KR20180001556A - Method for manufacturing article having surface treated layer - Google Patents

Abstract

The present invention provides a method for producing an article comprising a substrate, a silicon oxide layer positioned on the substrate, and a surface treatment layer formed on the silicon oxide layer, wherein the silicon oxide layer is formed by chemical vapor deposition And a method for producing a surface treatment layer by using a surface treatment agent containing a fluorine-containing silane compound on the obtained silicon oxide layer.

Description

Method for manufacturing article having surface treated layer

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

It is known that any kind of fluorine-containing compound can provide excellent water repellency, oil repellency, and antifouling property when used in surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a " surface treatment layer ") is a so-called functional thin film which is applied to various substrates such as glass, plastic, fiber and building materials.

As such a fluorine-containing silane compound, there is known a perfluoropolyether group-containing silane compound having a perfluoropolyether group in its molecular backbone and a hydrolyzable group bonded to Si atoms at the molecular end or terminal end. For example, Patent Document 1 discloses a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at a molecular end or a terminal end. In Patent Document 1, a surface treatment layer is formed by forming a SiO ₂ layer on the outermost surface of a substrate and applying a surface treatment agent containing a fluorine-containing silane compound on the SiO ₂ layer.

Japanese Patent Application Laid-Open No. 2013-117012

The surface treatment layer is required to have high durability in order to provide desired functions to the substrate over a long period of time. Since the layer obtained from the surface treatment agent containing the perfluoropolyether group-containing silane compound can exert such a function even in a thin film, it is preferably used for optical members such as glasses and touch panels requiring transparency or transparency In particular, in these applications, further improvement in friction durability is required.

As a pretreatment for forming a surface treatment layer as described in Patent Document 1, there is known a method of forming a SiO ₂ layer on the outermost surface of a substrate and then applying a surface treatment agent thereon. However, It has been found that when the SiO ₂ layer is formed by physical vapor deposition (PVD method), the friction durability and the durability of sweat are not sufficient.

Accordingly, it is an object of the present invention to provide a method for producing an article having a surface treatment layer which is more excellent in friction durability and sweat durability (i.e., acid and alkali resistance).

As a result of intensive investigations, the inventors of the present invention have found that by forming a silicon oxide layer formed on the outermost layer of a substrate by using a chemical vapor deposition method (CVD method: Chemical Vapor Deposition) instead of a PVD method such as vacuum deposition, And an article having a surface treatment layer excellent in sweat durability can be provided.

According to a first aspect of the present invention,

A silicon oxide layer positioned on the substrate,

A surface treatment layer formed on the silicon oxide layer

A method for producing an article,

Forming a silicon oxide layer using a chemical vapor deposition method, and

And a surface treatment layer is formed by using a surface treatment agent containing a fluorine-containing silane compound on the obtained silicon oxide layer

Is provided.

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

According to the present invention, there is provided a surface treatment layer having water repellency, oil repellency, antifouling property, and excellent friction durability and sweat durability by forming a silicon oxide layer using a CVD method and forming a surface treatment layer thereon The article can be manufactured.

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

An article produced by the production method of the present invention comprises a substrate, a silicon oxide layer positioned on the substrate, and a surface treatment layer formed on the silicon oxide layer.

First, a substrate is prepared. The substrate that can be used in the present invention may be a substrate, a glass, a sapphire glass, a resin (natural or synthetic resin, for example, a general plastic material, (Ceramic, semiconductor, silicon, germanium, etc.), fiber (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, ≪ / RTI > Preferably, the substrate is glass.

Preferable examples of the glass include soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass and quartz glass, and chemically reinforced soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass Particularly preferred.

The shape of the substrate is not particularly limited. The surface area of the substrate on which the silicon oxide layer and the surface treatment layer should be formed may be at least a part of the surface of the substrate, and may be suitably determined in accordance with the use of the article to be produced, the specific specification, and the like.

(Or film), for example, a hard coating 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 the mineral available for the anti-reflection _{layer, 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 an article to be manufactured is an optical glass part for a touch panel, a transparent electrode, for example, a thin film made of indium tin oxide (ITO) or indium zinc oxide may be provided on a part of the surface of a substrate (glass) . In addition, the base material may be formed of an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a fogging film layer, a hard coating layer, a polarizing film, .

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

As the pretreatment, though not particularly limited, cleaning with an oxidizing agent solution such as H ₂ O ₂ or H ₂ SO ₄ , or alcohol such as ethanol can be mentioned. The cleaning with H ₂ O ₂ / H ₂ SO ₄ / H ₂ O mixed solution (1 to 5: 1 to 5: 1 to 20) or ethanol is preferable, and the cleaning with H ₂ O ₂ / H ₂ SO ₄ / H ₂ O It is more preferable to wash with the mixed solution.

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

The silicon oxide layer is formed by a CVD method. The CVD method is a method in which a material to be a raw material is supplied in a gaseous state and reacted at the substrate surface to form a nonvolatile film. Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD, and the like. Preferably, plasma CVD is used.

As the silicon source in the CVD method, a silicon compound is used. Examples of the silicon compound include silane compounds such as SiH ₄ and Si ₂ H _6, and organic silicon compounds such as triethoxysilane and tetraethoxysilane. Preferably, the 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 depending on 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 in accordance with the kind of the CVD method used, the film thickness of the silicon oxide layer, and the like. For example, in the case where the silicon oxide layer is formed by plasma CVD, it is preferable to perform 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 to 400 占 폚, preferably 150 to 300 占 폚, for example 200 占 폚;

Process pressure: 50 to 500 Pa, preferably 100 to 300 Pa, such as 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 further preferably 10 to 20 nm . By setting the film thickness of the silicon oxide layer within the above range, it is possible to form a surface treatment layer having higher friction durability on the silicon oxide layer. In the present specification, the film thickness of the silicon fluoride layer is a value measured by an ellipsometer.

The silicon oxide layer formed by the CVD method may have a surface roughness (Ra: center line 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 a part, more preferably at least 50% of the entire silicon oxide layer, more preferably at least 80% of the entire silicon oxide layer. The amorphous phase in the silicon oxide layer can be confirmed by measuring the intensity of the diffraction peak due to crystallization by X-ray diffraction (XRD).

The silicon oxide layer formed by the CVD method preferably has a density of 2.25 g / cm3 to 2.60 g / cm3, more preferably 2.30 g / cm3 to 2.50 g / cm3, still more preferably 2.35 g / Cm 3 to 2.45 g / cm 3, for example, a density of 2.38 g / cm 3 to 2.42 g / cm 3. The density of the silicon oxide layer can be measured by X-ray reflectometry (XRR).

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% For example, 9 at% or less, 8 at% or less, 7 at% or less, or 6 at% or less. For example, the hydrogen concentration in the membrane may be in the range of 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% Or 1 to 6 at%, or 2 to 9 at%, 3 to 8 at%, 4 to 7 at%, or 5 to 6 at%. The hydrogen concentration in the film of the silicon oxide layer can be measured by Rutherford backscattering spectrometry (RBS).

The Si / O composition ratio (molar ratio) in the silicon oxide layer formed by the CVD method may be 1.5 or less, preferably 0.5 or more. The Si / O composition ratio may preferably be 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 the Rutherford backscattering spectrometry (RBS) method.

In one form, 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.

As the pretreatment, for example, ion cleaning may be mentioned. The ion cleaning is not particularly limited, but oxygen ion cleaning and argon ion cleaning are preferable, and oxygen ion cleaning is more preferable.

The conditions for the ion cleaning may vary depending on the type of gas used, but in the case of oxygen ion cleaning, the conditions are as follows. However, the ion cleaning is not limited to the following conditions as long as it can remove impurities on the silicon oxide layer.

(Oxygen ion cleaning condition)

Acceleration voltage: 500 to 1500 V, preferably 800 to 1200 V, typically 1000 V

Acceleration current: 100 to 1000 mA, preferably 300 to 700 mA, typically 500 mA

Gas volume: 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

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

The fluorine-containing silane compound preferably contains a perfluoropolyether group and includes, for example, at least one of the following general formulas (A1), (A2), (B1), (B2), (C1) (D1) and (D2):

[Wherein:

PFPE is, independently at each occurrence,

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -

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 is enclosed in parentheses with suffixes a, b, c, The order of existence of the true repeat units is arbitrary in the formula.)

≪ / RTI >

Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted at each occurrence independently by one or more fluorine atoms;

R ¹ in each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

R ² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;

R ¹¹ in each occurrence independently represents a hydrogen atom or a halogen atom;

R ¹² in each occurrence independently represents a hydrogen atom or a lower alkyl group;

n is independently an integer of 0 to 3 for each (-SiR ¹ _n R ² _{3 -n} ) unit;

Provided that at least one R < ² > is present in the formulas (A1), (A2), (B1) and (B2);

X ¹ each independently represents a single bond or an organic group having 2 to 10 carbon atoms;

X ² represents, at each occurrence, each independently a single bond or a divalent organic group;

t is, independently at each occurrence, an integer of 1 to 10;

a is independently an integer of 1 to 9;

? 'are each independently an integer of 1 to 9;

X ⁵ are each independently a single bond or a divalent to 10 represents an organic group;

is independently an integer of 1 to 9;

is independently an integer of 1 to 9;

X ⁷ each independently represent a single bond or an organic group having 2 to 10 carbon atoms;

y is independently an integer of 1 to 9;

y 'are each independently an integer of 1 to 9;

R ^a in each occurrence independently represents -Z-SiR ⁷¹ _p R ⁷² _q R ⁷³ _r ;

Z represents, at each occurrence, each independently an oxygen atom or a divalent organic group;

R ⁷¹ in each occurrence independently represents R ^{a '} ;

R ^{a '} is the same as R ^a ;

In R ^a , at most 5 Si atoms are connected in a straight chain through the group Z;

R ⁷² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;

R ⁷³ in each occurrence independently represents a hydrogen atom or a lower alkyl group;

p is, independently at each occurrence, an integer of 0 to 3;

q is, independently at each occurrence, an integer of 0 to 3;

r is, independently at each occurrence, an integer of 0 to 3;

With the proviso that the sum of p, q and r in the (Z-SiR ⁷¹ _p R ⁷² _q R ⁷³ _r ) unit is 3, and in the formulas (C1) and (C2), at least one R ⁷² is present;

R ^b in each occurrence independently represents a hydroxyl group or a hydrolyzable group;

R ^c represents, at each occurrence, each independently a hydrogen atom or a lower alkyl group;

k is, independently at each occurrence, an integer of 1 to 3;

l is, independently at each occurrence, an integer of 0 to 2;

m is, independently at each occurrence, an integer of 0 to 2;

However, in the unit in which? Is attached and parenthesized, the sum of k, l, and m is 3;

X ⁹ each independently represent a single bond or an organic group of 2 to 10 carbon atoms;

? are each independently an integer of 1 to 9;

? 'are each independently an integer of 1 to 9;

R ^d are each independently -Z ² -CR ⁸¹ R ⁸² _{p2 q2} R ⁸³ represents an _r2 at each occurrence;

Z ² represents, at each occurrence, each independently an oxygen atom or a divalent organic group;

R ⁸¹ independently represents R ^{d '} at each occurrence;

R ^{d '} is the same as R ^d ;

Of R ^d , there are at most 5 C connected in a straight chain through the group Z ² ;

R ⁸² in each occurrence independently represents -Y-SiR ⁸⁵ _{n 2} R ⁸⁶ _{3 -n 2} ;

Y represents, at each occurrence, each independently a divalent organic group;

R ⁸⁵ in each occurrence independently represents a hydroxyl group or a hydrolyzable group;

R ⁸⁶ in each occurrence independently represents a hydrogen atom or a lower alkyl group;

n2 _{^{is, (-Y-SiR 85 n2 R}} 86 3 -n2) units each independently represents an integer of 0 to 3;

R ⁸³ in each occurrence independently represents a hydrogen atom or a lower alkyl group;

p2 is, independently at each occurrence, an integer of 0 to 3;

q2 are each independently an integer of 0 to 3 at each occurrence;

r2 is, independently at each occurrence, an integer of 0 to 3;

R ^e in each occurrence independently represents -Y-SiR ⁸⁵ _n2 R ⁸⁶ _{3 -n 2} ;

R ^f represents, at each occurrence, each independently a hydrogen atom or a lower alkyl group;

k2 are each independently an integer of 0 to 3 at each occurrence;

l2 is, independently at each occurrence, an integer of 0 to 3;

m2 are each independently an integer of 0 to 3 at each occurrence;

Provided that at least one R ⁸⁵ is present in the formulas (D1) and (D2)].

≪ / RTI >

As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen, and means a group in which one hydrogen atom has been removed from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with one or more substituents, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and the like. The "aliphatic hydrocarbon group" may be any of linear, branched or cyclic, and may be either saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures. Such a hydrocarbon group may have one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like in its terminal or molecular chain.

As used herein, the substituent of the " hydrocarbon group " is not particularly limited and includes, for example, a halogen atom; A C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _3-10 cycloalkyl group, a C _3-10 unsaturated cycloalkyl group, an optionally substituted 5- or 6- Membered heterocyclic group, a 5- to 10-membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, a C _6-10 aryl group and a 5- to 10-membered heteroaryl group.

As used herein, a "2- to 10-valent organic group" means a 2- to 10-membered group containing carbon. Such a 2 to 10-valent organic group is not particularly limited, but a 2 to 10-valent group in which 1 to 9 hydrogen atoms are further removed from a hydrocarbon group can be exemplified. For example, the divalent organic group is not particularly limited, but a divalent group obtained by removing one hydrogen atom from a hydrocarbon group can be exemplified.

Description of the perfluoropolyether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and do.

Compounds of formula (A1) and (A2):

In the formula, PFPE is _{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - , and corresponds to the perfluoro polyether groups. 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 or more and 200 or less, for example, an integer of 1 to 200, and more preferably, an integer of 0 or more and 100 or less. 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. The order of existence of each repeating unit in parentheses with a, b, c, or d is arbitrary in the equation. Of these repeating _{units, - (OC 4 F 8)} - _{is, - (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)) - which is, but even during, preferably - (OCF ₂ CF ₂ CF ₂ CF ₂ ) -. - (OC ₃ F ₆₎ - _{is, - (OCF 2 CF 2 CF} 2) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - which is, but even during, Preferably - (OCF ₂ CF ₂ CF ₂ ) -. Further, - (OC ₂ F ₄ ) - may be any of - (OCF ₂ CF ₂ ) - and - (OCF (CF ₃ )) -, but is preferably - (OCF ₂ CF ₂ ) -.

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

In a further aspect, PFPE _{is, - (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 C and d are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less, and subscripts a, b, c, or d the present order of the repeating units closely tied in parentheses is optionally a) in the formula, preferably a _{- (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 form, PFPE is represented by - (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, Is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit in parentheses with the suffix c or d is arbitrary in the formula).

In another aspect, the PFPE is a group represented by - (OC ₂ F ₄ -R ¹⁵ ) _{n "} -, wherein R ¹⁵ is selected from OC ₂ F ₄ , OC ₃ F _6, and OC ₄ F ₈ Or a combination of two or three groups independently selected from these groups. As the combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , But are not limited to, -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 OC 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 -. The above n "is an integer of 2 to 100, An integer of 2 to 50 All. In the formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either linear or branched, and preferably straight-chain. In this form, 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 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 by one or more fluorine atoms may be straight chain, branched chain, or straight chain or branched chain Is an alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms.

The Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted by one or more fluorine atoms, more preferably a CF ₂ HC _1-15 fluoroalkylene group, still more preferably a carbon number 1 To 16 perfluoroalkyl groups.

The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched and is preferably a straight or branched perfluoroalkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, Is a straight-chain 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 formulas, R ¹ in each occurrence 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.

In the formula, R ² represents a hydroxyl group or a hydrolyzable group in each occurrence independently of each other.

The term "hydrolyzable group" as used herein means a group which can be removed from the main skeleton of the compound by a hydrolysis reaction. Examples of the hydrolyzable group include -OR, -OCOR, -ON = CR ₂ , -NR ₂ , -NHR, halogen (wherein R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), etc. , And preferably -OR (i.e., an 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; And substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly a non-substituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but hydrolyzable groups may be generated by hydrolysis.

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

In the formula, R ¹² in each occurrence 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 formula, n is an ^{_{(-SiR 1 n R 2 3 -n}} ) independently selected from the integers from 0 to 3 per unit, preferably from 0 to 2, more preferably zero. However, in the formula, all n's are not 0 at the same time. In other words, at least one of R ² is present in the formula.

In the formula, X ¹ represents, independently of each other, a single bond or an organic group having 2 to 10 carbon atoms. The X ¹ is preferably a compound represented by the formula (A1) or (A2) in which a perfluoropolyether moiety (i.e., an Rf-PFPE moiety or a -PFPE moiety) that mainly provides water repellency and surface slip property , And a linker connecting a silane moiety (i.e., a group bracketed with &thetas;) that provides bonding ability of the substrate. Accordingly, the X ¹ may be any organic group provided that the compound represented by the formula (A1) or (A2) can be stably present.

In the above formula,? Is an integer of 1 to 9 and? 'Is an integer of 1 to 9. These α and α ', can be varied depending on the valence of X ^1. In the formula (A1), the sum of α and α 'are 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, eg, α is 9 and α' is 1, α is 5 and α 'is 5 or α is 1 And alpha 'can be 9. In addition, when X ¹ is a divalent organic date, α and α 'it is 1. In the formula (A2),? Is a value obtained by subtracting 1 from the mantissa of X ¹ .

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

In one form, X &^lt; ¹ > is a 2- to 4-membered organic group, [alpha] is 1 to 3, and [alpha] 'is 1.

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

Examples of X ¹ include, but are not particularly limited to,

- (R ³¹ ) _{p '} - (X ^a ) _q' -

[Wherein:

R ³¹ represents a single bond, - (CH ₂ ) _{s '} - or an 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, still 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 group, -C (O) O-, -Si (R ³³ ) ₂ -, - _{^{(R 33) 2 O) m}} '-Si (R 33) 2 -, -CONR 34 -, -O-CONR 34 -, -NR 34 - , and - (CH _{2) n'} - group is selected from the group consisting of And,

R ³³ in each occurrence 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, more preferably a methyl group,

R ³⁴ in each occurrence independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group)

m 'is, at each occurrence, independently an integer of 1 to 100, preferably an integer of 1 to 20,

n 'in each occurrence is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,

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,

Herein, at least one of p 'and q' is 1, and the order of existence of each repeating unit in parenthesis with p 'or q' is arbitrary.

And the like. Here, R ³¹ and X ^a (typically hydrogen atoms of R ³¹ and X ^a ) are substituted by one or more substituents selected from a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group .

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, 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 ) may be substituted by one or more substituents selected from a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group.

Preferably, X < ¹ >

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.

Lt; / RTI >

More preferably, X < ¹ >

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.

to be.

Wherein X < ^c >

-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 formula, X is ^d,

-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.

.

More preferably, X < ¹ >

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.

Lt; / RTI >

More preferably, X < ¹ >

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 )

V is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3, and R < ³³ >, m ', s', t 'and u' .]

to be.

In the above formulas, - (C _v H _2v ) - may be a straight chain or a branched chain, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) _{, -CH (CH 3) CH 2} - may be.

The X ¹ group may be 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) .

In one form, the group X ¹ may be other than the -OC _1-6 alkylene group.

In another form, the X ¹ group includes, for example, the following groups:

[Wherein R ⁴¹ is each 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;

D,

-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 means phenyl), and

(Wherein R ⁴² represents, independently of each other, 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)

≪ / RTI >

E is - (CH ₂ ) _n - (n is an integer of 2 to 6)

D binds to the PFPE of the backbone of the molecule and E binds to the group opposite to PFPE.

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 means phenyl),

-CONH- (CH ₂ ) ₆ -,

_{-CON (CH 3) - (CH} 2) 6 -,

-CON (Ph) - (CH ₂ ) ₆ - (wherein Ph means 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 -,

-OCFHCF ₂ -,

And the like.

In yet another aspect, 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, and the sum of x, y and z is 1 or more, and the order of existence of each repeating unit in parentheses is arbitrary in the formula.

(Wherein R ²⁶ represents a hydrogen atom or an organic group) or a divalent organic group (for example, a hydrogen atom or an organic group) in each occurrence of R ¹⁶ is independently an oxygen atom, phenylene, carbazolylene, -NR ²⁶ - to be. Preferably, R ¹⁶ is an oxygen atom or a bivalent polar group.

The "bivalent polar group" is not particularly limited, and -C (O) -, -C (═NR ²⁷ ) -, and -C (O) NR ²⁷ - (wherein R ²⁷ 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, such as methyl, ethyl or n-propyl, which may be substituted by one or more fluorine atoms.

In the formula, R ¹⁷ in each occurrence is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. 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 trifluoro A methyl group, or a pentafluoroethyl group, more preferably a trifluoromethyl group.

In this form, X ¹ is preferably a group represented by the formula: - (O) _x - (CF ₂ ) _y - (CH ₂ ) _z - wherein x, y and z are as defined above, The order of occurrence of each repeating unit in parentheses is arbitrary in the formula).

Examples of the group represented by the formula: - (O) _x - (CF ₂ ) _y - (CH ₂ ) _z - include - (O) _{x '} - (CH ₂ ) _{z " 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 integers from 1 to 10, z '''' is 0, Or 1). These groups also have a left end bonded 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, Fluoromethyl group.

And each of e is independently 0 or 1.

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

In another aspect, examples of X &^lt; ¹ > groups include the following groups:

[Wherein,

R ⁴¹ each 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;

For each X < ^{1 >} group, any of T may be any of the following groups bonded 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 stands for phenyl), or

[Wherein 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]

Some of the other T's have carbon atoms in the groups opposite to the PFPE of the molecular backbone (that is, in the formulas (A1), (A2), (D1) and (D2) - (CH ₂ ) _{n "} - (n" is an integer of 2 to 6) which is bonded to the Si atom in the _formula (B2), (C1) and (C2) A phenyl group or a C _1-6 alkoxy group.

In this form, X ¹ , X ⁵ , X ⁷ and X ⁹ may each independently be an organic group having from 3 to 10 carbon atoms.

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

In the formula, X ² represents a single bond or a divalent organic group for each occurrence in 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).

Preferred compounds represented by the formulas (A1) and (A2) are represented by the following formulas (A1 ') and (A2'):

[Wherein:

PFPE are each independently represented by the formula:

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -

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 is enclosed in parentheses with suffixes a, b, c, The order of existence of the true repeat units is arbitrary in the formula.)

≪ / RTI >

Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted at each occurrence independently by one or more fluorine atoms;

R ¹ in each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

R ² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;

R ¹¹ in each occurrence independently represents a hydrogen atom or a halogen atom;

R ¹² in each occurrence independently represents a hydrogen atom or a lower alkyl group;

n is an integer of 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;

and t is an integer of 1 to 10.]

≪ / RTI >

A compound represented by the formula (A1) and (A2) are, for example, a polyether derivative perfluoro corresponding to Rf-PFPE- part as a raw material and, after the introduction of iodine at the terminal, -CH ₂ CR ¹² (X ² -SiR ¹ _n R ²³ _-n ) -.

Compounds of formula (B1) and (B2):

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

In the formula, X ⁵ represents, independently of each other, a single bond or an organic group having 2 to 10 carbon atoms. X ⁵ is a compound represented by the general formula (B1) or (B2) wherein a perfluoropolyether moiety (Rf-PFPE moiety or -PFPE moiety), which mainly provides water repellency and surface slip property, (Specifically, -SiR ^& _lt ; ^{1 >} _n R < ² _> _3-n ) Accordingly, the X ⁵ may be any organic group as long as the compound represented by the formula (B1) and (B2) can be stably present.

In the above formula,? Is an integer of 1 to 9 and? 'Is an integer of 1 to 9. These β and β 'are determined according to the valence of X ³ , and in 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, eg, β is 9, β' is 1, β is 5 and β 'is 5 or β is 1 And β 'can be 9. Further, when X < ⁵ > is a divalent organic group, [beta] and [beta] 'are 1. In the formula (B2), β is a value obtained by subtracting 1 from the value of X ⁵ singer.

The above-mentioned X ⁵ is preferably 2 to 7, more preferably 2 to 4, still more preferably a divalent organic group.

In one form, X < ⁵ > is an organic group having 2 to 4 carbon atoms, beta is 1 to 3, and beta 'is 1.

In another form, X < ⁵ > is a divalent organic group, [beta] is 1, and [beta] 'is 1. In this case, the formulas (B1) and (B2) are expressed by the following formulas (B1 ') and (B2').

Examples of the above-mentioned X ⁵ include, but are not particularly limited to, the same as those described for X ¹ .

Among them, preferable specific X < ⁵ >

-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 means phenyl),

-CONH- (CH ₂ ) ₆ -,

_{-CON (CH 3) - (CH} 2) 6 -,

-CON (Ph) - (CH ₂ ) ₆ - (wherein Ph means 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 -,

-OCFHCF ₂ -,

And the like.

Preferred compounds represented by the formulas (B1) and (B2) are represented by the following formulas (B1 ') and (B2'):

[Wherein:

PFPE are each independently represented by the formula:

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -

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 is enclosed in parentheses with suffixes a, b, c, The order of existence of the true repeat units is arbitrary in the formula.)

≪ / RTI >

Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted at each occurrence independently by one or more fluorine atoms;

R ¹ in each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

R ² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;

n is an integer of 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 -

≪ / RTI >

The compounds represented by the above formulas (B1) and (B2) can be produced by a known method, for example, a 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 formula (B1-4) or (B2-4):

[Wherein:

PFPE are each independently represented by the formula:

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -

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 is enclosed in parentheses with suffixes a, b, c, The order of existence of the true repeat units is arbitrary in the formula.)

≪ / RTI >

Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted at each occurrence independently by one or more fluorine atoms;

X ^{5 '} each independently represents a single bond or an organic group of 2 to 10 carbon atoms;

is independently an integer of 1 to 9;

is independently an integer of 1 to 9;

R ⁸² is a single bond or a divalent organic group.]

A compound represented by, HSiM ₃ (wherein, M, are each independently a halogen atom, R ¹ or R ^2, R ¹ is, are each independently hydrogen atom or an alkyl group containing 1 to 22 carbon atoms, in each occurrence, R ² is, by respectively independently a hydroxyl group or a hydrolyzable group), and the reaction in each occurrence, and if necessary converting the halogen atom in R ¹ or R ^2, formula (B1 ") or (B2"):

Wherein PFPE, Rf, X ^{5 '} ,?,?' And R ⁸² are as defined above;

and n is an integer of 0 to 3.]

. ≪ / RTI >

In the formula (B1 ") or (B2"), since _{^{X 5 'R 82 -CH 2 CH}} 2 - the part to correspond to the X ⁵ in the formula (B1) or (B2).

Compounds of formula (C1) and (C2):

In the formulas (C1) and (C2), Rf and PFPE have the same meanings as those in the formulas (A1) and (A2).

In the formula, X ⁷ independently represents a single bond or an organic group having 2 to 10 carbon atoms. X ⁷ is a compound represented by the formulas (C1) and (C2), which comprises a perfluoropolyether moiety (Rf-PFPE moiety or -PFPE moiety) mainly providing water repellency and surface slipperiness, silane binding unit which is provided with the understanding that (specifically, -SiR ^a R ^b _{k l m} R ^c group) linker linking. Accordingly, the X ⁷ can be any organic group as long as the compound represented by the formula (C1) and (C2) can be stably present.

Is an integer of 1 to 9, and? 'Is an integer of 1 to 9. These γ and γ 'are determined according to the valence of X ⁷ , and in 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 y and y 'is 10, for example, y is 9, y' is 1, y is 5 and y ' And γ 'can be 9. When X < ⁷ > is a divalent organic group, [gamma] and [gamma] 'are 1. In the formula (C1), γ is a value obtained by subtracting 1 from the value of X ⁷ singer.

X ⁷ is preferably 2 to 7, more preferably 2 to 4, and most preferably a divalent organic group.

In one form, X ⁷ is a 2- to 4-membered organic group, y is 1 to 3, and y 'is 1.

In another form, X ⁷ is a divalent organic group, y is 1, and y 'is 1. In this case, the expressions (C1) and (C2) are expressed by the following expressions (C1 ') and (C2').

Examples of X ⁷ include, but are not limited to, the same as those described for X ¹ .

Among them, 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 means phenyl),

-CONH- (CH ₂ ) ₆ -,

_{-CON (CH 3) - (CH} 2) 6 -,

-CON (Ph) - (CH ₂ ) ₆ - (wherein Ph means 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 -,

-OCFHCF ₂ -,

And the like.

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

In the formulas, Z represents an oxygen atom or a divalent organic group for each occurrence independently of each other.

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

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 an integer of 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 by, 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 formulas, R ⁷¹ independently represents R ^{a '} in each occurrence. R ^{a '} is the same as R ^a .

In R ^a , ^a maximum of 5 Si atoms connected in a straight chain through the Z group is present. That is, in the R ^a, R ⁷¹ is at least one, if any, the number of Si atoms to exist at least two Si atoms are connected by a straight chain through a group Z in R ^a, coupled to a straight chain through a group such Z is Up to five. In addition, the "number of Si atoms connected in a linear chain through the Z group in R ^a " is equivalent to the number of -Z-Si- connected in a straight chain in R ^a .

For example, in the following, an Si atom is connected through the group Z in R ^a .

In the above formula, * denotes a site bonding to Si of the main chain, and Is that a predetermined group other than ZSi is bonded, that is, all three bonding hands of Si atoms are bonded to each other. , It means the end point of the repetition of ZSi. In addition, the number of the right shoulder of Si means the number of Si connected in a straight line through the sen Z from *. That is, in the chain in which the SiS ² repeats the ZSi repetition, "the number of Si atoms connected in a linear chain through the Z group in R ^a " is 2, and similarly, the repetition of ZSi repeats with Si ³ , Si ^4, and Si ⁵ Quot; the number of Si atoms connected in a linear chain through the Z group in R ^a " is 3, 4 and 5, respectively. As is clear from the above formula, ^a plurality of ZSi chains exist in R ^a , and they do not have to be the same length, but may have arbitrary lengths.

In a preferred form, as shown below, " the number of Si atoms connected in a straight chain through the Z group in R ^a " is one (left formula) or two (right formula) in all the chains .

In one form, the number of Si atoms connected in a straight chain through the Z group in R ^a is one or two, preferably one.

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

The term "hydrolyzable group" as used herein means a group capable of undergoing a hydrolysis reaction. Examples of the hydrolyzable group include -OR, -OCOR, -ON = C (R) ₂ , -N (R) ₂ , -NHR, halogen (wherein R represents a substituted or unsubstituted C1- , And 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; And substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly a non-substituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but hydrolyzable groups may be generated by hydrolysis.

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 represents, independently at each occurrence, 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, still more preferably a methyl group.

Wherein p is, independently at each occurrence, an integer of 0 to 3; q is, independently at each occurrence, an integer of 0 to 3; r is an integer of 0 to 3 independently for each occurrence. Provided that the sum of p, q and r is 3.

In a preferred form, ^(if the R ^{a 'do} not exist, R ^a) R ^a of the of the terminal R ^a according to, wherein q is preferably 2 or more, for example 2 or 3, more preferably Lt; / RTI >

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

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

Wherein R ^b is preferably a group selected from the group consisting of a hydroxyl group, -OR, -OCOR, -ON = C (R) ₂ , -N (R) ₂ , -NHR, halogen (wherein R represents a substituted or unsubstituted An alkyl group having 1 to 4 carbon atoms), and is preferably -OR. R represents an unsubstituted alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; And substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly a non-substituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but hydrolyzable groups may be generated by hydrolysis. More preferably, R ^c is -OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

Wherein R ^c represents, independently at each occurrence, 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, still more preferably a methyl group.

Wherein each occurrence of k in each occurrence is independently an integer of 0 to 3; l is, independently at each occurrence, an integer of 0 to 3; m is an integer of 0 to 3 independently for each occurrence. The sum of k, l and m is 3.

The compounds represented by the above formulas (C1) and (C2) can be obtained by, for example, using a perfluoropolyether derivative corresponding to the Rf-PFPE- portion as a raw material, introducing a hydroxyl group into the terminal, And then reacting the silyl derivative having a halogen atom with a group having an unsaturated bond and introducing a hydroxyl group to the terminal of the silyl group and reacting the silyl derivative with a group having the introduced unsaturated bond. For example, it can be obtained as follows.

Preferred compounds represented by the formulas (C1) and (C2) are represented by the following formulas (C1 ") and (C2"):

[Wherein:

PFPE are each independently represented by the formula:

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -

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 is enclosed in parentheses with suffixes a, b, c, The order of existence of the true repeat units is arbitrary in the formula.)

≪ / RTI >

Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted at each occurrence independently by one or more fluorine atoms;

X ⁷ represents -CH ₂ O (CH ₂ ) ₂ -, -CH ₂ O (CH ₂ ) ₃ - or -CH ₂ O (CH ₂ ) ₆ -;

R ^a in each occurrence independently represents -Z-SiR ⁷¹ _p R ⁷² _q R ⁷³ _r ;

Z represents a C _1-6 alkylene group;

R ⁷¹ in each occurrence independently represents R ^{a '} ;

R ^{a '} is the same as R ^a ;

In R ^a , at most 5 Si atoms are connected in a straight chain through the group Z;

R ⁷² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;

R ⁷³ in each occurrence independently represents a hydrogen atom or a lower alkyl group;

p is, independently at each occurrence, an integer of 0 to 2;

q is an integer of 1 to 3, preferably 3, each independently in each occurrence;

r is, independently at each occurrence, an integer of 0 to 2;

With the proviso that in one R ^a , the sum of p, q and r is 3. [

≪ / RTI >

The compounds represented by the above formulas (C1) and (C2) can be produced, for example, as follows. (C1-4) or (C2-4):

[Wherein:

PFPE are each independently represented by the formula:

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -

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 is enclosed in parentheses with suffixes a, b, c, The order of existence of the true repeat units is arbitrary in the formula.)

≪ / RTI >

Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted at each occurrence independently by one or more fluorine atoms;

X ^{7 '} each independently represents a single bond or an organic group of 2 to 10 carbon atoms;

y is independently an integer of 1 to 9;

y 'are each independently an integer of 1 to 9;

R ⁸² is a single bond or a divalent organic group.]

Of a compound represented by, HSiR ⁸³ _k R ^b _l R ^c _m (formula, R ⁸³ is a chlorine atom as a halogen atom, e.g., fluorine atom, chlorine atom, bromine atom or iodine atom, preferably, R ^b is , And each occurrence of R ^c independently represents a hydrogen atom or a lower alkyl group, k is an integer of 1 to 3, and l and m are each independently a hydrogen atom or a hydrolyzable group at each occurrence, (C1-5) or (C2-5): wherein R < 1 > and R < 2 > are independently an integer of 0 to 2 and the sum of k,

Wherein, Rf, PFPE, R ^82, R ^83, R ^b, R ^c, γ, γ ', X ^7', k, l and m, is the same as significant.]

≪ / RTI >

Hal is a halogen atom (for example, I, Br, Cl, F or the like), Hal-JR ⁸⁴ -CH = CH ₂ , (C1-6) or (C2-6): wherein J is Mg, Cu, Pd or Zn, and R ⁸⁴ is a single bond or a divalent organic group,

Wherein, Rf, PFPE, R ^82, R ^84, R ^b, R ^c, γ, γ ', X ^7', k, l and m, is the same as significant.]

≪ / RTI >

The compound represented by the formula (C1-6) or (C2-6) obtained is represented by HSiM _{3 wherein} M is independently a halogen atom, R ⁷² or R ⁷³ and R ⁷² is a R ⁷³ and R ⁷³ independently represent a hydrogen atom or a lower alkyl group in each occurrence) to convert the halogen atom to R ⁷² or R ⁷³ as necessary, 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, independently at each occurrence, an integer of 1 to 3;

r is independently an integer of 0 to 2 in each occurrence.]

Can be obtained.

In the formula (C1 ''') or (C2'''), the moiety from X ^{7 '} to R ⁸² -CH ₂ CH ₂ - corresponds to X ⁷ in the formula (C1) or (C2) , -R ⁸⁴ -CH ₂ CH ₂ - corresponds to Z in the formula (C1) or (C2).

(D1) and (D2):

Of the formulas (D1) and (D2), Rf and PFPE are the same as those described in the formulas (A1) and (A2).

In the formula, X ⁹ represents, independently of each other, a single bond or an organic group having 2 to 10 carbon atoms. X ⁹ is a compound represented by the general formula (D1) or (D2) and contains a perfluoropolyether moiety (i.e., Rf-PFPE moiety or -PFPE moiety) which mainly provides water repellency and surface slip property , And a linker connecting a moiety (i.e., a group bracketed with &thetas;) providing bonding ability with a substrate. Accordingly, the X ⁹ may be any organic group as long as the compound represented by the formula (D1) or (D2) can be stably present.

In the formula, 隆 is an integer of 1 to 9, and 隆 'is an integer of 1 to 9. The δ and δ ', can be varied depending on the valence of X ^9. In the formula (D1), the sum of δ and δ 'is the same as the valence of X ^9. For example, when X is a 10-valent organic group, the sum of delta and delta is 10, for example, delta is 9 and delta is 1, delta is 5 and delta is 5 or delta is 1 Also, δ 'can be 9. In addition, when X ⁹ is a divalent organic group, 隆 and 隆 'are 1. In the expression (D2), δ is a value obtained by subtracting 1 from the valence of X ^9.

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

In one form, X ⁹ is a 2 to 4-membered organic group, 隆 is 1 to 3, and 隆 'is 1.

In another aspect, X ⁹ is a divalent organic group, 隆 is 1, and 隆 'is 1. In this case, the expressions (D1) and (D2) are expressed by the following expressions (D1 ') and (D2').

Examples of X ⁹ include, but are not limited to, the same as those described for X ¹ .

Among them, preferred specific X < ⁹ >

-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 means phenyl),

-CONH- (CH ₂ ) ₆ -,

_{-CON (CH 3) - (CH} 2) 6 -,

-CON (Ph) - (CH ₂ ) ₆ - (wherein Ph means 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 -,

-OCFHCF ₂ -,

And the like.

In the formula, R ^d represents each independently -Z ² -CR ⁸¹ R ⁸² _{p2 q2 r2} R ⁸³ at each occurrence.

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

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, 1 to 6 And h is an integer of 0 to 6, for example, an integer of 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 by, 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 '} is the same as R ^d .

In R ^d , a maximum of 5 Cs connected in a straight chain through the Z ² group is present. That is, when there is at least one R ⁸¹ in the R ^d , there are two or more Si atoms connected in a straight chain through the Z ² group in R ^d , and the C atoms connected in a straight chain through the Z ² group The maximum number is five. Further, "the number of C atoms that are connected via a straight chain group Z ² of R ^d" means, it is equal to the number of iterations of the -Z ² -C- connected in a straight chain in R ^d. This is similar to the description about R ^a in the formulas (C1) and (C2).

In a preferred form, " the number of C atoms connected in a straight chain through the Z ² group in R ^d " is 1 (left equation) or 2 (right equation) in all chains.

In one form, the number of C atoms connected in a straight chain through the Z ² group in R ^d is one or two, preferably one.

In the formula, R ⁸² represents -Y-SiR ⁸⁵ _{n 2} R ⁸⁶ _{3 -2n} .

Y represents a divalent organic group in each occurrence independently of each other.

In a preferred form, Y represents a C _1-6 alkylene group, - (CH ₂ ) _{g '} -O- (CH ₂ ) _h' - wherein g 'is an integer of 0 to 6, (CH ₂ ) _{i '} -, wherein i' represents an integer of 0 to 6 (preferably 0 to 6), and h 'is an integer of 0 to 6, for example, an integer of 1 to 6) Lt; / RTI > These groups may be substituted by, 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 form, Y can be a C _1-6 alkylene group, -O- (CH ₂ ) _{h '} - or -phenylene- (CH ₂ ) _i' -. When Y is the above-mentioned group, the light resistance, in particular ultraviolet light resistance, can be higher.

R ⁵ represents a hydroxyl group or a hydrolyzable group in each occurrence independently of each other.

The term "hydrolyzable group" as used herein means a group capable of undergoing a hydrolysis reaction. Examples of the hydrolyzable group include -OR, -OCOR, -ON = C (R) ₂ , -N (R) ₂ , -NHR, halogen (wherein R represents a substituted or unsubstituted C1- , And 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; And substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly a non-substituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but hydrolyzable groups may be generated by hydrolysis.

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 in each occurrence independently of each other. 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, 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 still more preferably 2 or 3, for each (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _{3 -n2} ) 3.

Each R ⁸³ 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, still more preferably a methyl group.

Wherein p2 is, independently at each occurrence, an integer of 0 to 3; q2 are each independently an integer of 0 to 3 at each occurrence; r2 is an integer of 0 to 3 independently for each occurrence. However, the sum of p2, q2 and r2 is 3.

In a preferred form, ^(if the R ^{d 'is} not present, R ^d) R ^d of of the terminal R ^d in the q2 is preferably at least 2, e.g. 2 or 3, more preferably Lt; / RTI >

In a preferred form, at least one of the 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 -Y-SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) ₃ . In the formula, the unit of (-Y-SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) is preferably (-Y-SiR ⁸⁵ ₃ ). In a more preferred form, the terminal portion 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 formulas, R ^e independently represents -Y-SiR ⁸⁵ _n2 R ⁸⁶ _{3 -n2} in each occurrence. Here, Y, R ⁸⁵ , R ⁸⁶ and n 2 are as defined in the above R ⁸² .

In the formula, R ^f represents a hydrogen atom or a lower alkyl group for each occurrence independently of each other. 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, still more preferably a methyl group.

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

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

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

In one form, 12 is 2 or 3, preferably 3.

At least one q2 of the formulas (D1) and (D2) is an integer of 1 to 3, or at least one of l is an integer 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 .

At least one of n2 in the formulas (D1) and (D2) is an integer of 1 to 3. That is, there is at least one R ⁸⁵ .

The perfluoro (poly) ether group-containing silane compound represented by the formula (D1) or (D2) can be produced by combining known methods. For example, the compound represented by the formula (D1 ') wherein X is a divalent compound can be produced in the following manner, although not limited thereto.

(Preferably allyl) containing a double bond, and a halogen (preferably an allyl group) are added to a polyhydric alcohol represented by HO-XC (YOH) ₃ (wherein X and Y are each independently a divalent organic group) Hal-XC (YOR-CH = CH ₂ ) _{3 wherein} Hal is a halogen such as Br and R is a divalent organic group such as an alkylene group. To obtain a double bond-containing halide. Subsequently, a perfluoropolyether group-containing alcohol represented by the terminal halogen and R ^PFPE -OH (wherein R ^PFPE is a perfluoropolyether group-containing group) is reacted to obtain R ^PFPE- OXC (YOR-CH = CH ₂ ) ₃ . Subsequently, R ^PFPE- OXC (YOR-CH ₂ -CH ₂ -SiR ⁸⁵ ₃ ) ₃ can be obtained by reacting the terminal -CH═CH ₂ with HSiCl ₃ and an alcohol or HSiR ⁸⁵ ₃ .

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, more preferably 30,000 or less Or less, more preferably 10,000 or less.

The number average molecular weight of the PFPE portion in the perfluoropolyether group-containing silane compound contained in the surface treatment agent used in the present invention is not particularly limited, but is preferably 4,000 to 30,000, more preferably 5,000 to 10,000 Lt; / RTI >

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. Examples of the solvent include, but are not limited to, perfluorohexane, CF ₃ CF ₂ CHCl ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFC ₂ F ₅ , 2,3,4,4,4,5,5,6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Aurora 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, perfluoro benzene, methylpentanoyl Hexafluoroisopropanol, HCF ₂ CF ₂ CH ₂ OH, methyltrifluoromethanesulfonate, 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 an integer of 0 or more and 1000 or less, and the order of existence of each repeating unit in parentheses, , And the sum of m and n is 1 or more), 1,1-dichloro-2,3,3,3-tetra 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- And 1,1,4,4,4-hexafluoro-2-butene. These solvents can be used singly or as a mixture of two or more kinds.

The surface treatment agent used in the present invention may contain other components in addition to the perfluoropolyether group-containing silane compound. Examples of such other components include, but are not limited to, fluoropolyether compounds (non-reactive), preferably perfluoropolyether compounds (hereinafter referred to as " fluorine-containing oils " (Hereinafter referred to as " silicone oil "), a catalyst and the like which can be understood as silicone oil (nonreactive silicone oil).

The fluorine-containing oil is not particularly limited, and examples thereof include compounds represented by the following general formula (3) (perfluoropolyether compounds).

^{_{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 formulas, Rf ¹ represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, Rf ² represents one or more of C _1-16 alkyl group optionally substituted by a fluorine atom (preferably, a C _1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, Rf ¹ and Rf ² are more preferably , Each independently represents a C _1-3 perfluoroalkyl group.

a ', b', c 'and d' each represent the number of four kinds of repeating units of the perfluoropolyether constituting the main skeleton of the polymer and are independently an integer of 0 to 300, ', c' and d 'is at least 1, preferably from 1 to 300, more preferably from 20 to 300. The order of existence of each repeating unit enclosed in parentheses with subscripts a ', b', c ', or d' is arbitrary in the equation. Of these repeating _{units, - (OC 4 F 8)} - _{is, - (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)) - which is, but even during, preferably - (OCF ₂ CF ₂ CF ₂ CF ₂ ) -. - (OC ₃ F ₆₎ - _{is, - (OCF 2 CF 2 CF} 2) -, - (OCF (CF 3) CF 2) - and - and even which _{of, - (OCF 2 CF (CF} 3)) Preferably - (OCF ₂ CF ₂ CF ₂ ) -. - (OC ₂ F ₄ ) - can be any of - (OCF ₂ CF ₂ ) - and - (OCF (CF ₃ )) -, preferably - (OCF ₂ CF ₂ ) -.

Examples of the perfluoropolyether compound represented by the above general formula (3) include compounds (any one or a mixture of two or more) represented by any one of the following general formulas (3a) and (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 )

In these formulas, Rf ¹ and Rf ² are as defined above; In formula (3a), b "is an integer of not less than 1 but not more than 100; in formula (3b), 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 to 300. The order of existence of each repeating unit in parentheses with suffixes "a "," b ", c ", and d "

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

Among the surface treatment agents used in the present invention, the fluorine-containing oil has a total of 100 parts by mass of the perfluoropolyether group-containing silane compounds (in the case of two or more kinds thereof, the total amount thereof, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, and more preferably 5 to 300 parts by mass.

The compound represented by formula (3a) and the compound represented by 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) since a higher surface slip property can be obtained. When these are used in combination, the mass ratio of the compound represented by formula (3a) to the compound represented by formula (3b) is preferably from 1: 1 to 1:30, more preferably from 1: 1 to 1:10 More preferable. According to such a mass ratio, it is possible to obtain a surface treatment layer excellent in balance between surface slip and friction durability.

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

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

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

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

In a preferred form, when the surface treatment layer is formed by the vacuum evaporation 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 having such an average molecular weight, more excellent friction durability and surface slipperiness can be obtained.

From another viewpoint, the fluorine-containing oil may be any compound represented by the general formula Rf ³ -F (wherein Rf ³ is a C _5-16 perfluoroalkyl group). It may also be a chlorotrifluoroethylene oligomer. The compound represented by Rf ³ -F and the chlorotrifluoroethylene oligomer have a high affinity with a compound represented by a fluorine-containing compound having a carbon-carbon unsaturated bond at the molecular end thereof, the terminal being a C _1-16 perfluoroalkyl group Is obtained.

The fluorine-containing oil also 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 straight-chain silicone oil may be a so-called straight silicone oil or a 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 a straight silicone oil with an alkyl, an aralkyl, a polyether, a higher fatty acid ester, a fluoroalkyl, an amino, an epoxy, a carboxyl, an alcohol or the like. The cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil and the like.

Among the surface treatment agents used in the present invention, such a silicone oil is preferably used in an amount of, for example, 0 to 300 parts by weight per 100 parts by weight (in the case of two or more kinds thereof, the total amount thereof) of the perfluoropolyether group- Mass part, preferably 0 to 200 mass parts.

Silicone oil also contributes to improving the surface slip property of the surface treatment layer.

Examples of the catalyst include acids (e.g., acetic acid, trifluoroacetic acid, etc.), bases (e.g., ammonia, triethylamine, diethylamine, etc.), transition metals .

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

The surface treatment layer may be formed, for example, by forming a film of a surface treatment agent containing a fluorine-containing silane compound on the surface of the silicon oxide layer and then post-treating the film as necessary to form a surface treatment layer .

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

Examples of the wet coating method include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating and the like.

Examples of the dry coating method include a PVD method, a CVD method, and a similar method. The PVD method is a method in which a solid raw material is heated (vacuum evaporated) in vacuum or irradiated with high-speed electrons or ions to impart physical energy to atoms of a solid surface to vaporize it and recombine it on a substrate to form a thin film . The PVD method is not particularly limited, and examples thereof include a vapor deposition method (usually a vacuum vapor deposition method) and sputtering. Specific examples of the vapor deposition method (vacuum deposition method in general) include resistance heating, electron beam, high frequency heating using microwave, ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and the like. Among them, the PVD method is preferable, and a vapor deposition method, for example, resistance heating deposition or electron beam deposition is preferable, and electron beam deposition is more preferable. By using the PVD method, a surface treatment layer having higher friction durability can be obtained.

It is also possible to coat by an atmospheric plasma method.

When the wet coating method is used, the surface treatment agent used in the present invention can be applied to the surface of the substrate after being diluted with a solvent. In view 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 perfluoro aliphatic hydrocarbons (for example, perfluorohexane, perfluoromethylcyclo Hexane and perfluoro-1,3-dimethylcyclohexane); Polyfluoroaromatic hydrocarbons (e. G., Bis (trifluoromethyl) benzene); Polyfluoroaliphatic hydrocarbons (for example, C ₆ F ₁₃ CH ₂ CH ₃ (for example, Asahikawa (registered trademark) AC-6000 available from Asahi Glass Co., Ltd.), 1,1,2,2, 3,3,4-heptafluorocyclopentane (for example, Aurora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.), hydrofluorocarbon (HFC) (for example, 1,1,1, (HFC-365mfc); hydrochlorofluorocarbons (e.g., HCFC-225 (Asahikawa.RTM. AK225)); hydrofluoroethers (HFE) , Perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) (for example Novec 7000, manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) ( (For example, Novec 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) (for example, Novec (manufactured by Sumitomo 3M Limited) Trade name) 72 00), perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (for example, Novec (trade name) 7300 manufactured by Sumitomo 3M Limited) Ether (the perfluoroalkyl group and the alkyl group should be linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, Asahikawa (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Butrel (registered trademark) sion of Mitsui-DuPont Fluorochemicals) The mixture may be used alone or as a mixture of two or more kinds. In order to adjust the solubility of the perfluoropolyether group-containing silane compound, for example, it may be mixed with another solvent.

In the case of using the dry coating method, the surface treatment agent used in the present invention may be directly applied to the dry coating method, or may be diluted with the above-mentioned solvent and then applied to the dry coating method.

When the surface treatment agent used in the dry coating method includes 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.

The solvent may be removed by, for example, vacuum distillation.

The temperature at the time of removing the reduced pressure distillation is preferably 0 to 200 占 폚, more preferably 10 to 80 占 폚. The pressure at the time of removing the reduced pressure distillation 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 a PVD treatment is performed using a surface treatment agent containing a solvent, the solvent is first distilled off under reduced pressure using a separate apparatus or the like, and the perfluoropolyether group-containing silane compound (and, if present, Fluorine-containing oil, silicone oil, etc.) may be supplied into the PVD apparatus to perform vacuum deposition.

The film formation is preferably carried out so that the surface treating agent in the film is present together with the catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of the wet coating method, a catalyst may be added to the diluting liquid of the surface treating agent immediately before the surface treating agent is diluted with a solvent and then applied to the surface of the substrate. In the case of the dry coating method, a surface treatment agent added with a catalyst is directly vapor-deposited (usually by vacuum evaporation), or a pellet-like material impregnated with a catalyst-added surface treatment agent is deposited on a porous metal such as iron or copper (Usually, vacuum deposition) treatment may be performed.

For the catalyst, any suitable acid or base may be used. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. As the base catalyst, for example, ammonia, organic amines and the like can be used.

Then, if necessary, the film is post-treated. This post-treatment is not particularly limited, and for example, water supply and dry heating may be sequentially performed, and more specifically, the following treatment may be carried out.

After the film of the surface treatment agent is formed 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 of supplying water is not particularly limited, and for example, a method of dew condensation caused by a temperature difference between a precursor film (and a substrate) and an ambient atmosphere, or spraying steam (steam) may be used.

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

The supply of water can be carried out, for example, in an atmosphere of 0 to 250 ° C, preferably 60 ° C or more, more preferably 100 ° C or more, preferably 180 ° C or less, more preferably 150 ° C or less have. By supplying water in such a temperature range, hydrolysis can proceed. The pressure at this time is not particularly limited, but can be easily set at normal pressure.

Subsequently, the precursor film is heated on the surface of the substrate in a drying atmosphere exceeding 60 캜. The drying and heating method is not particularly limited and the precursor film together with the substrate may be heated at a temperature exceeding 60 캜, preferably exceeding 100 캜, for example, at a temperature of 250 캜 or lower, preferably 180 캜 or lower, It may be disposed under an atmosphere of unsaturated water vapor pressure. The pressure at this time is not particularly limited, but can be easily set at normal pressure.

Under such an atmosphere, groups bonded to Si after hydrolysis are quickly dehydrated and condensed between PFPE-containing silane compounds of the present invention. Also, between the compound and the substrate, the reaction rapidly occurs between a group bonded to Si after hydrolysis of the compound and a reactive group present on the surface of the substrate, and when the reactive group present on the surface of the substrate is a hydroxyl group, dehydration and condensation are performed. As a result, a bond is formed between the perfluoropolyether group-containing silane compound and the substrate.

The moisture supply and the drying heating may be performed continuously by using superheated water vapor.

The superheated steam is a gas obtained by heating saturated steam to a temperature higher than the boiling point. Under superatmospheric pressure, the superheated steam is heated at a temperature exceeding 100 캜, generally not higher than 500 캜, for example, not higher than 300 캜, Is a gas which has become unsaturated steam pressure by the heating of the furnace. In the present invention, from the viewpoint of suppressing decomposition of the perfluoropolyether group-containing silane compound, superheated water vapor of preferably 250 deg. C or lower, preferably 180 deg. C or lower is used for water supply and drying heating. When the substrate on which the precursor film is formed is exposed to superheated water vapor, 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, thereby supplying moisture to the precursor film. Finally, 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 superheated steam, and the moisture content on the surface of the precursor film gradually decreases. While the moisture content of the surface of the precursor film is lowered, that is, while the precursor film is in a dry atmosphere, the surface precursor film of the substrate is heated to a temperature of the superheated water vapor (a temperature exceeding 100 캜 under atmospheric pressure) do. Therefore, when superheated water vapor is used, water supply and dry heating can be continuously performed only by exposing the substrate on which the precursor film is formed to superheated water vapor.

The post-treatment can be carried out as described above. It should be noted that this post-treatment can be carried out to further improve the friction durability, but is not essential in producing the article of the present invention. For example, it is only necessary to apply the surface treatment agent to the surface of the base material and leave it as it is.

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 to produce the article of the present invention. The surface treated layer thus obtained has high friction durability. The surface-treated layer has water repellency, oil repellency, antifouling property (for example, adhesion of contamination such as fingerprints and the like) and waterproofness Etc.), surface slipperiness (or lubricity, for example, wiping of contamination such as fingerprints, excellent touch on fingers), and the like, and can be preferably used as a functional thin film .

The article obtained by the present invention is not particularly limited, but may be an optical member. Examples of the optical member include optical members such as a cathode ray tube (CRT: e.g., a TV, a personal computer monitor), a liquid crystal display, a plasma display, an organic EL display, an inorganic thin film EL dot matrix A display such as a display, a rear projection display, a fluorescent display (VFD), a field emission display (FED) or the like, or a front shield, an antireflection plate, a polarizer, an antiglare plate, Processed; Lenses such as glasses; A touch panel sheet of a device such as a cellular phone, a portable information terminal, and the like; A disc surface of an optical disc such as a Blu-ray (registered trademark) disc, a DVD disc, a CD-R, or an MO; Optical fiber; The display surface of the watch, etc.

The article obtained by the present invention can also be a ceramics product, a drawing, a foaming product, a leather product, a medical product and a plaster

In addition, 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 the optical member, the thickness of the surface treatment layer is preferably 1 to 50 nm, preferably 1 to 30 nm, more preferably 1 to 15 nm in view of optical performance, surface slipperiness, friction durability and antifouling property Do.

The above-described article of the present invention has high friction durability and high acid alkali resistance, and is excellent in water repellency, oil repellency and antifouling property (for example, adhesion of contamination such as fingerprints and the like) (To prevent water from entering into electronic parts or the like), surface slipperiness (or lubricity, for example, wiping of contamination such as fingerprints, or excellent touch on 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 has excellent surface slip property and acid alkali resistance due to this feature. By forming the silicon oxide layer by the CVD method, it is possible to form a silicon oxide layer having a specific Ra, an silicon oxide layer having an amorphous structure, a silicon oxide layer having a specific density, or a silicon oxide layer having a hydrogen concentration in a specific film have.

Thus, in one aspect,

A silicon oxide layer positioned on the substrate,

A surface treatment layer formed on the silicon oxide layer

.

And the surface roughness (Ra: center line average roughness) of the silicon oxide layer is 0.2 nm or less.

In a preferred form, Ra may be 0.15 nm or less.

In another aspect,

A silicon oxide layer positioned on the substrate,

A surface treatment layer formed on the silicon oxide layer

.

And at least a part of the silicon oxide layer is amorphous.

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

In another aspect,

A silicon oxide layer positioned on the substrate,

A surface treatment layer formed on the silicon oxide layer

.

Wherein the silicon oxide layer has a density of 2.25 g / cm < 3 > to 2.60 g / cm < 3 >.

In a preferred form the density of the silicon oxide layer is from 2.30 g / cm3 to 2.50 g / cm3, preferably from 2.35 g / cm3 to 2.45 g / cm3, for example from 2.38 g / cm3 to 2.42 g / Lt; / RTI >

In another aspect,

A silicon oxide layer positioned on the substrate,

A surface treatment layer formed on the silicon oxide layer

.

And the hydrogen concentration in the film of the silicon oxide layer is 1 to 10 at%.

In a preferred form, the hydrogen concentration in the film of the silicon oxide layer may be at least 2 at%, at least 3 at%, at least 4 at%, or at least 5 at%, and may be at most 9 at%, at most 8 at%, at most 7 at%, or at most 6 at%. For example, the hydrogen concentration in the film of the silicon oxide layer may be in the range of 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 to 6 at%, or 2 to 9 at%, 3 to 8 at%, 4 to 7 at%, or 5 to 6 at%.

In another aspect,

A silicon oxide layer positioned on the substrate,

A surface treatment layer formed on the silicon oxide layer

.

And the Si / O composition ratio (molar ratio) in the silicon oxide layer is 0.6 to 1.5.

In a preferred form, the Si / O composition ratio in the silicon oxide layer may be 1.5 or less, preferably 0.5 or more. The Si / O composition ratio may preferably be 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.

Example

The article of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1

· Formation of a silicon oxide layer

As the substrate, a chemically tempered glass ("Gorilla" glass, thickness 0.7 mm, manufactured by Corning) was prepared. The surface of the substrate was washed with a mixed solution of H ₂ SO ₄ / H ₂ O ₂ / H ₂ O (1: 1: 5), and SiH ₄ gas was used as a silicon source and N ₂ O gas was used as an oxygen source , And plasma CVD was performed using a Trias CVD apparatus manufactured by Tokyo Electron to form a silicon oxide (SiO) layer on the surface of the substrate.

(Plasma CVD film forming conditions)

RF power density: 1.0 W / cm < 2 >

Substrate temperature: 200 DEG C

Process pressure: 150 Pa

Material gas flow rate ratio (volume ratio): SiH ₄ : N ₂ O: H ₂ = 1: 30: 100

Film forming speed: 0.7 nm / sec

Processing time: 100 seconds

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

· Preparation of surface treatment materials

A fluorine-containing compound represented by the following formula (average composition) was dissolved in hydrofluoroether (Noveb HFE7200, manufactured by 3M Co., Ltd.) so as to have a concentration of 20 wt% to prepare a surface treatment agent.

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 the value of 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 the vacuum vapor deposition were set to a pressure of 3.0 x 10 < ^-3 > Pa, and 2 mg of the surface treatment agent (i.e., 0.4 mg of the perfluoropolyether group-containing silane compound) was added per one chemically tempered glass (55 mm x 100 mm) Lt; / RTI > Thereafter, the chemically tempered glass with a vapor deposition film was allowed to stand for 24 hours in an atmosphere at a temperature of 20 캜 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 condition was changed. Further, the film thickness of the silicon oxide layer measured by an ellipsometer was 30 nm.

(Plasma CVD film forming conditions)

RF power density: 1.0 W / cm < 2 >

Substrate temperature: 200 DEG 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 / sec

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 treatment time of CVD was changed to 30 seconds. The film thickness of the silicon oxide layer measured by an ellipsometer was 15 nm.

Comparative Example 1

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 silicon oxide layer was formed by a PVD method (electron beam (EB) deposition) instead of the CVD method . Further, the film thickness of the silicon oxide layer measured by the ellipsometer was 70 nm.

(EB deposition condition)

· Pressure: 2 × 10 ^-2 Pa

· Substrate temperature: room temperature (about 25 ℃)

· Material: SiO ₂ crystal

· Deposition 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 treatment time of the PVD method (electron beam (EB) deposition) was changed to 80 seconds. Further, the film thickness of the silicon oxide layer measured by 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 deposition treatment time of the PVD method (electron beam (EB) deposition) was changed to 50 seconds. The film thickness of the silicon oxide layer measured by an ellipsometer was 15 nm.

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

(evaluation)

· Friction durability evaluation

For the surface treatment layers of Examples 1 to 3 and Comparative Examples 1 to 3, the static contact angle of water was measured. The static contact angle of water was measured with a contact angle measuring apparatus (manufactured by Kyowa Chemical Industry Co., Ltd.) with 1 mu L of water.

First, as an initial evaluation, the static contact angle of water was measured (the number of times of friction was 0) in a state where nothing had yet contacted the surface after forming the surface treatment layer.

Thereafter, as a friction durability evaluation, a steel wool friction durability evaluation was carried out. Specifically, the substrate on which the surface treatment layer was formed was placed horizontally, a steel wool (number # 0000, dimension 5 mm x 10 mm x 10 mm) was brought into contact with the exposed top surface of the surface treatment layer, a load of 1,000 gf was applied thereon Thereafter, the steel wool was reciprocated (distance: 120 mm (reciprocating), speed: 60 rpm) while the load was applied. The static contact angle (degree) of water was measured at a constant number of reciprocations. Evaluation was stopped when the measured value of the contact angle became less than 100 degrees. The results are shown in the following table.

Example 4

The same procedures as in Example 3 were carried out except that 0.25 mg of the surface treatment agent (that is, 0.05 mg of the perfluoropolyether group-containing silane compound) was vapor-deposited per one piece of the chemically tempered glass (55 mm x 100 mm) An article having a silicon oxide and a surface treatment layer was obtained. The film thickness of the silicon oxide layer measured by an ellipsometer was 15 nm.

Comparative Example 4

A substrate was prepared in the same manner as in Comparative Example 3 except that 0.25 mg of the surface treatment agent (that is, 0.05 mg of the perfluoropolyether group-containing silane compound) was deposited per one chemical-tempered glass (55 mm x 100 mm) An article having an oxide and a surface treatment layer was obtained. The film thickness of the silicon oxide layer measured by an ellipsometer was 15 nm.

· Cold resistance test (acid, alkali durability test)

The surface treatment layers of Example 4 and Comparative Example 4 were evaluated for durability against artificial perspiration.

Specifically, about 50 μL of artificial sweat having a pH of 8.7 and a pH of 4.5 having the following composition was allowed to stand on the surfaces of the articles obtained in Example 4 and Comparative Example 4, and under the conditions of heating and humidifying at 60 ° C. and 90 RH% . Thereafter, the artificial sweat on the surface was wiped off and the surface was rinsed with distilled water and ethanol, and then the static contact angle (degree) of water was measured. The results are shown in the following table.

· Composition of artificial sweat at pH 8.7

Pure water is added to 10 g of NaCl, 2.5 g of Na ₂ HPO ₄ .12H ₂ O and ₄ g of (NH ₄ ) ₂ CO ₃ to make a total of 1000 ml.

Composition of artificial sweat at pH 4.5

Pure water is added to 10 g of NaCl, 2.5 g of Na ₂ HPO ₄ .12H ₂ O and ₁ g of CH ₃ CH (OH) COOH to make a total of 1000 ml.

From the results shown in Tables 2 and 3, Examples 1 to 3, in which the silicon oxide layer was formed by the CVD method, were more excellent in friction durability than Comparative Examples 1 to 3 using the PVD method, 4, and excellent in acid and alkali durability. That is, it has been confirmed that 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 more excellent friction durability and further superior resistance to acid and alkali.

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

Claims (24)

A substrate,
A silicon oxide layer positioned on the substrate,
A surface treatment layer formed on the silicon oxide layer
A method for producing an article,
Forming a silicon oxide layer using a chemical vapor deposition method, and
And a surface treatment layer is formed by using a surface treatment agent containing a fluorine-containing silane compound on the obtained silicon oxide layer
≪ / RTI > The production method according to claim 1, wherein the chemical vapor deposition method is performed using a reaction gas containing silane or disilane. The manufacturing method according to claim 1 or 2, wherein the silicon oxide layer has a thickness of 5 to 100 nm. The production 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 production method according to any one of claims 1 to 4, comprising ion cleaning the surface of the silicon oxide layer after formation of the silicon oxide layer and before formation of the surface treatment layer. The method according to any one of claims 1 to 5, wherein the surface treatment layer is formed using a physical vapor deposition method. The fluorine-containing silane compound according to any one of claims 1 to 6, wherein the fluorine-containing silane compound is a compound represented by any of the following formulas (A1), (A2), (B1), (B2), (C1) And (D2):

[Wherein:
PFPE is, independently at each occurrence,
- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -
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 is enclosed in parentheses with suffixes a, b, c, The order of existence of the true repeat units is arbitrary in the formula.)
≪ / RTI >
Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted at each occurrence independently by one or more fluorine atoms;
R ¹ in each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
R ² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;
R ¹¹ in each occurrence independently represents a hydrogen atom or a halogen atom;
R ¹² in each occurrence independently represents a hydrogen atom or a lower alkyl group;
n is independently an integer of 0 to 3 for each (-SiR ¹ _n R ² _{3 -n} ) unit;
Provided that at least one R < ² > is present in the formulas (A1), (A2), (B1) and (B2);
X ¹ each independently represents a single bond or an organic group having 2 to 10 carbon atoms;
X ² represents, at each occurrence, each independently a single bond or a divalent organic group;
t is, independently at each occurrence, an integer of 1 to 10;
a is independently an integer of 1 to 9;
? 'are each independently an integer of 1 to 9;
X ⁵ are each independently a single bond or a divalent to 10 represents an organic group;
is independently an integer of 1 to 9;
is independently an integer of 1 to 9;
X ⁷ each independently represent a single bond or an organic group having 2 to 10 carbon atoms;
y is independently an integer of 1 to 9;
y 'are each independently an integer of 1 to 9;
R ^a in each occurrence independently represents -Z-SiR ⁷¹ _p R ⁷² _q R ⁷³ _r ;
Z represents, at each occurrence, each independently an oxygen atom or a divalent organic group;
R ⁷¹ in each occurrence independently represents R ^{a '} ;
R ^{a '} is the same as R ^a ;
In R ^a , at most 5 Si atoms are connected in a straight chain through the group Z;
R ⁷² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;
R ⁷³ in each occurrence independently represents a hydrogen atom or a lower alkyl group;
p is, independently at each occurrence, an integer of 0 to 3;
q is, independently at each occurrence, an integer of 0 to 3;
r is, independently at each occurrence, an integer of 0 to 3;
With the proviso that the sum of p, q and r is 3 for each of -Z-SiR ⁷¹ _p R ⁷² _q R ⁷³ _r , and at least one R ⁷² is present in formulas (C1) and (C2);
R ^b in each occurrence independently represents a hydroxyl group or a hydrolyzable group;
R ^c represents, at each occurrence, each independently a hydrogen atom or a lower alkyl group;
k is, independently at each occurrence, an integer of 1 to 3;
l is, independently at each occurrence, an integer of 0 to 2;
m is, independently at each occurrence, an integer of 0 to 2;
However, in the unit in which? Is attached and parenthesized, the sum of k, l, and m is 3;
X ⁹ each independently represent a single bond or an organic group of 2 to 10 carbon atoms;
? are each independently an integer of 1 to 9;
? 'are each independently an integer of 1 to 9;
R ^d are each independently -Z ² -CR ⁸¹ R ⁸² _{p2 q2} R ⁸³ represents an _r2 at each occurrence;
Z ² represents, at each occurrence, each independently an oxygen atom or a divalent organic group;
R ⁸¹ independently represents R ^{d '} at each occurrence;
R ^{d '} is the same as R ^d ;
Of R ^d , there are at most 5 C connected in a straight chain through the group Z ² ;
R ⁸² in each occurrence independently represents -Y-SiR ⁸⁵ _{n 2} R ⁸⁶ _{3 -n 2} ;
Y represents, at each occurrence, each independently a divalent organic group;
R ⁸⁵ in each occurrence independently represents a hydroxyl group or a hydrolyzable group;
R ⁸⁶ in each occurrence independently represents a hydrogen atom or a lower alkyl group;
n2 _{^{is, (-Y-SiR 85 n2 R}} 86 3 -n2) units each independently represents an integer of 0 to 3;
R ⁸³ in each occurrence independently represents a hydrogen atom or a lower alkyl group;
p2 is, independently at each occurrence, an integer of 0 to 3;
q2 are each independently an integer of 0 to 3 at each occurrence;
r2 is, independently at each occurrence, an integer of 0 to 3;
R ^e in each occurrence independently represents -Y-SiR ⁸⁵ _n2 R ⁸⁶ _{3 -n 2} ;
R ^f represents, at each occurrence, each independently a hydrogen atom or a lower alkyl group;
k2 are each independently an integer of 0 to 3 at each occurrence;
l2 is, independently at each occurrence, an integer of 0 to 3;
m2 are each independently an integer of 0 to 3 at each occurrence;
Provided that at least one R ⁸⁵ is present in the formulas (D1) and (D2)].
Lt; RTI ID = 0.0 > 1, < / RTI > 8. The compound according to claim 7, wherein PFPE is a compound represented by the following formulas (a) to (c):
_{(a) - (OC 3 F} 6) b -
Wherein, 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 -
A and b each independently represents 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 the sum of a, b, c, And the order of existence of each repeating unit in parentheses with suffixes a, b, c, or d is arbitrary in the formula.]
(c) - (OC ₂ F ₄ -R ¹⁵ ) _{n "} -
[In the formula (c), R ¹⁵ are each independently a group selected from _{OC 2 F 4, OC 3 F} 6 and OC ₄ F _8, n "is an integer of 2 or more to 100 or less.]
. ≪ / RTI > The method according to claim 7 or 8, wherein in the 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 ,
OC ₂ F ₄ is OCF ₂ CF ₂
≪ / RTI > 10. The method according to any one of claims 1 to 9, wherein the surface treating agent further contains one or more other components selected from a fluorine-containing oil, a silicone oil, and a catalyst. 11. The method according to claim 10, wherein 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)
[Wherein:
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, a fluorine atom or a hydrogen atom of 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
a ', b', c 'and d' each represent the number of four kinds of repeating units of the perfluoropolyether constituting the main skeleton of the polymer and are independently an integer of 0 to 300, ', c', and d 'are at least 1, and the order of existence of each repeating unit in parentheses with suffixes a', b ', c', or d 'is arbitrary in the formula.
≪ / RTI > or a pharmaceutically acceptable salt thereof. 12. The method according to claim 10 or 11, wherein the fluorine-containing oil is a compound represented by 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 )
[Wherein:
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, a fluorine atom or a hydrogen atom of 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
In the formula (3a), b "is an integer of 1 or more and 100 or less;
In formula (3b), a "and b" are each independently an integer of 0 or more and 30 or less, c "and d" are independently integers of 1 or more and 300 or less;
The order of existence of each repeating unit enclosed in parentheses with suffixes "a", "b", c "or d" is optional in the formula.]
Lt; RTI ID = 0.0 > 1, < / RTI > 13. The method according to any one of claims 1 to 12,
Forming a silicon oxide layer on a substrate by chemical vapor deposition; and
A surface treatment layer is formed by using a surface treatment agent containing a fluorine-containing silane compound on a silicon oxide layer
≪ / RTI > The method of claim 13, wherein the chemical vapor deposition is a silicon source SiH _4, Si ₂ H _6, using a silane in silane or tetra the tree, and as an oxygen source manufacture, characterized in that is carried out by using an oxygen gas, Way. 15. The method according to claim 13 or 14, wherein before the silicon oxide layer is formed, the substrate surface is pretreated with an oxidant solution cleaning or an alcohol cleaning. The method according to any one of claims 13 to 15, further comprising pretreating the silicon oxide layer by ion cleaning before forming the surface treatment layer. 17. The method according to claim 16, wherein the ion cleaning is oxygen ion cleaning or argon ion cleaning. 18. The method according to any one of claims 1 to 17, wherein the substrate is a glass substrate. 19. The method according to any one of claims 1 to 18, wherein the article is an optical member. An article obtained by the production method according to any one of claims 1 to 19. And
A silicon oxide layer positioned on the substrate,
A surface treatment layer formed on the silicon oxide layer
.
Wherein at least a part of the silicon oxide layer is amorphous. And
A silicon oxide layer positioned on the substrate,
A surface treatment layer formed on the silicon oxide layer
.
Wherein the silicon oxide layer has a density of 2.25 g / cm3 to 2.60 g / cm3. And
A silicon oxide layer positioned on the substrate,
A surface treatment layer formed on the silicon oxide layer
.
Wherein the hydrogen concentration in the film of the silicon oxide layer is 1 to 10 at%. And
A silicon oxide layer positioned on the substrate,
A surface treatment layer formed on the silicon oxide layer
.
Wherein the molar ratio of the Si / O composition in the silicon oxide layer is from 0.6 to 1.5.