf-PFPE unit or -PFPE- parts) _{^{(specifically, -SiR a k R b l R}} c m group) silane unit that provides a binding capability to a substrate is understood as a linker linking. Therefore, X ⁷ may be any organic group as long as the compounds represented by formulas (C1) and (C2) can exist stably.

In the above formula, γ is an integer of 1 to 9, and γ ′ is an integer of 1 to 9. These γ and γ ′ are determined according to the valence of X ⁷ , and in the formula (C1), the sum of γ and γ ′ is the same as the valence of X ⁷ . For example, when X ⁷ is a 10-valent organic group, the sum of γ and γ ′ is 10, for example, γ is 9 and γ ′ is 1, γ is 5 and γ ′ is 5, or γ is 1 and γ. 'Can be nine. Further, when X ⁷ is a divalent organic group, γ and γ ′ are 1. In formula (C1), gamma is a value obtained by subtracting 1 from the valence of the values of X ^7.

X ⁷ is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.

In one embodiment, X ⁷ is a divalent to tetravalent organic group, γ is 1 to 3, and γ ′ is 1.

In another embodiment, X ⁷ is a divalent organic group, γ is 1 and γ ′ is 1. In this case, the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).

Examples of X ⁷ are not particularly limited, and examples thereof include those similar to those described for X ¹ .

などが挙げられる。 Among these, preferable specific X ⁵ is —CH ₂ O (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ —,
—CH ₂ O (CH ₂ ) ₆ —,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _2- ,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CF 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 OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —
—CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₃ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _3- ,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _2- ,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
-(CH ₂ ) _6- ,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
—CON (Ph) — (CH ₂ ) ₃ — (wherein Ph represents phenyl),
-CONH- (CH ₂ ) _6- ,
-CON (CH ₃ )-(CH ₂ ) _6- ,
—CON (Ph) — (CH ₂ ) ₆ — (wherein Ph represents phenyl),
—CONH— (CH ₂ ) ₂ NH (CH ₂ ) ₃ —,
—CONH— (CH ₂ ) ₆ NH (CH ₂ ) ₃ —,
—CH ₂ O—CONH— (CH ₂ ) ₃ —,
—CH ₂ O—CONH— (CH ₂ ) ₆ —,
-S- (CH ₂ ) _3- ,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂ (CH ₂ ) _2- ,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂₀ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —
-C (O) O- (CH ₂ ) _3- ,
-C (O) O- (CH ₂ ) _6- ,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ —CH (CH ₃ ) —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₃ —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ —CH (CH ₃ ) —CH ₂ —,
-OCH _2- ,
—O (CH ₂ ) ₃ —,
-OCHFCF _2- ,

Etc.

In the above formula, R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence.

In the formula, Z represents an oxygen atom or a divalent organic group independently at each occurrence.

Z is preferably a divalent organic group, and forms a siloxane bond with the Si atom (Si atom to which R ^a is bonded) at the end of the molecular main chain in formula (C1) or formula (C2). Does not include things.

Z is preferably a C _1-6 alkylene group, — (CH ₂ ) _g —O— (CH ₂ ) _h — (wherein g is an integer of 1 to 6, and h is 1 to 6 Or -phenylene- (CH ₂ ) _i- (wherein i is an integer of 0 to 6), more preferably a C _1-3 alkylene group. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

In the formula, R ⁷¹ represents R ^{a ′} independently at each occurrence. R ^{a ′} has the same meaning as R ^a .

During R ^a, Si is connected to the linear through the Z group is a five at the maximum. That is, in the above R ^a , when at least one R ⁷¹ is present, there are two or more Si atoms linearly linked via a Z group in R ^a , The maximum number of Si atoms connected in a chain is five. The "number of Si atoms linearly linked via a Z group in R ^a" is equal to -Z-Si- repeating number of which is connected to a linear during R ^a.

For example, an example in which Si atoms are linked through a Z group in R ^a is shown below.

In the above formula, * means a site bonded to Si of the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end point of ZSi repetition. The number on the right shoulder of Si means the number of appearances of Si connected in a straight line through the Z group counted from *. That is, the chain in which ZSi repeat is completed in Si ² has “the number of Si atoms linearly linked through the Z group in ^Ra ”, and similarly, Si ³ , Si ⁴ And the chain in which the ZSi repetition is completed in Si ⁵ has “number of Si atoms linearly linked through the Z group in R ^a ” being 3, 4 and 5, respectively. As is apparent from the above equation, is in the R ^a, but ZSi chain there are multiple, they need not be all the same length, each may be of any length.

In a preferred embodiment, as shown below, “the number of Si atoms connected linearly via the Z group in R ^a ” is one (left formula) or two (right formula) in all chains. Formula).

In one embodiment, the number of Si atoms connected in a straight chain via a Z group in R ^a is 1 or 2, preferably 1.

In the formula, R ⁷² independently represents a hydroxyl group or a hydrolyzable group at each occurrence.

The “hydrolyzable group” as used herein means a group capable of undergoing a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N═C (R) ₂ , —N (R) ₂ , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.

Preferably, R ⁷² is —OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

In the formula, R ⁷³ independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

Where p is independently an integer from 0 to 3 at each occurrence; q is independently an integer from 0 to 3 at each occurrence; and r is independently at each occurrence. And an integer from 0 to 3. However, the sum of p, q and r is 3.

In a preferred embodiment, ^{'(if R a'} is absent, ^{R a)} terminal of ^{R a} in ^{R a} in the above q is preferably 2 or more, for example 2 or 3, more preferably 3.

In the above formulas (C1) and (C2), at least one R ⁷² is present.

In the above formula, R ^b represents a hydroxyl group or a hydrolyzable group independently at each occurrence.

R ^b is preferably a hydroxyl group, —OR, —OCOR, —O—N═C (R) ₂ , —N (R) ₂ , —NHR, halogen (in these formulas, R is substituted or unsubstituted) An alkyl group having 1 to 4 carbon atoms), preferably —OR. R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group. More preferably, R ^c is —OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

In the above formula, R ^c independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

Where k is independently an integer from 0 to 3 at each occurrence; l is independently an integer from 0 to 3 at each occurrence; and m is independently at each occurrence. And an integer from 0 to 3. However, the sum of k, l and m is 3.

The compounds represented by the above formulas (C1) and (C2) have, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, a hydroxyl group introduced at the terminal, and then an unsaturated bond at the terminal A group is introduced, the group having an unsaturated bond is reacted with a silyl derivative having a halogen atom, a hydroxyl group is further introduced into the terminal of the silyl group, and the introduced group having an unsaturated bond is reacted with the silyl derivative. Can be obtained. For example, it can be obtained as follows.

［式中：
　ＰＦＰＥは、それぞれ独立して、式：
　　　－（ＯＣ_４Ｆ_８）_ａ－（ＯＣ_３Ｆ_６）_ｂ－（ＯＣ_２Ｆ_４）_ｃ－（ＯＣＦ_２）_ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり； 
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｘ^７は、－ＣＨ_２Ｏ（ＣＨ_２）_２－、－ＣＨ_２Ｏ（ＣＨ_２）_３－または－ＣＨ_２Ｏ（ＣＨ_２）_６－を表し；
　Ｒ^ａは、各出現においてそれぞれ独立して、－Ｚ－ＳｉＲ^７１ _ｐＲ^７２ _ｑＲ^７３ _ｒを表し；
　Ｚは、Ｃ_１－６アルキレン基を表し；
　Ｒ^７１は、各出現においてそれぞれ独立して、Ｒ^ａ’を表し；
　Ｒ^ａ’は、Ｒ^ａと同意義であり；
　Ｒ^ａ中、Ｚ基を介して直鎖状に連結されるＳｉは最大で５個であり；
　Ｒ^７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ^７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｐは、各出現においてそれぞれ独立して、０～２の整数であり；
　ｑは、各出現においてそれぞれ独立して、１～３の整数、好ましくは３であり；
　ｒは、各出現においてそれぞれ独立して、０～２の整数であり；
　ただし、一のＲ^ａにおいて、ｐ、ｑおよびｒの和は３である。］
で表される化合物である。 Preferred compounds represented by the formulas (C1) and (C2) are represented by the following formulas (C1 ″) and (C2 ″):

[Where:
Each PFPE is independently of the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
X ⁷ represents —CH ₂ O (CH ₂ ) ₂ —, —CH ₂ O (CH ₂ ) ₃ — or —CH ₂ O (CH ₂ ) ₆ —;
R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence;
Z represents a C _1-6 alkylene group;
R ⁷¹ independently represents R ^{a ′} at each occurrence;
R ^{a ′} is synonymous with R ^a ;
In R ^a , the maximum number of Si linearly linked via the Z group is 5;
R ⁷² independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁷³ independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p is independently an integer from 0 to 2 at each occurrence;
q is independently an integer from 1 to 3, preferably 3 at each occurrence;
r is independently an integer from 0 to 2 at each occurrence;
However, in one R ^a , the sum of p, q and r is 3. ]
It is a compound represented by these.

［式中：
　ＰＦＰＥは、それぞれ独立して、式：
　　　－（ＯＣ_４Ｆ_８）_ａ－（ＯＣ_３Ｆ_６）_ｂ－（ＯＣ_２Ｆ_４）_ｃ－（ＯＣＦ_２）_ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｘ^７’は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　γは、それぞれ独立して、１～９の整数であり；
　γ’は、それぞれ独立して、１～９の整数であり；
　Ｒ^８２は、単結合または２価の有機基である。］
で表される化合物を、ＨＳｉＲ^８３ _ｋＲ^ｂ _ｌＲ^ｃ _ｍ（式中、Ｒ^８３はハロゲン原子、例えばフッ素原子、塩素原子、臭素原子またはヨウ素原子、好ましくは塩素原子であり、Ｒ^ｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し、Ｒ^ｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し、ｋは１～３の整数であり、ｌおよびｍは、それぞれ独立して、０～２の整数であり、ｋ、ｌおよびｍの和は３である。）で表される化合物と反応させて、式（Ｃ１－５）または（Ｃ２－５）：

［式中、Ｒｆ、ＰＦＰＥ、Ｒ^８２、Ｒ^８３、Ｒ^ｂ、Ｒ^ｃ、γ、γ’、Ｘ^７’、ｋ、ｌおよびｍは、上記と同意義である。］
で表される化合物を得る。 The compounds represented by the above formulas (C1) and (C2) can be produced, for example, as follows. The following formula (C1-4) or (C2-4):

[Where:
Each PFPE is independently of the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
Each X ^{7 ′} independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer from 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R ⁸² is a single bond or a divalent organic group. ]
In a compound represented ^{_{by, HSiR 83 k R b l R}} c m ( ^{wherein, R 83} is a halogen atom, such as fluorine atom, chlorine atom, bromine atom or iodine atom, preferably a chlorine atom, ^{R b} is Each occurrence independently represents a hydroxyl group or a hydrolyzable group, R ^c independently represents each occurrence a hydrogen atom or a lower alkyl group, k is an integer of 1 to 3, And m are each independently an integer of 0 to 2, and the sum of k, l and m is 3.) and is reacted with a compound represented by formula (C1-5) or (C2- 5):

[Wherein, Rf, PFPE, R ⁸² , R ⁸³ , R ^b , R ^c , γ, γ ′, X ^{7 ′} , k, l and m are as defined above. ]
To obtain a compound represented by:

［式中、Ｒｆ、ＰＦＰＥ、Ｒ^８２、Ｒ^８４、Ｒ^ｂ、Ｒ^ｃ、γ、γ’、Ｘ^７’、ｋ、ｌおよびｍは、上記と同意義である。］
で表される化合物を得る。 The obtained compound represented by the formula (C1-5) or (C2-5) is converted into Hal-JR ⁸⁴ —CH═CH ₂ (wherein Hal is a halogen atom (eg, I, Br, Cl, F, etc.), J represents Mg, Cu, Pd or Zn, and R ⁸⁴ represents a single bond or a divalent organic group.) And is reacted with a compound represented by formula (C1-6) Or (C2-6):

[Wherein, Rf, PFPE, R ⁸² , R ⁸⁴ , R ^b , R ^c , γ, γ ′, X ^{7 ′} , k, l and m are as defined above. ]
To obtain a compound represented by:

［式中、Ｒｆ、ＰＦＰＥ、Ｒ^７２、Ｒ^７３、Ｒ^８２、Ｒ^８４、Ｒ^ｂ、Ｒ^ｃ、γ、γ’、Ｘ^７’、ｋ、ｌおよびｍは、上記と同意義であり；
　ｑは、各出現においてそれぞれ独立して、１～３の整数であり；
　ｒは、各出現においてそれぞれ独立して、０～２の整数である。］
で表される化合物を得ることができる。 The obtained compound represented by the formula (C1-6) or (C2-6) is converted into HSiM ₃ (wherein M is independently a halogen atom, R ⁷² or R ⁷³ , and R ⁷² is Each independently at each occurrence represents a hydroxyl group or a hydrolyzable group, and R ⁷³ each independently at each occurrence represents a hydrogen atom or a lower alkyl group.) , The halogen atom is converted to R ⁷² or R ⁷³ to give the formula (C1 ′ ″) or (C2 ′ ″):

[Wherein, Rf, PFPE, R ⁷² , R ⁷³ , R ⁸² , R ⁸⁴ , R ^b , R ^c , γ, γ ′, X ^{7 ′} , k, l and m are as defined above;
q is an integer of 1 to 3 independently at each occurrence;
r is an integer of 0 to 2 independently at each occurrence. ]
Can be obtained.

In formula (C1 ′ ″) or (C2 ′ ″), the portion from X ^{7 ′} to R ⁸² —CH ₂ CH ₂ — corresponds to X ⁷ in formula (C1) or (C2), and —R ⁸⁴ —CH ₂ CH ₂ — corresponds to Z in formula (C1) or (C2).

Formulas (D1) and (D2):

In the above formulas (D1) and (D2), Rf and PFPE have the same meaning as described for the above formulas (A1) and (A2).

In the above formulas, X ⁹ each independently represents a single bond or a divalent to 10-valent organic group. The X ⁹ is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (D1) and (D2). It is understood that this is a linker that connects a moiety that provides a binding ability to the substrate (that is, a group that is bracketed with δ). Therefore, X ⁹ may be any organic group as long as the compounds represented by formulas (D1) and (D2) can exist stably.

In the above formula, δ is an integer of 1 to 9, and δ ′ is an integer of 1 to 9. These [delta] and [delta] 'may vary depending on the valence of X ^9. In formula (D1), the sum of [delta] and [delta] 'is the same as the valence of X ^9. For example, when X is a 10-valent organic group, the sum of δ and δ ′ is 10, for example, δ is 9 and δ ′ is 1, δ is 5 and δ ′ is 5, or δ is 1 and δ ′. Can be nine. In addition, when X ⁹ is a divalent organic group, δ and δ ′ are 1. In formula (D2), [delta] is a value obtained by subtracting 1 from the valence of X ^9.

X ⁹ is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.

In one embodiment, X ⁹ is a divalent to tetravalent organic group, δ is 1 to 3, and δ ′ is 1.

In another embodiment, X ⁹ is a divalent organic group, δ is 1 and δ ′ is 1. In this case, the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).

Examples of X ⁹ are not particularly limited, and examples thereof include those similar to those described with respect to X ¹ .

などが挙げられる。 Among these, preferable specific X ⁹ is
—CH ₂ O (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ —,
—CH ₂ O (CH ₂ ) ₆ —,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _2- ,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CF 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 OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ —
—CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₃ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _3- ,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _2- ,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
-(CH ₂ ) _6- ,
— (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
—CON (Ph) — (CH ₂ ) ₃ — (wherein Ph represents phenyl),
-CONH- (CH ₂ ) _6- ,
-CON (CH ₃ )-(CH ₂ ) _6- ,
—CON (Ph) — (CH ₂ ) ₆ — (wherein Ph represents phenyl),
—CONH— (CH ₂ ) ₂ NH (CH ₂ ) ₃ —,
—CONH— (CH ₂ ) ₆ NH (CH ₂ ) ₃ —,
—CH ₂ O—CONH— (CH ₂ ) ₃ —,
—CH ₂ O—CONH— (CH ₂ ) ₆ —,
-S- (CH ₂ ) _3- ,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —,
-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂ (CH ₂ ) _2- ,
—CONH— (CH ₂ ) ₃ Si (CH ₃ ) ₂ O (Si (CH ₃ ) ₂ O) ₂₀ Si (CH ₃ ) ₂ (CH ₂ ) ₂ —
-C (O) O- (CH ₂ ) _3- ,
-C (O) O- (CH ₂ ) _6- ,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ —CH (CH ₃ ) —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ — (CH ₂ ) ₃ —,
—CH ₂ —O— (CH ₂ ) ₃ —Si (CH ₃ ) ₂ — (CH ₂ ) ₂ —Si (CH ₃ ) ₂ —CH (CH ₃ ) —CH ₂ —,
-OCH _2- ,
—O (CH ₂ ) ₃ —,
-OCHFCF _2- ,

Etc.

In the above formula, R ^d independently represents —Z ² —CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 at each occurrence.

In the formula, Z ² represents an oxygen atom or a divalent organic group independently at each occurrence.

Z ² is preferably a C _1-6 alkylene group, — (CH ₂ ) _g —O— (CH ₂ ) _h — (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6). And h is an integer from 0 to 6, for example an integer from 1 to 6, or -phenylene- (CH ₂ ) _i- (where i is an integer from 0 to 6), and more A C _1-3 alkylene group is preferred. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

In the formula, R ⁸¹ independently represents R ^{d ′} at each occurrence. R ^{d ′} has the same meaning as R ^d .

In R ^d , the maximum number of C linked in a straight chain via the Z ² group is 5. That is, the in R ^d, when R ⁸¹ is present at least one, but Si atoms linked in R ^d in Z ² group via a linear there are two or more, via such Z ² group The maximum number of C atoms connected in a straight line is five. The phrase "through the Z ² group in R ^d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 ^-C- being linearly linked in a R ^d Become. This is the same as the description regarding R ^a in the formulas (C1) and (C2).

In a preferred embodiment, the “number of C atoms connected in a straight chain via a Z ² group in R ^d ” is 1 (left formula) or 2 (right formula) in all chains.

In one embodiment, the number of C atoms connected in a straight chain via a Z ² group in R ^d is 1 or 2, preferably 1.

In the formula, R ⁸² represents —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-2n .

Y represents a divalent organic group independently at each occurrence.

In a preferred embodiment, Y is a C _1-6 alkylene group, — (CH ₂ ) _{g ′} —O— (CH ₂ ) _{h ′} — (wherein g ′ is an integer from 0 to 6, for example from 1 to 6 Is an integer, h ′ is an integer from 0 to 6, for example, an integer from 1 to 6, or —phenylene- (CH ₂ ) _{i ′} — (where i ′ is an integer from 0 to 6) ). These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

In one embodiment, Y can be a C _1-6 alkylene group, —O— (CH ₂ ) _{h ′} — or —phenylene- (CH ₂ ) _{i ′} —. When Y is a group as described above, light resistance, particularly ultraviolet light resistance can be further increased.

R ⁵ represents a hydroxyl group or a hydrolyzable group independently at each occurrence.

The “hydrolyzable group” as used herein means a group capable of undergoing a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N═C (R) ₂ , —N (R) ₂ , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.

Preferably, R ⁸⁵ is —OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably an ethyl group or a methyl group, particularly a methyl group).

R ⁸⁶ represents a hydrogen atom or a lower alkyl group independently at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

n2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably, for each unit (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ). 3.

R ⁸³ represents a hydrogen atom or a lower alkyl group independently at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

Where p2 is independently an integer from 0 to 3 at each occurrence; q2 is independently an integer from 0 to 3 at each occurrence; and r2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of p2, q2 and r2 is 3.

In a preferred embodiment, ^{'(if R d'} is absent, ^{R d)} end of ^{R d} in ^{R d} in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.

In a preferred embodiment, at least one of the terminal ends of R ^d is —C (—Y—SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) ₂ or —C (—Y—SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) ₃ , preferably —C ( may be _{^{-Y-SiR 85 q2 R 86 r2}} ) 3. _{^{Wherein, (- Y-SiR 85 q2}} R 86 r2) units is preferably ^{(-Y-SiR 85} _3). In a further preferred embodiment, the terminal portions of R ^d may be all —C (—Y—SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) ₃ , preferably —C (—Y—SiR ⁸⁵ ₃ ) ₃ .

In the above formula, R ^e independently represents —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 at each occurrence. Here, Y, R ⁸⁵ , R ⁸⁶ and n2 are as defined in R ⁸² above.

In the above formula, R ^f independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

Wherein k2 is independently an integer of 0 to 3 at each occurrence; l2 is independently an integer of 0 to 3 at each occurrence; and m2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of k2, l2, and m2 is 3.

In one embodiment, at least one k2 is 2 or 3, preferably 3.

In one embodiment, k2 is 2 or 3, preferably 3.

In one embodiment, l2 is 2 or 3, preferably 3.

In the above formulas (D1) and (D2), at least one q2 is an integer of 1 to 3, or at least one l is an integer 3 of 1 to 3. That is, there is at least one —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 group. Preferably, at least one q2 is 2 or 3, or at least one l is 2 or 3. That is, there are at least two —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 groups in the formula.

In the above formulas (D1) and (D2), at least one n2 is an integer of 1 to 3. That is, at least one ^{R 85} is present.

The perfluoro (poly) ether group-containing silane compound represented by the formula (D1) or the formula (D2) can be produced by combining known methods. For example, the compound represented by the formula (D1 ′) in which X is divalent is not limited, but can be produced as follows.

A group containing a double bond (preferably a polyhydric alcohol represented by HO—X—C (YOH) ₃ (wherein X and Y are each independently a divalent organic group)) Is allyl), and halogen (preferably bromo), and Hal—X—C (Y—O—R—CH═CH ₂ ) ₃ (where Hal is halogen, eg Br, R is A double bond-containing halide represented by a valent organic group such as an alkylene group. Next, a terminal halogen is reacted with a perfluoropolyether group-containing alcohol represented by R ^PFPE —OH (wherein R ^PFPE is a perfluoropolyether group-containing group), and R ^PFPE − O—X—C (Y—O—R—CH═CH ₂ ) ₃ is obtained. The terminal —CH═CH ₂ is then reacted with HSiCl ₃ and alcohol or HSiR ⁸⁵ ₃ to give R ^PFPE —O—X—C (Y—O—R—CH ₂ —CH ₂ —SiR ⁸⁵ ₃ ) ₃ Can be obtained.

The number average molecular weight of the perfluoropolyether group-containing silane compound contained in the surface treatment agent used in the present invention is preferably 5,000 or more, more preferably 6,000 or more, preferably 100,000 or less. Preferably it is 30,000 or less, More preferably, it is 10,000 or less.

The number average molecular weight of the PFPE moiety in the perfluoropolyether group-containing silane compound contained in the surface treating agent used in the present invention is not particularly limited, but is preferably 4,000 to 30,000, more preferably It can be 5,000 to 10,000.

In the present invention, the “number average molecular weight” is measured by GPC (gel permeation chromatography) analysis.

The surface treatment agent used in the present invention may be diluted with a solvent. Such a solvent is not particularly limited. For example, perfluorohexane, CF ₃ CF ₂ CHCl ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFC ₂ F ₅ , 1,1,1, 2,2,3,3,4,5,5,6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name Etc.), C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , CF ₃ CH ₂ OCF ₂ CHF ₂ , C ₆ F ₁₃ CH═CH ₂ , xylene hexafluoride, perfluorobenzene, methyl pentadeca fluoro heptyl ketone, trifluoroethanol, pentafluoropropanol, _{hexafluoroisopropanol, HCF 2 CF 2 CH 2 OH} , Mechirutorifuru B methanesulfonate, trifluoroacetic acid and _{CF 3 O (CF 2 CF 2} O) m (CF 2 O) n CF 2 CF 3 [ wherein, m and n are each independently zero or greater than 1,000 integer, The order of presence of each repeating unit with m or n enclosed in parentheses is arbitrary in the formula, provided that the sum of m and n is 1 or more.], 1,1-dichloro-2,3, 3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4 , 4-Hexafluoro-2-butene And a solvent selected from the group, which can be used alone or as a mixture of two or more.

The surface treatment agent used in the present invention may contain other components in addition to the perfluoropolyether group-containing silane compound. Such other components are not particularly limited. For example, (non-reactive) fluoropolyether compounds, preferably perfluoropolyether compounds (hereinafter referred to as “fluorinated oils”) that can be understood as fluorine-containing oils. ), A (non-reactive) silicone compound (hereinafter referred to as “silicone oil”), a catalyst and the like that can be understood as silicone oil.

Although it does not specifically limit as said fluorine-containing oil, For example, the compound (perfluoro polyether compound) represented by the following General formula (3) is mentioned.
Rf ¹ — (OC ₄ F ₈ ) _{a ′} — (OC ₃ F ₆ ) _{b ′} — (OC ₂ F ₄ ) _{c ′} — (OCF ₂ ) _{d ′} —Rf ² (3)
In the formula, Rf ¹ represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, and Rf ² represents _Represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom, and Rf ¹ and Rf ² Are more preferably each independently a C _1-3 perfluoroalkyl group.
a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 300, The sum of ', b', c 'and d' is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of presence of each repeating unit in parentheses with subscripts a ′, b ′, c ′ or d ′ is arbitrary in the formula. Among these repeating units, — (OC ₄ F ₈ ) — represents — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —, — (OCF (CF ₃ ) CF ₂ CF ₂ ) —, — (OCF ₂ CF (CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ))-,-(OC (CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C (CF ₃ ) ₂ )-,-(OCF (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-may be used, but preferably — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —. -(OC ₃ F ₆ )-is any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))- Of these, — (OCF ₂ CF ₂ CF ₂ ) — is preferable. — (OC ₂ F ₄ ) — may be either — (OCF ₂ CF ₂ ) — or — (OCF (CF ₃ )) —, but is preferably — (OCF ₂ CF ₂ ) —.

As an example of the perfluoropolyether compound represented by the above general formula (3), it may be a compound represented by any one of the following general formulas (3a) and (3b) (one kind or a mixture of two or more kinds). ).
Rf ^1- (OCF ₂ CF ₂ CF ₂ ) _{b ''} -Rf ² (3a)
Rf ¹ — (OCF ₂ CF ₂ CF ₂ CF ₂ ) _{a ″} — (OCF ₂ CF ₂ CF ₂ ) _{b ″} — (OCF ₂ CF ₂ ) _{c ″} — (OCF ₂ ) _{d ″} —Rf ^2. .. (3b)
In these formulas, Rf ¹ and Rf ² are as described above; in formula (3a), b ″ is an integer of 1 to 100; in formula (3b), a ″ and b ″ are Each independently represents an integer of 0 or more and 30 or less, for example, 1 or more and 30 or less, and c ″ and d ″ are each independently an integer of 1 or more and 300 or less. The order of existence of each repeating unit with subscripts a ″, b ″, c ″, d ″ and parentheses is arbitrary in the formula.

The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.

In the surface treatment agent used in the present invention, the fluorine-containing oil is based on a total of 100 parts by mass of the perfluoropolyether group-containing silane compound (in the case of two or more, respectively, the same applies to the following). For example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.

The compound represented by the general formula (3a) and the compound represented by the general formula (3b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (3b) rather than the compound represented by the general formula (3a) because higher surface slip properties can be obtained. When these are used in combination, the mass ratio of the compound represented by the general formula (3a) and the compound represented by the general formula (3b) is preferably 1: 1 to 1:30, and preferably 1: 1 to 1 : 10 is more preferable. According to such a mass ratio, a surface treatment layer having an excellent balance between surface slipperiness and friction durability can be obtained.

In one embodiment, the fluorine-containing oil contains one or more compounds represented by the general formula (3b). In such an embodiment, the mass ratio of the sum of the perfluoropolyether group-containing silane compounds in the surface treatment agent to the compound represented by the formula (3b) is preferably 10: 1 to 1:10, and preferably 4: 1 to 1: 4 is more preferable.

In one embodiment, the average molecular weight of the compound represented by the formula (3a) is preferably 2,000 to 8,000.

In one embodiment, the average molecular weight of the compound represented by the formula (3b) is preferably 8,000 to 30,000.

In another embodiment, the average molecular weight of the compound represented by formula (3b) is preferably 3,000 to 8,000.

In a preferred embodiment, when the surface treatment layer is formed by a vacuum deposition method, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the perfluoropolyether group-containing silane compound. By setting such an average molecular weight, more excellent friction durability and surface slipperiness can be obtained.

From another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf ³ -F (wherein Rf ³ is a C _5-16 perfluoroalkyl group). Moreover, a chlorotrifluoroethylene oligomer may be sufficient. The compound represented by Rf ³ -F and the chlorotrifluoroethylene oligomer are a compound represented by a fluorine-containing compound having a carbon-carbon unsaturated bond at the molecular end, the terminal of which is a C _1-16 perfluoroalkyl group. This is preferable in that high affinity can be obtained.

Fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.

As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be so-called straight silicone oil and modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.

In the surface treatment agent used in the present invention, the silicone oil is, for example, 0 with respect to 100 parts by mass in total of the perfluoropolyether group-containing silane compound (in the case of 2 or more types, these are also the same). It can be contained in an amount of up to 300 parts by weight, preferably 0 to 200 parts by weight.

Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.

The catalyst accelerates the hydrolysis and dehydration condensation of the perfluoropolyether group-containing silane compound and promotes the formation of the surface treatment layer.

As a method for forming the surface treatment layer, for example, a film of a surface treatment agent containing a fluorine-containing silane compound is formed on the surface of the silicon oxide layer, and this film is post-treated as necessary, whereby the surface treatment is performed. The method of forming a layer is mentioned.

The film formation of the surface treatment agent can be performed by applying the surface treatment agent to the surface of the silicon oxide layer so as to cover the surface. The coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.

Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

Examples of dry coating methods include PVD, CVD, and similar methods. PVD is a method in which a solid material is heated in a vacuum (vacuum deposition) or irradiated with high-speed electrons or ions to give physical energy to atoms on the surface of the solid and vaporize it. This is a method of forming a thin film by recombining with the above method. Although it does not specifically limit as PVD method, For example, a vapor deposition method (usually vacuum vapor deposition method), sputtering, etc. are mentioned. Specific examples of the vapor deposition method (usually vacuum vapor deposition method) include resistance heating, high-frequency heating using an electron beam, microwave, and the like, an ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods. Among them, the PVD method is preferable, and the evaporation method such as resistance heating evaporation or electron beam evaporation is preferable, and electron beam evaporation is more preferable. By using the PVD method, a surface treatment layer having higher friction durability can be obtained.

Furthermore, coating by the atmospheric pressure plasma method is also possible.

When the wet coating method is used, the surface treatment agent used in the present invention can be diluted with a solvent and then applied to the substrate surface. From the viewpoint of the stability of the surface treatment agent used in the present invention and the volatility of the solvent, the following solvents are preferably used: C _5-12 perfluoroaliphatic hydrocarbons (eg, perfluorohexane, perfluoromethyl) Cyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg C ₆ F ₁₃ CH ₂ CH ₃ (eg Asahi Culin (registered trademark AC-6000) manufactured by Asahi Glass Co., Ltd., 1,1,2,2,3,4,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by Nippon Zeon Co., Ltd.) Hydrofluorocarbon (HFC) (eg, 1,1,1,3,3-pentafluorobutane (HF) -365mfc)); hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether _{(C 3 F 7 OCH 3)} ( e.g., Novec (trade name) 7000 manufactured by Sumitomo 3M Limited, perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether ( C ₄ F ₉ OC ₂ H ₅ ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (for example, Sumitomo Novec made by 3M Co., Ltd. Name) 7300) alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or _{CF 3 CH 2 OCF 2 CHF 2} ( e.g., Asahi Glass Asahi Co., Ltd. Klin (registered trademark) AE-3000)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Bertrell (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), etc. These solvents can be used alone or in combination as a mixture of two or more thereof, for example, for adjusting the solubility of the perfluoropolyether group-containing silane compound. Can also be mixed.

When the dry coating method is used, the surface treatment agent used in the present invention may be directly subjected to the dry coating method, or may be diluted with the above-described solvent and then subjected to the dry coating method.

When the surface treatment agent used in the dry coating method contains a solvent, the solvent in the surface treatment agent may be removed in advance. By removing the solvent, a surface treatment layer having higher friction durability can be obtained.

Examples of the method for removing the solvent include distillation under reduced pressure.

The temperature during distillation under reduced pressure is preferably 0 to 200 ° C., more preferably 10 to 80 ° C. The pressure at the time of distillation under reduced pressure is preferably 1 × 10 ⁻⁴ Pa to 1 × 10 ³ Pa, more preferably 1 × 10 ⁻² Pa to 1 × 10 ² Pa.

For example, when PVD treatment is performed using a surface treatment agent containing a solvent, the solvent is first distilled off under reduced pressure using another apparatus or the like, and the residue is a perfluoropolyether group-containing silane compound (and, if present, contained). Other components such as fluorine oil and silicone oil) can be supplied into the PVD apparatus and vacuum deposition can be performed.

The film formation is preferably carried out so that the surface treatment agent is present in the film together with a catalyst for hydrolysis and dehydration condensation. For simplicity, in the case of the wet coating method, after diluting the surface treatment agent with a solvent, the catalyst may be added to the diluted solution of the surface treatment agent immediately before application to the substrate surface. In the case of the dry coating method, the catalyst-treated surface treatment agent is directly vapor-deposited (usually vacuum deposition), or a pellet form in which a porous metal such as iron or copper is impregnated with the catalyst-treated surface treatment agent. Vapor deposition (usually vacuum deposition) may be performed using a substance.

Any suitable acid or base can be used for the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Moreover, as a base catalyst, ammonia, organic amines, etc. can be used, for example.

Next, the membrane is post-treated as necessary. Although this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.

After forming a film of the surface treatment agent on the surface of the silicon oxide as described above, moisture is supplied to this film (hereinafter also referred to as “precursor film”). The method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.

When moisture is supplied to the precursor film, water acts on a hydrolyzable group bonded to Si of the perfluoropolyether group-containing silane compound in the surface treatment agent, so that the compound can be rapidly hydrolyzed. It is considered possible.

The supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. By supplying moisture in such a temperature range, hydrolysis can be advanced. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.

Next, the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 ° C. The drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower. What is necessary is just to arrange | position in the atmosphere of saturated water vapor pressure. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.

In such an atmosphere, the groups bonded to Si after hydrolysis rapidly undergo dehydration condensation between the PFPE-containing silane compounds of the present invention. Moreover, between such a compound and a base material, it reacts rapidly between the group couple | bonded with Si after the hydrolysis of the said compound, and the reactive group which exists in the base-material surface, and it exists in the base-material surface. When the reactive group is a hydroxyl group, dehydration condensation is performed. As a result, a bond is formed between the perfluoropolyether group-containing silane compound and the substrate.

The above water supply and drying heating may be continuously performed by using superheated steam.

Superheated steam is a gas obtained by heating saturated steam to a temperature higher than the boiling point, and exceeds 100 ° C. under normal pressure, generally 500 ° C. or lower, for example, 300 ° C. or lower, and has a boiling point. It is a gas that has become an unsaturated water vapor pressure by heating to a temperature exceeding. In the present invention, from the viewpoint of suppressing the decomposition of the perfluoropolyether group-containing silane compound, preferably, superheated steam at 250 ° C. or lower, preferably 180 ° C. or lower is used for moisture supply and drying heating. When the substrate on which the precursor film is formed is exposed to superheated water vapor, first, dew condensation occurs on the surface of the precursor film due to the temperature difference between the superheated water vapor and the relatively low temperature precursor film. Moisture is supplied to the membrane. Eventually, as the temperature difference between the superheated steam and the precursor film becomes smaller, the moisture on the surface of the precursor film is vaporized in a dry atmosphere by the superheated steam, and the moisture content on the surface of the precursor film gradually decreases. While the amount of moisture on the surface of the precursor film is reduced, that is, while the precursor film is in a dry atmosphere, the precursor film on the surface of the substrate comes into contact with the superheated steam, thereby the temperature of the superheated steam ( It will be heated to a temperature exceeding 100 ° C. under normal pressure. Therefore, if superheated steam is used, moisture supply and drying heating can be carried out continuously only by exposing the substrate on which the precursor film is formed to superheated steam.

Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the surface treatment agent to the substrate surface, it may be left still.

As described above, the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured. The surface treatment layer obtained by this has high friction durability. In addition to high friction durability, this surface treatment layer has water repellency, oil repellency, antifouling properties (for example, preventing adhesion of dirt such as fingerprints), depending on the composition of the surface treatment agent used. As a functional thin film, it can be waterproof (to prevent water from entering electronic parts, etc.), surface slippery (or lubricity, for example, wiping off dirt such as fingerprints, and excellent touch to fingers). It can be suitably used.

The article obtained by the present invention is not particularly limited, but may be an optical member. Examples of the optical member include the following optical members: For example, a cathode ray tube (CRT: eg, TV, personal computer monitor), liquid crystal display, plasma display, organic EL display, inorganic thin film EL dot matrix display, rear projection type Display such as display, fluorescent display tube (VFD), field emission display (FED), front protective plate, antireflection plate, polarizing plate, antiglare plate, or antireflection film treatment on the surface of these displays Lenses such as eyeglasses; Touch panel sheets for devices such as mobile phones and personal digital assistants; Disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; Optical fa Eber: Clock display surface.

Articles obtained by the present invention can further include ceramic products, coated surfaces, fabric products, leather products, medical products, plasters, etc.

The article obtained by the present invention may be a medical device or a medical material.

The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, preferably 1 to 30 nm, more preferably 1 to 15 nm. Optical performance, surface slipperiness, friction durability, and antifouling properties From the point of view, it is preferable.

The above-mentioned article of the present invention has high friction durability and high acid-alkali resistance, and depending on the composition of the surface treatment agent used, water repellency, oil repellency, antifouling (for example, adhesion of dirt such as fingerprints) ), Waterproofness (preventing water intrusion into electronic parts, etc.), surface slipperiness (or lubricity, for example, wiping off dirt such as fingerprints, and excellent touch feeling to fingers).

The article of the present invention is characterized in that a silicon oxide layer on which a surface treatment layer is formed is formed by a chemical vapor deposition method, and this feature provides excellent surface slip and acid-alkali resistance. Have. By forming a silicon oxide layer by a CVD method, a silicon oxide layer having a specific Ra, a silicon oxide layer having an amorphous structure, a silicon oxide layer having a specific density, or a specific hydrogen concentration in the film A silicon oxide layer can be formed.

Accordingly, in one aspect, the present invention provides a substrate, a silicon oxide layer located on the substrate,
An article comprising a surface treatment layer formed on the silicon oxide layer,
Provided is an article characterized in that the silicon oxide layer has a surface roughness (Ra: center line average roughness) of 0.2 nm or less.

In a preferred embodiment, Ra can be 0.15 nm or less.

In another aspect, the present invention provides a substrate, a silicon oxide layer located on the substrate,
An article comprising a surface treatment layer formed on the silicon oxide layer,
An article is provided wherein at least a portion of the silicon oxide layer is amorphous.

In a preferred embodiment, the silicon oxide layer may be amorphous at 50% or more of the entire silicon oxide layer, more preferably 80% or more of the entire silicon oxide layer.

In another aspect, the present invention provides a substrate, a silicon oxide layer located on the substrate,
An article comprising a surface treatment layer formed on the silicon oxide layer,
The silicon oxide layer provides an article characterized by having a density of ^{2.25g / cm 3 ~ 2.60g / cm} 3.

In a preferred embodiment, the density of the silicon oxide layer ^is 2.30g / cm 3 ~ 2.50g / cm 3, preferably a density of ^{2.35g / cm 3 ~ 2.45g / cm} 3, for example 2.38g / Cm ³ to 2.42 g / cm ³ .

In another aspect, the present invention provides a substrate, a silicon oxide layer located on the substrate,
An article comprising a surface treatment layer formed on the silicon oxide layer,
Provided is an article characterized in that the hydrogen concentration in the film of the silicon oxide layer is 1 to 10 at%.

In a preferred embodiment, the hydrogen concentration in the film of the silicon oxide layer is 2 at% or more, 3 at% or more, 4 at% or more or 5 at% or more, 9 at% or less, 8 at% or less, 7 at% or less or 6 at% or less. obtain. For example, the hydrogen concentration in the silicon oxide layer is 1 to 10 at%, 2 to 10 at%, 3 to 10 at%, 4 to 10 at%, or 5 to 10 at%, or 1 to 9 at%, 1 to 8 at%, 1 It can be ˜7 at% or 1 to 6 at%, or 2 to 9 at%, 3 to 8 at%, 4 to 7 at%, or 5 to 6 at%.

In another aspect, the present invention provides a substrate, a silicon oxide layer located on the substrate,
An article comprising a surface treatment layer formed on the silicon oxide layer,
There is provided an article characterized in that the Si / O composition ratio (mol ratio) in the silicon oxide layer is 0.6 to 1.5.

In a preferred embodiment, the Si / O composition ratio in the silicon oxide layer may be 1.5 or less, preferably greater than 0.5. The Si / O composition ratio is preferably 0.6 to 1.5, more preferably 0.7 to 1.3, such as 0.7 to 1.2, 0.8 to 1.3 or 0.8 to 1. .2.

The article of the present invention will be described more specifically through the following examples, but the present invention is not limited to these examples.

Example 1
-Formation of a silicon oxide layer As a base material, chemically strengthened glass (Corning company make, "gorilla" glass, thickness 0.7mm) was prepared. The surface of the substrate is washed with a mixed solution of H ₂ SO ₄ / H ₂ O ₂ / H ₂ O (1: 1: 5), SiH ₄ gas is used as the silicon source, and N ₂ O gas is used as the oxygen source. Then, plasma CVD was performed with a Tokyo Electron TriasCVD apparatus to form a silicon oxide (SiO) layer on the substrate surface.

(Plasma CVD film formation conditions)
RF power density: 1.0 W / cm ²
Substrate temperature: 200 ° C
Process pressure: 150 Pa
Material gas flow ratio (volume ratio): SiH ₄ : N ₂ O: H ₂ = 1: 30: 30
Deposition rate: 0.7 nm / second Processing time: 100 seconds

The film thickness of the obtained silicon oxide layer was measured with an ellipsometer (manufactured by HORIBA Jobin Yvon). The film thickness of the silicon oxide layer was 70 nm.

-Preparation of surface treatment material A surface treatment agent was prepared by dissolving a fluorine-containing compound represented by the following formula (average composition) in hydrofluoroether (manufactured by 3M, Novec HFE7200) to a concentration of 20 wt%.
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _m CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si [CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] ₃
(M = 21, Mn = 3980)
* The value of m is a value measured from ¹⁹ F-NMR, and Mn is a value measured from GPC.

Formation of surface treatment layer The silicon oxide layer obtained above was subjected to O ₂ ion cleaning at an acceleration voltage of 1000 V, an acceleration current of 500 mA, and a pressure of 2 × 10 ⁻² Pa. Subsequently, the surface treatment agent prepared above was vacuum-deposited on the silicon oxide layer. The processing conditions for vacuum deposition were a pressure of 3.0 × 10 ⁻³ Pa and a surface treatment agent of 2 mg (that is, 0.4 mg of a perfluoropolyether group-containing silane compound) per piece of chemically strengthened glass (55 mm × 100 mm). ) Was evaporated. Thereafter, the chemically strengthened glass with a deposited film was allowed to stand for 24 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 65% to obtain an article having a silicon oxide and a surface treatment layer on the substrate.

Example 2
An article having a silicon oxide and a surface treatment layer on a substrate was obtained in the same manner as in Example 1 except that the plasma film conditions were changed. The film thickness of the silicon oxide layer measured with an ellipsometer was 30 nm.

(Plasma CVD film formation conditions)
RF power density: 1.0 W / cm ²
Substrate temperature: 200 ° C
Process pressure: 150 Pa
Material gas flow rate ratio (volume ratio): SiH ₄ : N ₂ O: H ₂ = 1: 30: 180
Deposition rate: 0.5 nm / second Processing time: 60 seconds

Example 3
An article having a silicon oxide and a surface treatment layer on a substrate was obtained in the same manner as in Example 2 except that the CVD treatment time was changed to 30 seconds. The film thickness of the silicon oxide layer measured with an ellipsometer was 15 nm.

Comparative Example 1
The silicon oxide layer and the surface treatment layer were formed on the substrate in the same manner as in Example 1 except that the silicon oxide layer was formed by the PVD method (electron beam (EB) deposition) instead of being formed by the CVD method. An article having The film thickness of the silicon oxide layer measured with an ellipsometer was 70 nm.
(EB deposition conditions)
・ Pressure: 2 × 10 ⁻² Pa
・ Substrate temperature: Room temperature
・ Raw material: SiO ₂ crystal ・ Vapor deposition processing time: 230 seconds

Comparative Example 2
An article having a silicon oxide and a surface treatment layer on a substrate was obtained in the same manner as in Comparative Example 1 except that the deposition process time of the PVD method (electron beam (EB) deposition) was changed to 80 seconds. The film thickness of the silicon oxide layer measured with an ellipsometer was 30 nm.

Comparative Example 3
An article having a silicon oxide and a surface treatment layer on a substrate was obtained in the same manner as in Comparative Example 1 except that the vapor deposition treatment time of the PVD method (electron beam (EB) vapor deposition) was changed to 50 seconds. The film thickness of the silicon oxide layer measured with an ellipsometer was 15 nm.

The characteristics of the base material obtained above are shown in the following table.

(Evaluation)
Friction durability evaluation The static contact angle of water was measured for the surface treatment layers of Examples 1 to 3 and Comparative Examples 1 to 3 described above. The static contact angle of water was measured with 1 μL of water using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.).

First, as an initial evaluation, after the surface treatment layer was formed, the static contact angle of water was measured with nothing touching the surface (the number of frictions was zero).

Then, steel wool friction durability evaluation was carried out as friction durability evaluation. Specifically, the base material on which the surface treatment layer is formed is horizontally arranged, and steel wool (count # 0000, dimensions 5 mm × 10 mm × 10 mm) is brought into contact with the exposed upper surface of the surface treatment layer, and 1,000 gf of the steel wool is placed thereon. A load was applied, and then the steel wool was reciprocated with the load applied (distance: 120 mm (reciprocation), speed: 60 rpm). The static contact angle (degree) of water was measured at every fixed number of reciprocations. The evaluation was stopped when the measured value of the contact angle was less than 100 degrees. The results are shown in the table below.

Example 4
Except that 0.25 mg of a surface treatment agent (that is, containing 0.05 mg of a perfluoropolyether group-containing silane compound) was vapor deposited per piece of chemically strengthened glass (55 mm × 100 mm), the same as in Example 3. An article having a silicon oxide and a surface treatment layer on the substrate was obtained. The film thickness of the silicon oxide layer measured with an ellipsometer was 15 nm.

Comparative Example 4
Except that 0.25 mg of surface treating agent (that is, containing 0.05 mg of a perfluoropolyether group-containing silane compound) was vapor deposited per piece of chemically strengthened glass (55 mm × 100 mm), the same as Comparative Example 3 An article having a silicon oxide and a surface treatment layer on the substrate was obtained. The film thickness of the silicon oxide layer measured with an ellipsometer was 15 nm.

・ Sweat resistance test (acid and alkali durability test)
The artificial sweat durability was evaluated for the surface treatment layers of Example 4 and Comparative Example 4 described above.

Specifically, about 50 μL of artificial sweat of pH 8.7 and pH 4.5 having the following composition was allowed to stand on the surface of the article obtained in Example 4 and Comparative Example 4, and 60 ° C. and 90 RH% applied. It was left for a predetermined time under warm and humid conditions. Thereafter, the artificial sweat on the surface was wiped off, the surface was further washed with distilled water and ethanol, and then the static contact angle (degree) of water was measured. The results are shown in the table below.

Composition of artificial sweat with pH 8.7 Add pure water to NaCl: 10 g, Na ₂ HPO ₄ · 12H ₂ O: 2.5 g, (NH ₄ ) ₂ CO ₃ : 4 g to make a total of 1000 ml.

-Composition of artificial sweat with pH 4.5 NaCl: 10 g, Na ₂ HPO ₄ · 12H ₂ O: 2.5 g, CH ₃ CH (OH) COOH: 1 g of pure water is added to make a total of 1000 ml.

From the results in Tables 2 and 3 above, Examples 1 to 3 in which the silicon oxide layer was formed using the CVD method were superior in friction durability to Comparative Examples 1 to 3 using the PVD method, It was confirmed that Example 4 was superior to Comparative Example 4 and superior in acid and alkali durability. That is, by forming the surface treatment layer on the silicon oxide layer formed by the CVD method, it is possible to form a surface treatment layer having better friction durability and more excellent acid and alkali resistance. Was confirmed.

The present invention can be suitably used for producing an article comprising a surface treatment layer having high friction durability and acid and alkali resistance on the surface.

Claims (24)

A substrate;
A silicon oxide layer located on the substrate;
A method for producing an article comprising a surface treatment layer formed on the silicon oxide layer,
Forming a silicon oxide layer using chemical vapor deposition, and forming a surface treatment layer on the obtained silicon oxide layer using a surface treatment agent containing a fluorine-containing silane compound; Manufacturing method including. The manufacturing method according to claim 1, wherein the chemical vapor deposition method is performed using a reactive gas containing silane or disilane. The method according to claim 1 or 2, wherein the silicon oxide layer has a thickness of 5 to 100 nm. The method according to any one of claims 1 to 3, wherein the silicon oxide layer has a surface roughness Ra of 0.2 nm or less. The method according to any one of claims 1 to 4, further comprising ion cleaning the surface of the silicon oxide layer after the formation of the silicon oxide layer and before the formation of the surface treatment layer. 6. The manufacturing method according to claim 1, wherein the surface treatment layer is formed using a physical vapor deposition method. The fluorine-containing silane compound has the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):

[Where:
PFPE has the formula:
-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n is an integer of 0 to 3, independently for each (-SiR ¹ _n R ² _3-n ) unit;
Provided that in formulas (A1), (A2), (B1) and (B2), at least one R ² is present;
Each X ¹ independently represents a single bond or a divalent to 10-valent organic group;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
each α is independently an integer from 1 to 9;
α ′ is each independently an integer of 1 to 9;
Each X ⁵ independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
X ⁷ each independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer from 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence;
Z represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R ⁷¹ independently represents R ^{a ′} at each occurrence;
R ^{a ′} is synonymous with R ^a ;
In R ^a , the maximum number of Si linearly linked via the Z group is 5;
R ⁷² independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁷³ independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p is independently an integer from 0 to 3 at each occurrence;
q is independently an integer from 0 to 3 at each occurrence;
r is independently an integer from 0 to 3 at each occurrence;
Provided that for each of —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r , the sum of p, q and r is 3, and in formulas (C1) and (C2), there is at least one R ⁷² ;
R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k is an integer of 1 to 3 independently at each occurrence;
l is an integer from 0 to 2 independently at each occurrence;
m is an integer from 0 to 2 independently at each occurrence;
Provided that the sum of k, l and m is 3 in the unit enclosed in parentheses with γ;
X ⁹ each independently represents a single bond or a divalent to 10-valent organic group;
each δ is independently an integer from 1 to 9;
each δ ′ is independently an integer from 1 to 9;
R ^d independently represents at each occurrence —Z ² —CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 ;
Z ² independently represents an oxygen atom or a divalent organic group at each occurrence;
R ⁸¹ independently represents R ^{d ′} at each occurrence;
R ^{d ′} is synonymous with R ^d ;
In R ^d , the maximum number of C linked in a straight chain via the Z ² group is 5;
R ⁸² independently represents at each occurrence —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ;
Y represents a divalent organic group independently at each occurrence;
R ⁸⁵ independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁸⁶ independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n2 independently represents an integer of 0 to 3 for each (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) unit;
R ⁸³ each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p2 is independently an integer from 0 to 3 at each occurrence;
q2 is independently an integer from 0 to 3 at each occurrence;
r2 is independently an integer from 0 to 3 at each occurrence;
R ^e independently represents at each occurrence —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ;
R ^f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k2 is independently an integer from 0 to 3 at each occurrence;
l2 is independently an integer from 0 to 3 at each occurrence;
m2 is an integer from 0 to 3 independently at each occurrence;
However, in formulas (D1) and (D2), at least one R ⁸⁵ is present. ]
The production method according to any one of claims 1 to 6, wherein the compound is one or more compounds represented by the formula: PFPE is independently represented by the following formulas (a) to (c):
(A)-(OC ₃ F ₆ ) _b-
[In formula (a), b is an integer of 1 or more and 200 or less];
(B)-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
[In the formula (b), a and b are each independently an integer of 0 or more and 30 or less, c and d are each independently an integer of 1 or more and 200 or less, and a, b, c And the sum of d is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the suffix a, b, c, or d is arbitrary in the formula. ]
(C)-(OC ₂ F ₄ —R ¹⁵ ) _{n ″} −
[In Formula (c), each R ¹⁵ is independently a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , and n ″ is an integer of 2 or more and 100 or less. .]
The manufacturing method according to claim 7, wherein the manufacturing method is any one of the following. In PFPE:
OC ₄ F ₈ is OCF ₂ CF ₂ CF ₂ CF ₂ ,
OC ₃ F ₆ is OCF ₂ CF ₂ CF ₂ ,
The manufacturing method according to claim 7, wherein OC ₂ F ₄ is OCF ₂ CF ₂ . The production method according to any one of claims 1 to 9, wherein the surface treatment agent further contains one or more other components selected from fluorine-containing oil, silicone oil, and catalyst. The fluorine-containing oil has the formula (3):
Rf ¹ — (OC ₄ F ₈ ) _{a ′} — (OC ₃ F ₆ ) _{b ′} — (OC ₂ F ₄ ) _{c ′} — (OCF ₂ ) _{d ′} —RF ² (3)
[Where:
Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
Rf ² represents an alkyl group having 1 to 16 carbon atoms, a fluorine atom or a hydrogen atom which may be substituted by one or more fluorine atoms;
a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 300, The sum of ', b', c 'and d' is at least 1, and the order of presence of each repeating unit in parentheses with the subscript a ', b', c 'or d' is Is optional. ]
The manufacturing method of Claim 10 which is one or more compounds represented by these. The fluorine-containing oil has the formula (3a) or (3b):
Rf ^1- (OCF ₂ CF ₂ CF ₂ ) _{b ''} -Rf ² (3a)
Rf ¹ — (OCF ₂ CF ₂ CF ₂ CF ₂ ) _{a ″} — (OCF ₂ CF ₂ CF ₂ ) _{b ″} — (OCF ₂ CF ₂ ) _{c ″} — (OCF ₂ ) _{d ″} —Rf ^2. .. (3b)
[Where:
Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
Rf ² represents an alkyl group having 1 to 16 carbon atoms, a fluorine atom or a hydrogen atom which may be substituted by one or more fluorine atoms;
In formula (3a), b ″ is an integer of 1 to 100;
In formula (3b), a ″ and b ″ are each independently an integer of 0 or more and 30 or less, and c ″ and d ″ are each independently an integer of 1 or more and 300 or less;
The order of presence of each repeating unit in parentheses with the suffix a ″, b ″, c ″ or d ″ is arbitrary in the formula. ]
The manufacturing method of Claim 10 or 11 which is one or more compounds represented by these. Preparing a substrate,
Forming a silicon oxide layer on the substrate using chemical vapor deposition, and forming a surface treatment layer on the silicon oxide layer using a surface treatment agent containing a fluorine-containing silane compound. The production method according to any one of claims 1 to 12. The chemical vapor deposition method is performed by using SiH ₄ , Si ₂ H ₆ , triethoxysilane or tetraethoxysilane as a silicon source, and using oxygen gas as an oxygen source. The manufacturing method as described. Furthermore, before forming a silicon oxide layer, the base-material surface is pre-processed by oxidant solution washing | cleaning or alcohol washing | cleaning, The manufacturing method of Claim 13 or 14 characterized by the above-mentioned. 16. The method according to claim 13, further comprising pre-treating the silicon oxide layer by ion cleaning before forming the surface treatment layer. The manufacturing method according to claim 16, wherein the ion cleaning is oxygen ion cleaning or argon ion cleaning. The production method according to any one of claims 1 to 17, wherein the substrate is a glass substrate. The manufacturing method according to any one of claims 1 to 18, wherein the article is an optical member. An article obtained by the manufacturing method according to any one of claims 1 to 19. A substrate and a silicon oxide layer located on the substrate;
An article comprising a surface treatment layer formed on the silicon oxide layer,
An article wherein at least a portion of the silicon oxide layer is amorphous. A substrate and a silicon oxide layer located on the substrate;
An article comprising a surface treatment layer formed on the silicon oxide layer,
The article of silicon oxide ^layer, characterized by having a density of 2.25g / cm 3 ~ 2.60g / cm 3. A substrate and a silicon oxide layer located on the substrate;
An article comprising a surface treatment layer formed on the silicon oxide layer,
An article, wherein the silicon oxide layer has a hydrogen concentration of 1 to 10 at%. A substrate and a silicon oxide layer located on the substrate;
An article comprising a surface treatment layer formed on the silicon oxide layer,
An article having a Si / O composition molar ratio in the silicon oxide layer of 0.6 to 1.5.