Patent Description:
Certain types of fluorine-containing silane compounds are known to be capable of providing excellent water-repellency, oil-repellency, antifouling properties, and the like when used in surface treatment of a substrate. A layer obtained from a surface-treating agent containing a fluorine-containing silane compound (hereinafter, also referred to as a "surface-treating layer") is applied as a so-called functional thin film to a large variety of substrates such as glass, plastics, fibers, sanitary articles, and building materials (<CIT> and <CIT>).

<CIT> discloses a composite article comprising a substrate and, on at least one face thereof, a multilayered coating comprising in this order (i) an abrasion-resistant layer having an index of refraction of > <NUM> and comprising inorganic oxide nanoparticles and a polymer binder; and (ii) an antireflection layer having an index of refraction of < <NUM> and comprising a fluorosilane polymer containing a perfluoropolyether group.

<CIT> relates to a method of depositing an anti-soiling composition on an antireflective substrate, wherein the anti-soiling composition is a specified fluorosilane polymer containing a perfluoropolyether group.

US-A_2006/<NUM> describes a low refractive index composition for antireflection coatings of an optical display component, which composition comprises the reaction product of (i) a reactive fluoropolymer, (ii) at least one amino organosilane ester coupling agent and (iii) a crosslinker which may be, among others, a perfluoropolyether multi-acrylate crosslinker.

<CIT> (<CIT>) relates to a compound suitable as antifouling agent, the compound being an isocyanuric acid derivative having a substituent which is a monovalent organic group containing a (per)fluoropolyether chain.

<CIT> (<CIT>) discloses an article comprising, in this order, (i) a zirconium oxide base material, (ii) an intermediate layer comprising one or more metal oxides and (iii) a layer formed from a surface treating agent comprising a fluorine-containing silane compound which preferably is a specified perfluoropolyether chain-containing compound.

<CIT> (<CIT>) addresses a water repellant alkali glass plate having a first coating layer comprising a silicon oxide hydroxide and a second coating layer comprising an organic fluoroalkyl- and silicon-containing compound.

The fluorine-containing silane compound described in <CIT> or <CIT>can provide a surface-treating layer having an excellent function, but a surface-treating layer having higher friction durability and chemical resistance is required.

An object of the present disclosure is to provide an article having a surface-treating layer having higher friction durability and chemical resistance.

The present provides an article (also referred to as "the present article" hereinafter) comprising:.

wherein, each independently at each occurrence,.

Also, the present invention provides a method (also referred to as "the present method" hereinafter) for producing an article comprising a substrate and, formed thereon, a surface-treating layer formed from a surface-treating agent containing at least one fluorine-containing silane compound of formula (<NUM>) or (<NUM>) as defined above, comprising:.

Yet further, the present invention provides the use (also referred to as ,"the present use" hereinafter) of a surface-treating agent containing at least one fluorine-containing silane compound of formula (<NUM>) or (<NUM>) as defined above for producing the above defined article.

According to the present invention, it is possible to provide an article having a surface-treating layer having better friction durability and chemical resistance.

The substrate usable in the present invention may be composed of any suitable material, for example, glass, resin (which may be natural or synthetic resin such as a commonly used plastic material), metal, ceramics, semiconductors (such as silicon and germanium), fiber (such as woven fabric and nonwoven fabric), fur, leather, wood, pottery, stone, building materials, and sanitary articles.

For example, when the article to be produced is an optical member, the material constituting the surface of the substrate may be a material for an optical member, such as glass or a transparent plastic. When the article to be produced is an optical member, some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (the outermost layer) of the substrate. The antireflection layer may be any of a single-layer antireflection layer and a multi-layer antireflection layer. Examples of inorganic substances usable in the antireflection layer include SiO<NUM>, SiO, ZrO<NUM>, TiO<NUM>, TiO, Ti<NUM>O<NUM>, Ti<NUM>O<NUM>, Al<NUM>O<NUM>, Ta<NUM>O<NUM>, Ta<NUM>O<NUM>, Nb<NUM>O<NUM>, HfO<NUM>, Si<NUM>N<NUM>, CeO<NUM>, MgO, Y<NUM>O<NUM>, SnO<NUM>, MgF<NUM>, and WO<NUM>. One of these inorganic substances may be used singly, or two or more may be used in combination (e.g., as a mixture). In the case of a multi-layer antireflection layer, SiO<NUM> and/or SiO is preferably used in the outermost layer thereof. When the article to be produced is an optical glass component for a touch panel, a part of the surface of the substrate (glass) may have a transparent electrode such as a thin film in which indium tin oxide (ITO) or indium zinc oxide is used. The substrate, according to its specific configuration, may have, for example, an insulating layer, an adhesive layer, a protecting layer, a decorated frame layer (I-CON), an atomizing film layer, a hard coating layer, a polarizing film, a phase difference film, or a liquid crystal display module.

The shape of the substrate is not limited, and may be, for example, in the form of a plate or a film. The surface region of the substrate on which a surface-treating layer is to be formed is at least a part of the substrate surface, and may be suitably determined according to the application and specific specifications of an article to be produced.

In one embodiment, the substrate, or at least the surface portion thereof, may be composed of a material originally having a hydroxyl group. Examples of the material include glass as well as metal (in particular, base metal) wherein a natural oxidized film or a thermal oxidized film is formed on the surface, ceramics, and semiconductors. Alternatively, when the substrate has an insufficient amount of a hydroxyl group or when the substrate originally does not have a hydroxyl group as in resin, a pre-treatment may be performed on the substrate to thereby introduce or increase a hydroxyl group on the surface of the substrate. Examples of such a pre-treatment include a plasma treatment (e.g., corona discharge) and ion beam irradiation. The plasma treatment can be suitably utilized to not only introduce or increase a hydroxyl group on the substrate surface, but also clean the substrate surface (e.g. remove foreign matter). Another example of the pre-treatment includes a method wherein a monolayer of a surface adsorbent having a carbon-carbon unsaturated bonding group is formed on the substrate surface by a LB method (a Langmuir-Blodgett method), or a chemical adsorption method beforehand, and thereafter cleaving the unsaturated bond under an atmosphere containing e.g. oxygen or nitrogen.

In another embodiment, the substrate may be that of which at least the surface consists of a material comprising other reactive group such as a silicone compound having one or more Si-H group or alkoxysilane.

In a preferable embodiment, the substrate is glass. The glass is preferably sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, or quartz glass, particularly preferably chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.

The intermediate layer is located on the substrate.

The intermediate layer may be formed so as to be in contact with the substrate, or may be formed on the substrate via another layer. In a preferable embodiment, the intermediate layer is formed so as to be in contact with the substrate.

The intermediate layer contains a composite oxide of Si and another metal, the other metal being Ta or Nb.

Here, the composite oxide includes not only a material in which oxides of a plurality of elements including Si constitute a homogeneous phase, a so-called solid solution, but also a material in which oxides of a plurality of elements constitute a heterogeneous phase, and a material in which oxides of a plurality of elements are mixed. For example, the composite oxide may include those having different oxidation states, such as SiOx (x = <NUM> to <NUM>) and MyOz (y = <NUM>-<NUM>, z = <NUM>-<NUM>). Further, the concentration of other metals may vary along the thickness direction of the intermediate layer, for example, may have a concentration gradient along the thickness direction of the intermediate layer, or may vary stepwise. Preferably, the composite oxide is constituted of a solid solution constituting a homogeneous phase.

In a further preferable embodiment, the other metal is Ta.

In one embodiment, the molar ratio of Si to the other metal is (<NUM>:<NUM>)-(<NUM>:<NUM>) (Si:other metal), preferably (<NUM>:<NUM>)-(<NUM>:<NUM>), more preferably (<NUM>:<NUM>)-(<NUM>:<NUM>), still more preferably (<NUM>:<NUM>)-(<NUM>:<NUM>), particularly preferably (<NUM>:<NUM>)-(<NUM>:<NUM>), and for example, may be (<NUM>:<NUM>)-(<NUM>:<NUM>), (<NUM>:<NUM>)-(<NUM>:<NUM>), or (<NUM>:<NUM>)-(<NUM>:<NUM>). When the molar ratio of Si to the other metal is in such a range, the durability of the surface-treating layer is improved. When the molar ratio of Si to the other metal varies depending on the depth, the molar ratio of Si to the other metal in the intermediate layer may be an average value thereof.

In one embodiment, the compositional features of the intermediate layer at the region of <NUM>-<NUM>, preferably <NUM>-<NUM>, more preferably <NUM>-<NUM>, and further preferably <NUM>-<NUM> from the outermost surface close to the surface-treating layer satisfy the molar ratio mentioned above. By setting the compositional features of the intermediate layer within the range of the molar ratio, the friction durability and the chemical resistance can be more reliably improved.

In the above embodiment, the compositional features from the outermost surface to a predetermined depth may be an average value of the concentrations from the outermost surface to a predetermined depth. For example, the average value of the compositional features from the outermost surface to <NUM>, <NUM> or <NUM> may be the average value of the compositional features measured every predetermined time and sputtered at a constant rate for a predetermined time. For example, the compositional features of the intermediate layer may be an average value of concentrations at the depths of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> and <NUM> from the outermost surface. For example, the compositional features of the intermediate layer at the region of <NUM>-<NUM> from the outermost surface may be an average value of concentrations at the depths of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> and <NUM> from the outermost surface, and the compositional features of the intermediate layer at the region of <NUM>-<NUM> from the outermost surface may be an average value of concentrations at the depths of <NUM>, <NUM>, <NUM>, <NUM> and <NUM> from the outermost surface.

The thickness of the intermediate layer is not limited, but may be, for example, <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM>. By setting the thickness of the intermediate layer to be <NUM> or more, the effect of improving the friction durability and chemical resistance of the surface-treating layer can be more reliably obtained. Further, by setting the thickness of the intermediate layer to be <NUM> or less, the transparency of the article can be further increased.

The method for forming the intermediate layer is not limited, but a method capable of simultaneously depositing Si and another metal is preferable, and for example, sputtering, ion beam assist, vacuum deposition (preferably an electron beam heating method), CVD (chemical vapor deposition), or atomic layer deposition can be used, and sputtering is preferably used.

A DC (direct current) sputtering method, an AC (alternating current) sputtering method, an RF (high frequency) sputtering method, or an RAS (radical assist) sputtering method can be used as the sputtering method. These sputtering methods may be either a two pole sputtering method or a magnetron sputtering method.

As a silicon target in sputtering, a target containing silicon (Si) or silicon oxide as a main component is used. It is desirable that a target containing silicon (Si) as a main component has a certain degree of conductivity so as to enable DC sputtering. Therefore, as the target containing silicon (Si) as a main component, it is preferable to use a target made of polycrystalline silicon or a target obtained by doping single crystal silicon with a known dopant such as phosphorus (P) or boron (B) within a range that does not impair the characteristics of the present invention. Such a target made of polycrystalline silicon and a target obtained by doping single crystal silicon with e.g. phosphorus (P) or boron (B) can be used in any of DC sputtering, AC sputtering, RF sputtering, and RAS sputtering.

When a film is formed by a sputtering method, a glass substrate is placed in a chamber containing a mixed gas atmosphere of an inert gas and an oxygen gas, and a target is selected as an adhesion layer forming material so as to have a desired compositional features to form a film. At this time, the kind of the inert gas in the chamber is not particularly limited, and various inert gases such as argon and helium can be used.

Although the pressure in the chamber by the mixed gas of the inert gas and the oxygen gas is not limited, it is easy to set the surface roughness of the film to a preferable range by setting the pressure in the chamber to <NUM> Pa or less. This is considered to be due to the following reasons. That is, when the pressure in the chamber by the mixed gas of the inert gas and the oxygen gas is <NUM> Pa or less, the average free path of the film formation molecules is secured, and the film formation molecules reach the substrate with more energy. Therefore, it is considered that the rearrangement of the film formation molecules is promoted and a film having a relatively dense and smooth surface is formed. The lower limit value of the pressure in the chamber by the mixed gas of the inert gas and the oxygen gas is not limited, but is preferably <NUM> Pa or more, for example.

When the high refractive index layer and the low refractive index layer are formed by the sputtering method, the layer thickness and compositional features of each layer can be adjusted by, for example, adjusting the discharge power, adjusting the film formation time, adjusting the ratio of the mixed gas of the inert gas and the oxygen gas, or the like.

By providing the intermediate layer, the durability of the surface-treating layer can be improved. The term "durability" refers to alkali resistance, hydrolysis resistance, and abrasion resistance.

From the viewpoint of both alkali resistance and abrasion resistance, the molar ratio of Si to the other metal is (<NUM>:<NUM>)-(<NUM>:<NUM>) (Si:other metal), preferably (<NUM>:<NUM>)-(<NUM>:<NUM>), more preferably (<NUM>:<NUM>)-(<NUM>:<NUM>), still more preferably (<NUM>:<NUM>)-(<NUM>:<NUM>), particularly preferably (<NUM>:<NUM>)-(<NUM>:<NUM>), and for example, may be (<NUM>:<NUM>)-(<NUM>:<NUM>), (<NUM>:<NUM>)-(<NUM>:<NUM>), or (<NUM>:<NUM>)-(<NUM>:<NUM>). When the molar ratio of Si to the other metal is in such a range, the alkali resistance and the friction durability of the surface-treating layer is improved.

The compositional features and ratio of the intermediate layer can be determined by the following surface analysis. X-ray photoelectron spectroscopy or time-of-flight secondary ion mass spectrometry can be used as the surface analysis method.

As an apparatus for performing X-ray photoelectron spectroscopy for measuring the compositional features and ratio of the intermediate layer, XPS, PHI <NUM> VersaProbe II manufactured by ULVAC-PHI, Inc. can be used. The measurement conditions of the XPS can be as follows: the X-ray source is <NUM> W monochromatic AlKα radiation; the photoelectron detection surface is <NUM> × <NUM>; the photoelectron detection angle is in the range of <NUM>-<NUM>° (for example, <NUM>°, <NUM>°, <NUM>°); the pass energy is <NUM> eV; and Ar ions are used as sputtering ions. The compositional features of the laminate can be determined by observing the peak areas of C1s, O1s, F1s, and Si2p orbitals, and the appropriate orbital of other metals under the above-described apparatus and measurement conditions and calculating the atomic ratio of carbon, oxygen, fluorine, silicon, and other metals. Examples of suitable orbits of the other metals include <NUM> orbits for atomic number <NUM> (B), 2p orbits for atomic numbers <NUM>, <NUM> and <NUM>-<NUM> (Al to Si and Sc to Ga), 3d orbits for atomic numbers <NUM>, <NUM> and <NUM>-<NUM> (Ge to As and Y to Te), and 4f orbits for atomic numbers <NUM>-<NUM> (Hf to Bi).

It is also possible to analyze the intermediate layer in the depth direction. The measurement conditions of the XPS can be as follows: the X-ray source is <NUM> W monochromatic AlKα radiation; the photoelectron detection surface is <NUM> × <NUM>; the photoelectron detection angle is in the range of <NUM>-<NUM>° (for example, <NUM>°, <NUM>°, <NUM>°); the pass energy is <NUM> eV; and Ar ions are used as sputtering ions. The surface layer of the laminate is etched by sputtering with Ar ions to a thickness of <NUM>-<NUM> in terms of SiO<NUM>, and the peak areas of O1s and Si2p orbitals, and appropriate orbitals of other metals are observed at the respective etched depths, and the atomic ratios of oxygen, silicon, and other metals are calculated, whereby the compositional features of the interior of the laminate can be determined. Examples of suitable orbits of the other metals include <NUM> orbits for atomic number <NUM> (B), 2p orbits for atomic numbers <NUM>, <NUM> and <NUM>-<NUM> (Al to Si and Sc to Ga), 3d orbits for atomic numbers <NUM>, <NUM> and <NUM>-<NUM> (Ge to As and Y to Te), and 4f orbits for atomic numbers <NUM>-<NUM> (Hf to Bi).

By adjusting the photoelectron detection angle of the XPS analysis, the detection depth can be appropriately adjusted. For example, a shallow angle close to <NUM>° allows a detection depth of about <NUM>, while a deep angle close to <NUM>° allows a detection depth of about <NUM>.

In the composition analysis by XPS analysis, when e.g. Si of the substrate is detected, the compositional features of the intermediate layer can be calculated by calculating the amount of Si of the detected substrate from the detected amount of a specific atom in the substrate, for example, a metal atom (for example, Al, Na, K, B, Ca, Mg, or Sn) contained in a trace amount when the substrate is glass, and subtracting the calculated amount from the measurement result.

The surface-treating layer is located directly on the intermediate layer. That is, the surface-treating layer is formed so as to be in contact with the intermediate layer.

The surface-treating layer can be formed from a surface-treating agent containing a fluorine-containing silane compound.

The fluorine-containing silane compound is at least one fluoropolyether group-containing compound of formula (<NUM>) or (<NUM>):.

The term "monovalent organic group", as used herein, represents a monovalent group containing carbon. The monovalent organic group is not limited, and may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group represents a group having one or more of e.g. N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, and carbonyloxy at the terminal of the hydrocarbon group or in the molecular chain thereof.

As used herein, the "divalent organic group" is not limited, and examples thereof include a divalent group where one hydrogen atom is further removed from a hydrocarbon group.

The "hydrocarbon group", as used herein, represents a group which contains carbon and hydrogen and which is obtained by removing one hydrogen atom from a molecule. The hydrocarbon group is not limited, and examples thereof include a C<NUM>-<NUM>-hydrocarbon group, optionally substituted with one or more substituents, such as an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The "aliphatic hydrocarbon group" may be either straight, branched, or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may have one or more of e.g. N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, and carbonyloxy at the terminal or in the molecular chain thereof.

The substituent of the "hydrocarbon group", as used herein, is not limited, and examples thereof include one or more groups selected from halogen, and C<NUM>-<NUM>-alkyl, C<NUM>-<NUM>-alkenyl, C<NUM>-<NUM>-alkynyl, C<NUM>-<NUM>-cycloalkyl, unsaturated C<NUM>-<NUM>-cycloalkyl, a5- to <NUM>-membered heterocyclyl, <NUM>- to <NUM>-membered unsaturated heterocyclyl, C<NUM>-<NUM>-aryl, and <NUM>- to <NUM>-membered heteroaryl each optionally substituted with one or more halogen atoms.

The alkyl group and the phenyl group may be herein unsubstituted or substituted, unless particularly noted. Each substituent of such groups is not limited, and examples thereof include one or more groups selected from halogen, C<NUM>-<NUM>-alkyl, C<NUM>-<NUM>-alkenyl and C<NUM>-<NUM>-alkynyl.

The term "hydrolyzable group", as used herein, represents a group which is able to undergo a hydrolysis reaction, i.e., represents a group that can be removed from the main backbone of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include -ORh, -OCORh, - O-N=CRh<NUM>, -NRh<NUM>, -NHRh and halogen (in these formulae, Rh represents a substituted or unsubstituted C<NUM>-<NUM>-alkyl).

In formula (<NUM>), RF1 each independently is Rf<NUM>-RF-Oq-, and in formula (<NUM>), RF2 is -Rf<NUM>p-RF-Oq-.

Rf<NUM> each independently is is C<NUM>-<NUM>-alkyl group optionally substituted with one or more F.

In the C<NUM>-<NUM>-alkyl group optionally substituted with one or more F, the "C<NUM>-<NUM>-alkyl " may be straight or branched, and is preferably straight or branched C<NUM>-<NUM>-alkyl, in particular C<NUM>-<NUM>-alkyl, more preferably straight C<NUM>-<NUM>-alkyl, and in particular C<NUM>-<NUM>-alkyl.

Rf1 is preferably C<NUM>-<NUM>-alkyl group that is substituted with one or more F, more preferably CF<NUM>H-(C<NUM>-<NUM>-perfluoroalkylene), and further preferably C<NUM>-<NUM>-perfluoroalkyl.

The C<NUM>-<NUM>-perfluoroalkyl group may be straight or branched, and is preferably a straight or branched C<NUM>-<NUM>-perfluoroalkyl, in particular C<NUM>-<NUM>-perfluoroalkyl, more preferably straight C<NUM>-<NUM>-perfluoroalkyl, in particular C<NUM>-<NUM>-perfluoroalkyl, and specifically -CF<NUM>, -CF<NUM>CF<NUM>, or - CF<NUM>CF<NUM>CF<NUM>.

Rf<NUM> is C<NUM>-<NUM>-alkylene optionally substituted with one or more F.

In the C<NUM>-<NUM>-alkylene group optionally substituted with one or more F, the "C<NUM>-<NUM>-alkylene " may be straight or branched, and is preferably straight or branched C<NUM>-<NUM>-alkylene, and more preferably straight C<NUM>-<NUM>-alkylene.

Rf2 is preferably a C<NUM>-<NUM>-alkylene substituted with one or more F, more preferably C<NUM>-<NUM>-perfluoroalkylene, and still more preferably C<NUM>-<NUM>-perfluoroalkylene.

The C<NUM>-<NUM>-perfluoroalkylene group may be straight or branched, and is preferably straight or branched C<NUM>-<NUM>-perfluoroalkylene, more preferably straight C<NUM>-<NUM>-perfluoroalkylene, and specifically -CF<NUM>-, -CF<NUM>CF<NUM>-, or - CF<NUM>CF<NUM>CF<NUM>-.

p is <NUM> or <NUM>. In one embodiment, p is <NUM>. In another embodiment, p is <NUM>.

q each independently is <NUM> or <NUM>. In one embodiment, q is <NUM>. In another embodiment, q is <NUM>.

In RF1 and RF2, RF each independently is a divalent fluoropolyether group.

RF is preferably a group of the formula:.

-(OC<NUM>F<NUM>)a-(OC<NUM>F<NUM>)b-(OC<NUM>F<NUM>)c-(OC<NUM>RFa<NUM>)d-(OC<NUM>F<NUM>)e-(OCF<NUM>)f-.

wherein RFa each independently is H, F or Cl; and a-f each independently are an integer of <NUM>-<NUM>, with (a+b+c+d+e+f) ≥ <NUM>, and the order of the repeating units in parentheses is not limited.

RFa is preferably H or F, and more preferably F.

a, b, c, d, e and f may preferably each independently be an integer of <NUM>-<NUM>.

(a+b+c+d+e+f) is preferably <NUM> or more, and more preferably <NUM> or more, for example, <NUM> or more, or <NUM> or more. (a+b+c+d+e+f) is preferably <NUM> or less, and more preferably <NUM> or less, and still more preferably <NUM> or less, for example, <NUM> or less, or <NUM> or less.

The repeating units in parentheses with a, b, c, d, e and f may be linear or branched.

Regarding the repeating units in parentheses with a, b, c, d, e and f, examples of (OC<NUM>F<NUM>)- are - (OCF<NUM>CF<NUM>CF<NUM>CF<NUM>CF<NUM>CF<NUM>)-, - (OCF (CF<NUM>)CF<NUM>CF<NUM>CF<NUM>CF<NUM>)-, - (OCF<NUM>CF(CF<NUM>)CF<NUM>CF<NUM>CF<NUM>)-, -(OCF<NUM>CF<NUM>CF(CF<NUM>)CF<NUM>CF<NUM>)-, - (OCF<NUM>CF<NUM>CF<NUM>CF(CF<NUM>)CF<NUM>)-, and -(OCF<NUM>CF<NUM>CF<NUM>CF<NUM>CF(CF<NUM>))-. Examples of -(OC<NUM>F<NUM>)- are -(OCF<NUM>CF<NUM>CF<NUM>CF<NUM>CF<NUM>)-, - (OCF (CF<NUM>)CF<NUM>CF<NUM>CF<NUM>)-, - (OCF<NUM>CF(CF<NUM>)CF<NUM>CF<NUM>)-, - (OCF<NUM>CF<NUM>CF(CF<NUM>)CF<NUM>)-, and -(OCF<NUM>CF<NUM>CF<NUM>CF(CF<NUM>))-. - (OC<NUM>F<NUM>)-may be -(OCF<NUM>CF<NUM>CF<NUM>CF<NUM>)-, -(OCF(CF<NUM>)CF<NUM>CF<NUM>)-, - (OCF<NUM>CF(CF<NUM>)CF<NUM>)-, -(OCF<NUM>CF<NUM>CF(CF<NUM>)) -, -(OC(CF<NUM>)<NUM>CF<NUM>)-, - (OCF<NUM>C(CF<NUM>)<NUM>)-, -(OCF(CF<NUM>)CF(CF<NUM>))-, -(OCF(C<NUM>F<NUM>)CF<NUM>)-, or - (OCF<NUM>CF(C<NUM>F<NUM>)) -. -(OC<NUM>F<NUM>)- (that is, in the above formula, RFa is F) may be any of -(OCF<NUM>CF<NUM>CF<NUM>)-, - (OCF(CF<NUM>)CF<NUM>)-, or - (OCF<NUM>CF(CF<NUM>)) -. -(OC<NUM>F<NUM>)- may be - (OCF<NUM>CF<NUM>) - or - (OCF(CF<NUM>))-.

In one embodiment, the repeating unit is linear. That is, -(OC<NUM>F<NUM>)- is -(OCF<NUM>CF<NUM>CF<NUM>CF<NUM>CF<NUM>CF<NUM>)-, -(OC<NUM>F<NUM>)- is - (OCF<NUM>CF<NUM>CF<NUM>CF<NUM>CF<NUM>)-, -(OC<NUM>F<NUM>)- is -(OCF<NUM>CF<NUM>CF<NUM>CF<NUM>)-, -(OC<NUM>F<NUM>)-is -(OCF<NUM>CF<NUM>CF<NUM>)-, and -(OC<NUM>F<NUM>)- is -(OCF<NUM>CF<NUM>)-. When the repeating unit is linear, the lubricity of the surface-treating layer is improved.

In one embodiment, the repeating unit is branched. When the repeating unit is branched, the dynamic friction coefficient of the surface-treating layer can be increased.

In one embodiment, RF is each independently at each occurrence a group of any of the following formulae (f1)-(f5) :.

-(OC<NUM>F<NUM>)c-(OC<NUM>F<NUM>)d-(OC<NUM>F<NUM>)e-(OCF<NUM>)f-     (f2).

wherein c and d each independently are an integer of <NUM>-<NUM>, e and f each independently are an integer of <NUM>-<NUM>, and (c+d+e+f) is an integer of <NUM>-<NUM>; and the order of the repeating units in parentheses is not limited;.

wherein R<NUM> is OCF<NUM> or OC<NUM>F<NUM>; R<NUM> is OC<NUM>F<NUM>, OC<NUM>F<NUM>, OC<NUM>F<NUM>, OC<NUM>F<NUM>, and OC<NUM>F<NUM>, or is a combination of two or three of groups; and g is an integer of <NUM>-<NUM>;.

-(OC<NUM>F<NUM>)a-(OC<NUM>F<NUM>)b-(OC<NUM>F<NUM>)c-(OC<NUM>F<NUM>)d-(OC<NUM>F<NUM>)e-(OCF<NUM>)f-     (f4).

wherein e is an integer of <NUM>-<NUM>, a, b, c, d, and f are each independently an integer of <NUM>-<NUM>, (a+b+c+d+e+f) is at least <NUM>, and the order of the repeating units in parentheses provided with a, b, c, d, e or f is not limited; and.

-(OC<NUM>F<NUM>)a-(OC<NUM>F<NUM>)b-(OC<NUM>F<NUM>)c-(OC<NUM>F<NUM>)d-(OC<NUM>F<NUM>)e-(OCF<NUM>)f-     (f5).

wherein f is an integer of <NUM>-<NUM>, a, b, c, d, and e are each independently an integer of <NUM>-<NUM>, (a+b+c+d+e+f) is at least <NUM>, and the order of the repeating units in parentheses provided with a, b, c, d, e or f is not limited.

In formula (f1), d is preferably an integer of <NUM>-<NUM>, more preferably <NUM>-<NUM>, still more preferably <NUM>-<NUM>, for example <NUM>-<NUM>. Formula (f1) is preferably a group represented by -(OCF<NUM>CF<NUM>CF<NUM>)d- or -(OCF(CF<NUM>)CF<NUM>)d-, and more preferably a group represented by -(OCF<NUM>CF<NUM>CF<NUM>)d-.

In formula (f2), e and f are each independently, preferably an integer of <NUM>-<NUM>, and more preferably <NUM>-<NUM>. Further, (a+b+c+d+e+f) is preferably <NUM> or more, and more preferably <NUM> or more, for example, <NUM> or more, or <NUM> or more. In one embodiment, formula (f2) is preferably a group represented by -(OCF<NUM>CF<NUM>CF<NUM>CF<NUM>)c-(OCF<NUM>CF<NUM>CF<NUM>)d-(OCF<NUM>CF<NUM>)e-(OCF<NUM>)f-. In another embodiment, formula (f2) may be a group represented by -(OC<NUM>F<NUM>)e-(OCF<NUM>)f-.

In formula (f3), R<NUM> is preferably OC<NUM>F<NUM>. In formula (f3), R<NUM> is preferably a group selected from OC<NUM>F<NUM>, OC<NUM>F<NUM>, and OC<NUM>F<NUM>, or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC<NUM>F<NUM> and OC<NUM>F<NUM>. Examples of the combination of <NUM> or <NUM> groups independently selected from OC<NUM>F<NUM>, OC<NUM>F<NUM>, and OC<NUM>F<NUM> include, but are not limited to, -OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>-, - OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>-, - OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-, - OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-, - OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-, -OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-, and -OC<NUM>F<NUM>OC<NUM>F<NUM>OC<NUM>F<NUM>-. In formula (f3), g is preferably an integer of <NUM> or more, and more preferably <NUM> or more. g is preferably an integer of <NUM> or less. In formula (f3), OC<NUM>F<NUM>, OC<NUM>F<NUM>, OC<NUM>F<NUM>, OC<NUM>F<NUM>, and OC<NUM>F<NUM> may be either straight or branched, and are preferably straight. In this embodiment, the formula (f3) is preferably -(OC<NUM>F<NUM>-OC<NUM>F<NUM>)g- or -(OC<NUM>F<NUM>-OC<NUM>F<NUM>)g-.

In formula (f4), e is preferably an integer of <NUM>-<NUM>, and more preferably <NUM>-<NUM>. (a+b+c+d+e+f) is preferably <NUM> or more, and more preferably <NUM> or more, such as <NUM>-<NUM>.

In formula (f5), f is preferably an integer of <NUM>-<NUM>, and more preferably <NUM>-<NUM>. (a+b+c+d+e+f) is preferably <NUM> or more, and more preferably <NUM> or more, such as <NUM>-<NUM>.

In one embodiment, RF is a group of formula (f1).

In one embodiment, RF is a group of formula (f2).

In one embodiment, RF is a group of formula (f3).

In one embodiment, RF is a group of formula (f4).

In one embodiment, RF is a group of formula (f5).

The ratio of e to f in RF (hereinafter, referred to as an "e/f ratio") is <NUM>-<NUM>, preferably <NUM>-<NUM>, more preferably <NUM>-<NUM>, further preferably <NUM>-<NUM> or less, and still more preferably <NUM>-<NUM>. With an e/f ratio of <NUM> or less, the lubricity, friction durability, and chemical resistance (such as durability against artificial sweat) of a surface-treating layer obtained from the compound are further increased. The smaller the e/f ratio is, the higher the lubricity and the friction durability of the surface-treating layer are. On the other hand, with an e/f ratio of <NUM> or more, the stability of the compound can be further increased. The larger the e/f ratio is, the higher the stability of the compound is.

In one embodiment, the e/f ratio is preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM>.

In one embodiment, from the viewpoint of heat resistance, the e/f ratio is preferably <NUM> or more, and more preferably <NUM>-<NUM>.

In the fluoropolyether group-containing compound, the number average molecular weight of the RF1 and RF2 moieties is not limited, and is, for example, <NUM>-<NUM>,<NUM>, preferably <NUM>,<NUM>-<NUM>,<NUM>, and more preferably <NUM>,<NUM>-<NUM>,<NUM>. Herein, the number average molecular weight of RF1 and RF2 is defined as a value obtained by <NUM>F-NMR measurement.

In another embodiment, the number average molecular weight of the RF1 and RF2 moieties may be <NUM>-<NUM>,<NUM>, preferably <NUM>,<NUM>-<NUM>,<NUM>, more preferably <NUM>,<NUM>-<NUM>,<NUM>, and still more preferably <NUM>,<NUM>-<NUM>,<NUM>, for example, <NUM>,<NUM>-<NUM>,<NUM>.

In another embodiment, the number average molecular weight of the RF1 and RF2 moieties may be <NUM>,<NUM>-<NUM>,<NUM>, preferably <NUM>,<NUM>-<NUM>,<NUM>, and more preferably <NUM>,<NUM>-<NUM>,<NUM>.

In the above formulae (<NUM>) and (<NUM>), RSi is each independently at each occurrence a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded, and at least one RSi is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

In a preferable embodiment, RSi is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.

In a preferable embodiment, RSi is a group of formula (S1), (S2), (S3), or (S4) described below.

R<NUM> is preferably, each independently, a hydrolyzable group.

R<NUM> is preferably, each independently, - ORh, -OCORh, - O-N=CRh<NUM>, -NRh<NUM>, -NHRh, or halogen, wherein Rh is optionally substituted C<NUM>-<NUM>-alkyl, and more preferably -ORh (that is, alkoxy). Examples of Rh include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among such groups, alkyl, in particular unsubstituted alkyl, is preferable, and methyl or ethyl is more preferable. In one embodiment, Rh is methyl, and in another embodiment, Rh is ethyl.

In R<NUM> the monovalent organic group is a group excluding the hydrolyzable group.

In R<NUM>, the monovalent organic group is preferably C<NUM>-<NUM>-alkyl, more preferably C<NUM>-<NUM>-alkyl, and further preferably methyl.

In the above formulae, n1 is an integer of <NUM>-<NUM> each independently in each (SiR<NUM>n1R<NUM><NUM>-n1) unit. However, in formula (S1) and (S2), at least one (SiR<NUM>n1R<NUM><NUM>-n1) unit in which n1 is <NUM>-<NUM> is present in the terminal RSiβ and RSiγ moieties of the formulae (<NUM>) and (<NUM>) (hereinafter, also simply referred to as "terminal moieties" of the formulae (<NUM>) and (<NUM>)). That is, in such terminal moieties, not all n1 are <NUM> at the same time. In other words, in the terminal moieties of the formulae (<NUM>) and (<NUM>), at least one Si atom to which the hydroxyl group or the hydrolyzable group is bonded is present.

n1 is preferably an integer of <NUM>-<NUM>, more preferably <NUM>-<NUM>, and further preferably <NUM>, each independently in each (SiR<NUM>n1R<NUM><NUM>-n1) unit.

In the above formulae, X<NUM> is each independently a single bond or a divalent organic group. Such a divalent organic group is preferably C<NUM>-<NUM>-alkylene. Such C<NUM>-<NUM>-alkylene may be straight or branched, but is preferably straight.

In a preferable embodiment, X<NUM> is each independently a single bond or straight C<NUM>-<NUM>-alkylene, preferably a single bond or straight C<NUM>-<NUM>-alkylene, more preferably a single bond or straight C<NUM>-<NUM>-alkylene, and still more preferably straight C<NUM>-<NUM>-alkylene.

In the above formula, R<NUM> is each independently H or a monovalent organic group. Such a monovalent organic group is preferably C<NUM>-<NUM>-alkyl. Such a C<NUM>-<NUM>-alkyl may be straight or branched, but is preferably straight.

In a preferable embodiment, R<NUM> is each independently H or straight C<NUM>-<NUM>-alkyl, preferably H or straight C<NUM>-<NUM>-alkyl, and preferably H or methyl.

In the above formula, t is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>.

In the above formula, R<NUM> is each independently H or halogen. Such a halogen atom is preferably I, Cl or F, and more preferably F. In a preferable embodiment, R<NUM> is H.

The right side of the structure denoted as Z<NUM> below binds to (SiR<NUM>p1R<NUM>q1R<NUM>r1).

In a preferable embodiment, Z<NUM> is a divalent organic group.

In a preferable embodiment, Z<NUM> does not contain a siloxane bond with the silicon atom to which the Z<NUM> binds. Preferably, in the formula (S3), (Si-Z<NUM>-Si does not contain a siloxane bond.

Z<NUM> is preferably C<NUM>-<NUM>-alkylene, -(CH<NUM>)z1-O-(CH<NUM>)z2-(wherein z1 is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z2 is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>) or, -(CH<NUM>)z3-phenylene-(CH<NUM>)z4- (wherein z3 is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z4 is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>). The C<NUM>-<NUM>-alkylene group may be straight or branched, but is preferably straight. These groups may be substituted with one or more substituents selected from, for example, F, C<NUM>-<NUM>-alkyl, C<NUM>-<NUM>-alkenyl, and C<NUM>-<NUM>-alkynyl, and are preferably unsubstituted.

In one embodiment, Z<NUM> is C<NUM>-<NUM>-alkylene or -(CH<NUM>)z3-phenylene-(CH<NUM>)z4-, preferably -phenylene-(CH<NUM>)z4-. When Z<NUM> is such a group, light resistance, in particular ultraviolet resistance, can be more increased.

In another embodiment, Z<NUM> is C<NUM>-<NUM>-alkylene. In one embodiment, Z<NUM> may be -CH<NUM>CH<NUM>CH<NUM>-. In another embodiment, Z<NUM> may be -CH<NUM>CH<NUM>-.

The right side of the structure denoted as Z<NUM>' below binds to (SiR<NUM>'p1'R<NUM>'q1'R<NUM>'r1').

In a preferable embodiment, Z<NUM>' is a divalent organic group.

In a preferable embodiment, Z<NUM>' does not contain a siloxane bond with the silicon atom to which the Z<NUM>' binds. Preferably, (Si-Z<NUM>'-Si) does not contain a siloxane bond.

Z<NUM>' is preferably C<NUM>-<NUM>-alkylene, -(CH<NUM>)z1'-O-(CH<NUM>)z2'-(wherein z1' is an integer of <NUM>-<NUM>; for example, an integer of <NUM>-<NUM>, and z2' is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>) or, -(CH<NUM>)z3'-phenylene-(CH<NUM>)z4'- (wherein z3' is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z4' is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>). Such C<NUM>-<NUM>-alkylene may be straight or branched, but is preferably straight. These groups may be substituted with one or more substituents selected from, for example, F, C<NUM>-<NUM>-alkyl, C<NUM>-<NUM>-alkenyl, and C<NUM>-<NUM>-alkynyl, and are preferably unsubstituted.

In one embodiment, Z<NUM>' is C<NUM>-<NUM>-alkylene or -(CH<NUM>)z3'-phenylene- (CH<NUM>)z4'-, preferably -phenylene- (CH<NUM>)z4'-. When Z<NUM>' is such a group, light resistance, in particular ultraviolet resistance, can be more increased.

In another embodiment, Z<NUM>' is C<NUM>-<NUM>-alkylene. In one embodiment, Z<NUM>' may be -CH<NUM>CH<NUM>CH<NUM>-. In another embodiment, Z<NUM>' may be -CH<NUM>CH<NUM>-.

The right side of the structure denoted as Z<NUM>" binds to (SiR<NUM>"q1"R<NUM>"r1").

In a preferable embodiment, Z<NUM>" is a divalent organic group.

In a preferable embodiment, Z<NUM>" does not contain a siloxane bond with the silicon atom to which the Z<NUM>" binds. Preferably, (Si-Z<NUM>"-Si) does not contain a siloxane bond.

Z<NUM>" is preferably C<NUM>-<NUM>-alkylene, -(CH<NUM>)z1"-O-(CH<NUM>)z2"-(wherein z1" is an integer of <NUM>-<NUM>; for example, an integer of <NUM>-<NUM>, and z2" is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>) or, -(CH<NUM>)z3"-phenylene-(CH<NUM>)z4"- (wherein z3" is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z4" is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>). Such C<NUM>-<NUM>-alkylene may be straight or branched, but is preferably straight. These groups may be substituted with one or more substituents selected from, for example, F, C<NUM>-<NUM>-alkyl, C<NUM>-<NUM>-alkenyl, and C<NUM>-<NUM>-alkynyl, and are preferably unsubstituted.

In one embodiment, Z<NUM>" is C<NUM>-<NUM>-alkylene or -(CH<NUM>)z3"-phenylene- (CH<NUM>)z4"-, preferably -phenylene- (CH<NUM>)z4"-. When Z<NUM>" is such a group, light resistance, in particular ultraviolet resistance, can be more increased.

In another embodiment, Z<NUM>" is C<NUM>-<NUM>-alkylene. In one embodiment, Z<NUM>" may be -CH<NUM>CH<NUM>CH<NUM>-. In another embodiment, Z<NUM>" may be -CH<NUM>CH<NUM>-.

R<NUM>" is preferably, each independently a hydrolyzable group.

R<NUM>" is preferably, each independently - ORh, -OCORh, - O-N=CRh<NUM>, -NRh<NUM>, -NHRh, or halogen, wherein Rh is optionally substituted C<NUM>-<NUM>-alkyl, more preferably -ORh (that is, alkoxy). Examples of Rh include unsubstituted alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl such as chloromethyl. Among such groups, alkyl, in particular unsubstituted alkyl, is preferable, and methyl or ethyl is more preferable. In one embodiment, Rh is methyl, and in another embodiment, Rh is ethyl.

In R<NUM>" the monovalent organic group is a group excluding the hydrolyzable group.

In R<NUM>", the monovalent organic group is preferably C<NUM>-<NUM>-alkyl, more preferably C<NUM>-<NUM>-alkyl, and further preferably methyl.

The total of q1" and r1" is <NUM> in (SiR<NUM>"q1"R<NUM>"r1") unit.

q1" is preferably an integer of <NUM>-<NUM>, more preferably <NUM>-<NUM>, and further preferably <NUM>, each independently in each (SiR<NUM>"q1"R<NUM>"r1") unit.

R<NUM>' is preferably, each independently a hydrolyzable group.

R<NUM>' is preferably, each independently, - ORh, -OCORh, -O-N=CRh<NUM>, -NRh<NUM>, -NHRh, or halogen, wherein Rh is optionally substituted C<NUM>-<NUM>-alkyl, more preferably -ORh (that is, alkoxy). Examples of Rh include unsubstituted alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl such as chloromethyl. Among such groups, alkyl, in particular unsubstituted alkyl, is preferable, and methyl or ethyl is more preferable. In one embodiment, Rh is methyl, and in another embodiment, Rh is ethyl.

In R<NUM>' the monovalent organic group is a group excluding the hydrolyzable group.

In R<NUM>', the monovalent organic group is preferably C<NUM>-<NUM>-alkyl, more preferably C<NUM>-<NUM>-alkyl, and further preferably methyl.

The total of p', q1' and r1' is <NUM> in (SiR<NUM>'p1'R<NUM>'q1'R<NUM>'r1') unit.

In one embodiment, p1' may be an integer of <NUM>-<NUM>, an integer of <NUM>-<NUM>, or <NUM>, each independently in each (SiR<NUM>'p1'R<NUM>'q1'R<NUM>'r1') unit. In a preferable embodiment, p1' is <NUM>.

In one embodiment, q1' is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>, each independently in each (SiR<NUM>'p1'R<NUM>'q1'R<NUM>'r1') unit.

In one embodiment, p1' is <NUM>, q1' is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>, and further preferably <NUM>, each independently in each (SiR<NUM>'p1'R<NUM>'q1'R<NUM>'r1') unit.

R<NUM> is preferably, each independently, - ORh, -OCORh, - O-N=CRh<NUM>, -NRh<NUM>, -NHRh, or halogen, wherein Rh is optionally substituted C<NUM>-<NUM>-alkyl, more preferably -ORh (that is, alkoxy). Examples of Rh include unsubstituted alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl such as a chloromethyl group. Among such groups, alkyl, in particular unsubstituted alkyl, is preferable, and methyl or ethyl is more preferable. In one embodiment, Rh is methyl, and in another embodiment, Rh is ethyl.

The total of p, q1 and r1 is <NUM> in (SiR<NUM>p1R<NUM>q1R<NUM>r1) unit.

In one embodiment, p1 may be an integer of <NUM>-<NUM>, an integer of <NUM>-<NUM>, or <NUM>, each independently in each (SiR<NUM>p1R<NUM>q1R<NUM>r1) unit. In a preferable embodiment, p1 is <NUM>.

In one embodiment, q1 is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>, each independently in each (SiR<NUM>p1R<NUM>q1R<NUM>r1) unit.

In one embodiment, p1 is <NUM>, q1 is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>, and further preferably <NUM>, each independently in each (SiR<NUM>p1R<NUM>q1R<NUM>r1) unit.

Rb1 is preferably, each independently, a hydrolyzable group.

Rb1 is preferably, each independently , - ORh, -OCORh, -O-N=CRh<NUM>, -NRh<NUM>, -NHRh, or halogen, wherein Rh is optionally substituted C<NUM>-<NUM>-alkyl, more preferably -ORh (that is, alkoxy). Examples of Rh include unsubstituted alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl such as chloromethyl. Among such groups, alkyl, in particular unsubstituted alkyl, is preferable, and methyl or ethyl is more preferable. In one embodiment, Rh is methyl, and in another embodiment, Rh is ethyl.

In Rc1 the monovalent organic group is a group excluding the hydrolyzable group.

In Rc1, the monovalent organic group is preferably C<NUM>-<NUM>-alkyl, more preferably C<NUM>-<NUM>-alkyl, and further preferably methyl.

The total of p, l1 and m1 is <NUM> in (SiRa1k1Rb1<NUM>RC1m1) unit.

In one embodiment, k1 is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>, each independently in each (SiRa1k1Rb1l1Rc1m1) unit. In a preferable embodiment, k1 is <NUM>.

In the formulae (<NUM>) and (<NUM>), when RSi is a group of formula (S3), preferably, at least two Si atoms to which OH or a hydrolyzable group is bonded are present in the terminal moieties of the formulae (<NUM>) and (<NUM>).

In a preferable embodiment, the group of formula (S3) has any one of -Z<NUM>-SiR<NUM>q1R<NUM>r1 (wherein q1 is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>, and r1 is an integer of <NUM>-<NUM>. ), -Z<NUM>'-SiR<NUM>'q1'R<NUM>'r1' (wherein q1' is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>, and r1' is an integer of <NUM>-<NUM>), or -Z<NUM>"-SiR<NUM>"q1"R<NUM>"r1" (wherein q1" is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>, and r1" is an integer of <NUM>-<NUM>).

In a preferable embodiment, in formula (S3), when R<NUM>' is present, in at least one, preferably all R<NUM>', q1" is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>.

In a preferable embodiment, in formula (S3), when R<NUM> is present, in at least one, preferably all R<NUM>, p1' is <NUM>, and q1' is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>.

In a preferable embodiment, in formula (S3), when Ra1 is present, in at least one, preferably all Ra1, p1 is <NUM>, and q1 is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>.

In a preferable embodiment, in formula (S3), k1 is <NUM> or <NUM>, preferably <NUM>, p1 is <NUM>, q1 is <NUM> or <NUM>, preferably <NUM>.

The right side of the structure denoted as Z<NUM> binds to (CR<NUM>p2R<NUM>q2R<NUM>r2).

Z<NUM> is preferably C<NUM>-<NUM>-alkylene, -(CH<NUM>)z5-O-(CH<NUM>)z6-(wherein z5 is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z6 is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>) or, -(CH<NUM>)z7-phenylene-(CH<NUM>)z8- (wherein z7 is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z8 is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>). Such C<NUM>-<NUM>-alkylene may be straight or branched, but is preferably straight. These groups may be substituted with one or more substituents selected from, for example, F, C<NUM>-<NUM>-alkyl, C<NUM>-<NUM>-alkenyl, and C<NUM>-<NUM>-alkynyl, and are preferably unsubstituted.

In one embodiment, Z<NUM> is C<NUM>-<NUM>-alkylene or -(CH<NUM>)z7-phenylene- (CH<NUM>)z8-, preferably -phenylene- (CH<NUM>)z8-. When Z<NUM> is such a group, light resistance, in particular ultraviolet resistance, can be more increased.

The right side of the structure denoted as Z<NUM>' binds to (CR<NUM>'q2'R<NUM>'r2').

Z<NUM>' is preferably C<NUM>-<NUM>-alkylene, -(CH<NUM>)z5'-O-(CH<NUM>)z6'-(wherein z5' is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z6' is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>) or, -(CH<NUM>)z7'-phenylene-(CH<NUM>)z8'- (wherein z7' is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z8' is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>). Such a C<NUM>-<NUM> alkylene group may be straight or branched, but is preferably straight. These groups may be substituted with one or more substituents selected from, for example, F, C<NUM>-<NUM>-alkyl, C<NUM>-<NUM>-alkenyl, and C<NUM>-<NUM>-alkynyl, and are preferably unsubstituted.

In one embodiment, Z<NUM>' is C<NUM>-<NUM>-alkylene or -(CH<NUM>)z7'-phenylene-(CH<NUM>)z8'-, preferably -phenylene- (CH<NUM>)z8'-. When Z<NUM>' is such a group, light resistance, in particular ultraviolet resistance, can be more increased.

The right side of the structure denoted as Z<NUM> binds to (SiR<NUM>n2R<NUM><NUM>-n2 ).

In one embodiment, Z<NUM> is an oxygen atom.

In one embodiment, Z<NUM> is a divalent organic group.

Z<NUM> is preferably C<NUM>-<NUM>-alkylene, -(CH<NUM>)z5"-O-(CH<NUM>)z6"-(wherein z5" is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z6" is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>) or, -(CH<NUM>)z7"-phenylene-(CH<NUM>)z8"- (wherein z7" is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>, and z8" is an integer of <NUM>-<NUM>; for example <NUM>-<NUM>). Such C<NUM>-<NUM>-alkylene may be straight or branched, but is preferably straight. These groups may be substituted with one or more substituents selected from, for example, F, C<NUM>-<NUM>-alkyl, C<NUM>-<NUM>-alkenyl, and C<NUM>-<NUM>-alkynyl, and are preferably unsubstituted.

In one embodiment, Z<NUM> is C<NUM>-<NUM>-alkylene or -(CH<NUM>)z7"-phenylene- (CH<NUM>)z8"-, preferably -phenylene- (CH<NUM>)z8"-. When Z<NUM> is such a group, light resistance, in particular ultraviolet resistance, can be more increased.

R<NUM> is preferably, each independently, - ORh, -OCORh, - O-N=CRh<NUM>, -NRh<NUM>, -NHRh, or halogen, wherein Rh is optionally substituted C<NUM>-<NUM>-alkyl, more preferably -ORh (that is, an alkoxy group). Examples of Rh include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl such as chloromethyl. Among such groups, alkyl, in particular unsubstituted alkyl, is preferable, and methyl or ethyl is more preferable. In one embodiment, Rh is methyl, and in another embodiment, Rh is ethyl.

In the above formula, n2 is an integer of <NUM>-<NUM> each independently in each (SiR<NUM>n2R<NUM><NUM>-n2) unit. However, in a case where RSi is a group represented by the formula (S4), at least one (SiR<NUM>n2R<NUM><NUM>-n2) unit in which n2 is <NUM>-<NUM> is present in the terminal moieties of the formulae (<NUM>) and (<NUM>). That is, in such terminal moieties, not all n2 are <NUM> at the same time. In other words, in the terminal moieties of the formulae (<NUM>) (<NUM>), at least one Si atom to which the hydroxyl group or the hydrolyzable group is bonded is present.

n2 is preferably an integer of <NUM>-<NUM>, more preferably <NUM>-<NUM>, and further preferably <NUM>, each independently in each (SiR<NUM>n2R<NUM><NUM>-n2) unit.

In another embodiment, in R<NUM>', the monovalent organic group is preferably C<NUM>-<NUM>-alkyl, and more preferably C<NUM>-<NUM>-alkyl.

The total of q2' and r2' is <NUM> in (SiR<NUM>'q2'R<NUM>'r2') unit.

q2' is preferably an integer of <NUM>-<NUM>, more preferably <NUM>-<NUM>, and further preferably <NUM>, each independently in each (SiR<NUM>'q2'R<NUM>'r2') unit.

In another embodiment, in R<NUM>, the monovalent organic group is preferably C<NUM>-<NUM>-alkyl, and more preferably C<NUM>-<NUM>-alkyl.

The total of p2, q2, and r2 is <NUM> in (CR<NUM>p2R<NUM>q2R<NUM>r2) unit.

In one embodiment, p2 may be an integer of <NUM>-<NUM>, an integer of <NUM>-<NUM>, or <NUM>, each independently in each (CR<NUM>p2R<NUM>q2R<NUM>r2) unit. In a preferable embodiment, p2 is <NUM>.

In one embodiment, q2 is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>, each independently in each (CR<NUM>p2R<NUM>q2R<NUM>r2) unit.

In one embodiment, p2 is <NUM>, q2 is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>, and further preferably <NUM>, each independently in each (CR<NUM>p2R<NUM>q2R<NUM>r2) unit.

In Rf1 the monovalent organic group is a group excluding the hydrolyzable group.

In Rf1, the monovalent organic group is preferably C<NUM>-<NUM>-alkyl, more preferably C<NUM>-<NUM>-alkyl, and further preferably methyl.

In another embodiment, in Rf1, the monovalent organic group is preferably C<NUM>-<NUM>-alkyl, and more preferably C<NUM>-<NUM>-alkyl.

The total of k2, l2, and m2 is <NUM> in (CRd1k2Re1l2Rf1m2) unit.

In one embodiment, when RSi is a group of formula (S4), two or more, for example, <NUM>-<NUM>, preferably <NUM>-<NUM>, more preferably <NUM>-<NUM>, further preferably <NUM>-<NUM>, particularly preferably <NUM> (SiR<NUM>n2R<NUM><NUM>-n2) units in which n2 is <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM> are present in each terminal moiety of the formula (<NUM>) and the formula (<NUM>).

In a preferable embodiment, in formula (S4), when R<NUM>' is present, in at least one, preferably all R<NUM>', n2 is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>.

In a preferable embodiment, in formula (S4), when R<NUM> is present, in at least one, preferably all R<NUM>, n2 is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>.

In a preferable embodiment, in formula (S4), when Re1 is present, in at least one, preferably all Re1, n2 is an integer of <NUM>-<NUM>, preferably <NUM> or <NUM>, more preferably <NUM>.

In a preferable embodiment, in formula (S4), k2 is <NUM>, l2 is <NUM> or <NUM>, preferably <NUM>, and n2 is <NUM> or <NUM>, preferably <NUM>.

In one embodiment, RSi is a group of formula (S2), (S3) or (S4).

In one embodiment, RSi is a group of formula (S1), (S3) or (S4).

In one embodiment, RSi is a group of formula (S3) or (S4).

In one embodiment, RSi is a group of formula (S1).

In one embodiment, RSi is a group of formula (S2).

In one embodiment, RSi is a group of formula (S3).

In one embodiment, RSi is a group of formula (S4).

In the formulae (<NUM>) and (<NUM>), XA is interpreted as a linker, connecting a fluoropolyether moiety (RF1 and RF2) which mainly provides, e.g., water-repellency and surface lubricity, and a moiety (RSi) providing binding ability to a substrate. Accordingly, XA may be a single bond or any group as long as the compound represented by the formula (I) or (<NUM>) can stably exist.

In the formula (<NUM>), α is an integer of <NUM>-<NUM>, and β is an integer of <NUM>-<NUM>. The integers represented by α and β may vary depending on the valence of XA. The sum (α+β) is the same as the valence of XA. For example, when XA is a decavalent organic group, (α+β) is <NUM>; for example, a case where α is <NUM> and β is <NUM>, and α is <NUM> and β is <NUM>, or α is <NUM> and β is <NUM>, can be considered. When XA is a divalent organic group, α and β each are <NUM>.

In the formula (<NUM>), y is an integer of <NUM>-<NUM>. y may vary according to the valence of XA. That is, y is a value obtained by subtracting <NUM> from the valence of XA.

Each XA is independently a single bond or a di- to decavalent organic group.

The di- to decavalent organic group in XA is preferably a di- to octavalent organic group. In one embodiment, the di- to decavalent organic group is preferably a di- to tetravalent organic group, and more preferably a divalent organic group. In another embodiment, the di- to decavalent organic group is preferably a tri- to octavalent organic group, and more preferably a tri- to hexavalent organic group.

In one embodiment, XA is a single bond or a divalent organic group, α is <NUM>, and β is <NUM>.

In one embodiment, XA is a single bond or a divalent organic group, γ is <NUM>.

In one embodiment, XA is a tri- to hexavalent organic group, α is <NUM>, and β is <NUM>-<NUM>.

In one embodiment, XA is a tri- to hexavalent organic group, and γ is <NUM>-<NUM>.

In one embodiment, XA is a trivalent organic group, α is <NUM>, and β is <NUM>.

In one embodiment, XA is a trivalent organic group, and γ is <NUM>.

When XA is a single bond or a divalent organic group, the formulae (<NUM>) and (<NUM>) are represented by the following formulae (<NUM>') and (<NUM>').

In another embodiment, XA is a divalent organic group.

In one embodiment, examples of XA include a single bond or a divalent organic group of the formula:.

Here, RA (typically, hydrogen atoms of RA) is optionally substituted with one or more substituents selected from F, C<NUM>-<NUM>-alkyl, and C<NUM>-<NUM>-fluoroalkyl. In a preferable embodiment, RA is not substituted with these groups.

In a preferable embodiment, XA is each independently - (R<NUM>)p5-(X<NUM>)q5-R<NUM>-. R<NUM> represents a single bond, -(CH<NUM>)t5-, o-, m-, or a p-phenylene, and is preferably -(CH<NUM>)t5-. t5 is an integer of <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM>. Here, R<NUM> (typically, hydrogen atoms of R<NUM>) is optionally substituted with one or more substituents selected from F, C<NUM>-<NUM>-alkyl, and C<NUM>-<NUM>-fluoroalkyl. In a preferable embodiment, R<NUM> is not substituted with these groups.

Preferably, XA may each independently be.

More preferably, XA may each independently be.

In a preferable embodiment, XA may each independently be.

In one embodiment, XA may each independently be.

In the above formula, -(CvH2v)- may be straight or branched and may be, for example, -CH<NUM>CH<NUM>-, -CH<NUM>CH<NUM>CH<NUM>-, - CH(CH<NUM>)-, or -CH(CH<NUM>)CH<NUM>-.

XA each independently is optionally substituted with one or more substituents selected from F, C<NUM>-<NUM>-alkyl, and C<NUM>-<NUM>-fluoroalkyl (preferably, C<NUM>-<NUM>-perfluoroalkyl). In one embodiment, XA is unsubstituted.

The left side of each formula of XA binds to RF1 or RF2, and the right side binds to RSi.

In one embodiment, XA may each independently be a group other than -O-(C<NUM>-<NUM>-alkylene).

In another embodiment, examples of XA include the following groups:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

Specific examples of the above-described XA include, for example:.

In yet another embodiment, XA is each independently a group of the formula -(R<NUM>)x1-(CFR<NUM>)y1-(CH<NUM>)z1-. In the formula, x1, y1 and z1 are each independently an integer of <NUM>-<NUM>, the sum of x1, y1 and z1 is <NUM> or more, and the order of the repeating units in parentheses is not limited.

In the above formulae, R<NUM> is each independently at each occurrence an oxygen atom, phenylene, carbazolylene, - NR<NUM>- (wherein R<NUM> is H or an organic group) or a divalent organic group. Preferably, R<NUM> is an oxygen atom or a divalent polar group.

Examples of the "divalent polar group" include, but are not limited to, -C(O)-, -C(=NR<NUM>)- and -C(O)NR<NUM>-(wherein R<NUM> is H or lower alkyl). The "lower alkyl " is, for example, C<NUM>-<NUM>-alkyl, such as methyl, ethyl or n-propyl, and these may be substituted with one or more F.

In the above formulae, R<NUM> is each independently H, F or lower fluoroalkyl, and preferably F. The "lower fluoroalkyl " is, for example, a C<NUM>-<NUM>-fluoroalkyl and preferably <NUM>-<NUM> carbon atoms, preferably C<NUM>-<NUM>-perfluoroalkyl, more preferably trifluoromethyl or pentafluoroethyl, and further preferably trifluoromethyl.

In still another embodiment, examples of the XA group include the following group:
<CHM>
<CHM>
<CHM>
wherein.

The radical scavenging group is not limited as long as it can capture a radical generated by light irradiation, and, for example, residues of a benzophenone, a benzotriazole, a benzoate, a phenyl salicylate, crotonic acid, a malonate, an organo-acrylate, a hindered amine, a hindered phenol or a triazine, is mentioned.

The UV absorbing group is not limited as long as it can absorb ultraviolet rays, and, for example, a residue of a benzotriazole, a hydroxybenzophenone, an ester of a substituted and unsubstituted benzoic acid or salicylic acid compound, an acrylate or an alkoxy cinnamate, an oxamide, an oxanilide, a benzoxazinone or a benzoxazole, is mentioned.

In a preferable embodiment, as a preferable radical scavenging group or UV absorbing group, the groups of the following formulae are mentioned.

In this embodiment, XA may each independently be a tri- to decavalent organic group.

In still another embodiment, examples of the XA group include the following group:
<CHM>.

In one embodiment, R<NUM> is a single bond, C<NUM>-<NUM>-alkylene, C<NUM>-<NUM>-cycloalkylene, C<NUM>-<NUM>-arylene, -R<NUM>-X<NUM>-R<NUM>-, -X<NUM>-R<NUM>-, or -R<NUM>-X<NUM>-. R<NUM> and R<NUM> are each independently a single bond, C<NUM>-<NUM>-alkylene, C<NUM>-<NUM>-cycloalkylene, or C<NUM>-<NUM>-arylene. X<NUM> is -O-, -S-, -CO-, -O-CO-, or -COO-.

In one embodiment, R<NUM> and R<NUM> are each independently a hydrocarbon or a group having at least one atom selected from N, O and S at the end or in the backbone of a hydrocarbon, preferably including C<NUM>-<NUM>-alkyl, -R<NUM>-R<NUM>-R<NUM>-, or -R<NUM>-CHR<NUM><NUM>-. Here, R<NUM> is each independently a single bond or C<NUM>-<NUM>-alkyl, preferably C<NUM>-<NUM>-alkyl. R<NUM> is N, O or S, preferably N or O. R<NUM> is -R<NUM>-R<NUM>-R<NUM>-, -R<NUM>-R<NUM>- or -R<NUM>-R<NUM>-. R<NUM> is each independently C<NUM>-<NUM>-alkyl. R<NUM> is N, O or S, preferably O.

The fluoropolyether group-containing compound of formula (<NUM>) (also "compound (<NUM>)" hereinafter) or (<NUM>) (also "compound (<NUM>)" hereinafter) is not particularly limited, but may have an average molecular weight of <NUM> × <NUM><NUM> to <NUM> × <NUM><NUM>. In particular, the compound preferably has a number average molecular weight of <NUM>,<NUM>-<NUM>,<NUM>, and more preferably <NUM>,<NUM>-<NUM>,<NUM>, from the viewpoint of friction durability. The "average molecular weight" refers to a number average molecular weight, and the "average molecular weight" is a value obtained by <NUM>F-NMR measurement.

In one embodiment, the fluorine-containing silane compound in the surface-treating agent used in the present disclosure is the compound (<NUM>), in another embodiment it is the compound (<NUM>), and in another embodiment it is the compound (<NUM>) and the compound (<NUM>).

In the surface-treating agent used in the present disclosure, the compound (<NUM>) is preferably <NUM>-<NUM> mol% based on the total of the compounds (<NUM>) and (<NUM>). The lower limit of the content of the compound (<NUM>) based on the total of the compounds (<NUM>) and (<NUM>)may be preferably <NUM> mol%, more preferably <NUM> mol%, further preferably <NUM> mol%, and still more preferably <NUM> mol%, particularly preferably <NUM> mol%, and especially <NUM> mol%. The upper limit of the content of the compound (<NUM>) based on the total of the compounds (<NUM>) and (<NUM>) may be preferably <NUM> mol%, more preferably <NUM> mol%, further preferably <NUM> mol%, and still more preferably <NUM> mol% or <NUM> mol%. The amount of compound (<NUM>) based on the total of the compounds (<NUM>) and (<NUM>) is preferably <NUM>-<NUM> mol%, more preferably <NUM>-<NUM> mol%, further preferably <NUM>-<NUM> mol%, still more preferably <NUM>-<NUM> mol%, and particularly preferably <NUM>-<NUM> mol%, for example, <NUM>-<NUM> mol%, or <NUM>-<NUM> mol%. With the compound (<NUM>) being within such a range, friction durability can be more increased.

The compounds (<NUM>) or (<NUM>) can be obtained, for example, by the methods described in e.g. <CIT> and <CIT>.

The surface-treating agent used in the present disclosure may include a solvent, a (unreactive) fluoropolyether compound which can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter, collectively referred to as "fluorine-containing oil"), a (unreactive) silicone compound which can be understood as a silicone oil (hereinafter, referred to as "silicone oil"), a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, and the like.

Examples of the solvent include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl <NUM>-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl <NUM>-methoxypropionate, ethyl <NUM>-methoxypropionate, methyl <NUM>-hydroxyisobutyrate, and ethyl <NUM>-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, <NUM>-hexanone, cyclohexanone, methyl amino ketone, and <NUM>-heptanone; glycol ethers such as ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, <NUM>-pentanol, octyl alcohol, <NUM>-methyl-<NUM>-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; and fluorine-containing solvents such as <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane, <NUM>,<NUM>-dichloro-<NUM>,<NUM>,<NUM>,<NUM>-tetrafluoroethane, dimethyl sulfoxide, <NUM>,<NUM>-dichloro-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentafluoropropane (HCFC <NUM>), Zeorora H, HFE <NUM>, HFE <NUM>, and HFE <NUM>. Alternatively, the solvent may be a mixed solvent of two or more of such solvents.

The fluorine-containing oil is not limited, and examples thereof include a compound (perfluoro(poly)ether compound) of formula (<NUM>):.

Rf<NUM>-(OC<NUM>F<NUM>)a'-(OC<NUM>F<NUM>)b'-(OC<NUM>F<NUM>)c'-(OCF<NUM>)d'-Rf<NUM>.

Examples of the perfluoro(poly)ether compound of formula (<NUM>) include a compound of any of the formulae (3a) and (3b) (which may be adopted singly or as a mixture of two or more kinds thereof).

Rf<NUM>-(OCF<NUM>CF<NUM>CF<NUM>)b"-Rf<NUM>.

Rf<NUM>-(OCF<NUM>CF<NUM>CF<NUM>CF<NUM>)a"-(OCF<NUM>CF<NUM>CF<NUM>)b"-(OCF<NUM>CF<NUM>)c"-(OCF<NUM>)d"-Rf<NUM>.

In such formulae, Rf<NUM> and Rf<NUM> are as described above; in formula (3a), b" is an integer of <NUM>-<NUM>; and, in formula (3b), a" and b" are each independently an integer of <NUM>-<NUM>, c" and d" are each independently an integer of <NUM>-<NUM>. The order of the repeating units in parentheses provided with a subscript a", b", c", or d" is not limited.

From another viewpoint, the fluorine-containing oil may be a compound of the formula Rf<NUM>-F wherein Rf<NUM> is C<NUM>-<NUM>-perfluoroalkyl. The fluorine-containing oil may be a chlorotrifluoroethylene oligomer.

The fluorine-containing oil may have an average molecular weight of <NUM>-<NUM>,<NUM>. The molecular weight of the fluorine-containing oil may be measured using GPC.

The fluorine-containing oil may be contained in an amount of, for example, <NUM>-<NUM> mass%, preferably <NUM>-<NUM> mass%, and more preferably <NUM>-<NUM> mass% based on the surface-treating agent. In one embodiment, the surface-treating agent is substantially free of the fluorine-containing oil. Being substantially free of the fluorine-containing oil means that the fluorine-containing oil is not contained at all, or an extremely small amount of the fluorine-containing oil may be contained.

In one embodiment, the average molecular weight of the fluorine-containing oil may be greater than the average molecular weight of the fluorine-containing silane compound. With such average molecular weights, better friction durability and surface lubricity can be obtained, in the case of forming the surface-treating layer by the vacuum deposition method.

In one embodiment, the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the fluorine-containing silane compound. With such average molecular weights, a cured product having high friction durability and high surface lubricity can be formed while suppressing the deterioration in transparency of the surface-treating layer obtained from the compound.

The fluorine-containing oil contributes to enhancing surface lubricity of the layer formed by the surface-treating agent.

For example, the silicone oil may be linear or cyclic silicone oil having <NUM>,<NUM> or less siloxane bonds. The linear silicone oil may be so-called straight silicone oil or modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, or alcohol. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.

The surface-treating agent can include, for example, <NUM>-<NUM> parts by mass (pbm), preferably <NUM>-<NUM> pbm of such silicone oil based on a total of <NUM> pbm of the fluorine-containing silane compound (in the case of two or more kinds, the total thereof, much the same is true on the following).

Silicone oil contributes to increasing the surface lubricity of the surface-treating layer.

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

The catalyst promotes hydrolysis and dehydration condensation of the fluorine-containing silane compound, and promotes formation of the layer to be formed by the surface-treating agent.

Examples of other components include, in addition to those described above, tetraethoxysilane, methyltrimethoxysilane, <NUM>-aminopropyltrimethoxysilane, <NUM>-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

The present surface-treating agent can be formed into a pellet by impregnating a porous material, for example, a porous ceramic material or a metal fiber for example that obtained by solidifying a steel wool, therewith. Such pellets can be used in, for example, vacuum deposition.

The thickness of the surface-treating layer is not limited. The thickness of the layer in the case of an optical member is in the range of <NUM>-<NUM>, <NUM>-<NUM>, and preferably <NUM>-<NUM>, from the viewpoint of optical performance, surface lubricity, friction durability, and antifouling properties.

The surface-treating layer can be formed, for example, by forming a layer of the surface-treating agent on the intermediate layer and post-treating the layer as necessary.

The layer of the surface-treating agent can be formed by applying the above surface-treating agent on the surface of the intermediate layer such that the composition coats the surface. The coating method is not limited. For example, a wet coating method and a dry coating method can be used.

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

Examples of the dry coating method include deposition (usually, vacuum deposition), sputtering, and CVD. Specific examples of the deposition method (usually, a vacuum deposition method) include resistive heating, highfrequency heating using electron beam, and microwave, and ion beam. Specific examples of the CVD method include plasma-CVD, optical CVD, and thermal CVD.

Furthermore, coating by an atmospheric pressure plasma method can be performed.

When using the wet coating method, the surface-treating agent can be applied to the intermediate layer after being diluted with a solvent. From the viewpoint of the stability of the surface-treating agent and the volatility of solvents, the following solvents are preferably used: perfluoroaliphatic C<NUM>-<NUM>-hydrocarbons (such as perfluorohexane, perfluoromethylcyclohexane, and perfluoro-<NUM>,<NUM>-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (such as bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (such as C<NUM>F<NUM>CH<NUM>CH<NUM> (such as Asahiklin (registered trademark) AC-<NUM> manufactured by Asahi Glass Co. , and <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-heptafluorocyclopentane (such as Zeorora (registered trademark) H manufactured by Zeon Corporation)); alkyl perfluoroalkyl ethers (the perfluoroalkyl group and the alkyl group may be linear or branched) such as hydrofluoroether (HFE) (such as perfluoropropylmethyl ether (C<NUM>F<NUM>OCH<NUM>) (such as Novec (trademark) <NUM> manufactured by Sumitomo <NUM> Limited), perfluorobutyl methyl ether (C<NUM>F<NUM>OCH<NUM>) (such as Novec (trademark) <NUM> manufactured by Sumitomo <NUM> Limited), perfluorobutyl ethyl ether (C<NUM>F<NUM>OC<NUM>H<NUM>) (such as Novec (trademark) <NUM> manufactured by Sumitomo <NUM> Limited), and perfluorohexyl methyl ether (C<NUM>F<NUM>CF(OCH<NUM>)C<NUM>F<NUM>) (such as Novec (trademark) <NUM> manufactured by Sumitomo <NUM> Limited), or CF<NUM>CH<NUM>OCF<NUM>CHF<NUM> (such as Asahiklin (registered trademark) AE-<NUM> manufactured by Asahi Glass Co. One of these solvents can be used singly, or two or more can be used as a mixture. In particular, hydrofluoroether is preferable, and perfluorobutyl methyl ether (C<NUM>F<NUM>OCH<NUM>) and/or perfluorobutyl ethyl ether (C<NUM>F<NUM>OC<NUM>H<NUM>) is particularly preferable.

When using the dry coating method, the surface-treating agent may be directly subjected to the dry coating method, or may be diluted with the above solvent before being subjected to the dry coating method.

A layer of the surface-treating agent is preferably formed such that the surface-treating agent coexists in the layer with a catalyst for hydrolysis and dehydrative condensation. Conveniently, in the case of a wet coating method, the surface-treating agent is diluted with a solvent, and then, immediately before application to the intermediate layer, a catalyst may be added to the diluted solution of the surface-treating agent. In the case of a dry coating method, the surface-treating agent to which a catalyst has been added is directly used to a deposition (usually vacuum deposition) treatment, or a pellet-like material may be used to a deposition (usually vacuum deposition) treatment, wherein the pellets is obtained by impregnating a porous body of metal such as iron or copper with the surface-treating agent to which the catalyst has been added.

The catalyst may be any suitable acid or base. The acid catalyst may be, for example, acetic acid, formic acid, or trifluoroacetic acid. The base catalyst may be, for example, ammonia or organic amine.

In the above-described manner, a layer derived from the surface-treating agent is formed on the intermediate layer surface, and the article of the present disclosure is produced. The surface-treating layer thus obtained has high friction durability. The layer may have not only high friction durability but also have, depending on the compositional features of the surface-treating agent used, water-repellency, oil-repellency, antifouling properties (e.g., preventing grime such as fingerprints from adhering), waterproof properties (e.g. preventing water from entering electronic components), surface lubricity (or lubricity, for example, such as removability by wiping of grim such as fingerprints, and excellent tactile sensations to the fingers, and may be suitably used as a functional thin film.

The present article may be an optical material having the surface-treating layer as an outermost layer.

The present article may be, but is not limited to, an optical member. Examples of the optical member include lenses of glasses; front surface protective plates, antireflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and display surfaces of watches and clocks.

The present article may be medical equipment or a medical material.

The present article has high chemical resistance and high friction durability by having an intermediate layer containing a composite oxide containing Si on a substrate and a surface-treating layer formed from a surface-treating agent containing a fluorine-containing silane compound thereon.

The present article can be obtained by forming an intermediate layer containing a composite oxide containing Si on a substrate and forming a surface-treating layer from a surface-treating agent containing a fluorine-containing silane compound thereon.

Typically, the present article can be produced by simultaneously depositing Si and another atom on the substrate.

Accordingly, the present method is a method for producing an article comprising a substrate and, formed thereon, a surface-treating layer formed from a surface-treating agent containing at least one fluorine-containing silane compound of formula (<NUM>) or (<NUM>) as defined herein, comprising:.

The present article may be produced by sequentially depositing Si and another atoms on the substrate.

Hereinafter, an article of the present disclosure will be described in Examples. In the Examples, all chemical formulae shown below indicate average compositional features, and the order of repeating units (such as (CF<NUM>CF<NUM>CF<NUM>O), (CF (CF<NUM>)CF<NUM>O), (CF<NUM>CF<NUM>O), and (CF<NUM>O)) constituting perfluoropolyether is not limited.

As the glass substrate, Gorilla Glass <NUM> (manufactured by Corning Inc. ) which had been subjected to chemical strengthening and surface polishing with a thickness of <NUM>, <NUM> x <NUM> was used, and after forming an intermediate layer, a surface-treating layer was formed on the intermediate layer to obtain a glass substrate with a surface-treating layer. Details are as follows.

The intermediate layer was formed by placing a silicon target and a tantalum target or a niobium target in an RAS or DC-sputtering apparatus, setting sputtering conditions for each example while introducing a mixed gas of argon and oxygen into the chamber, and forming intermediate layers made of composite oxides of silicon and tantalum or niobium in a thickness of <NUM>-<NUM> at various film formation rate ratios (Si/Ta).

The formation of the surface-treating layer was conducted using an apparatus capable of performing resistance heating vapor deposition. Specifically, a composition containing a fluorine-containing organosilicon compound was introduced into a heating vessel, the vessel was evacuated with a vacuum pump to distill off the solvent, and the heating vessel was heated to form a surface-treating layer on the intermediate layer. As the fluorine-containing organosilicon compound, compounds having the following structure were used.

CF<NUM>O(CF<NUM>CF<NUM>O)<NUM>(CF<NUM>O)<NUM>CF<NUM>CH<NUM>OCH<NUM>CH<NUM>CH<NUM>Si[CH<NUM>CH<NUM>CH<NUM>Si(OCH<NUM>)<NUM> ]<NUM>.

CF<NUM>CF<NUM>CF<NUM>O(CF<NUM>CF<NUM>CF<NUM>O)<NUM>CF<NUM>CF<NUM>(CH<NUM>CH[Si (OCH<NUM>)<NUM>])<NUM>H.

CF<NUM>CF<NUM>CF<NUM>O(CF<NUM>CF<NUM>CF<NUM>O)<NUM>CF<NUM>CF<NUM>CONHCH<NUM>CH<NUM>CH<NUM>Si(OCH<NUM>)<NUM>.

CF<NUM>CF<NUM>CF<NUM>O(CF<NUM>CF<NUM>CF<NUM>O)<NUM>CF<NUM>CF<NUM>CONHCH<NUM>C[CH<NUM>CH<NUM>CH<NUM>Si(OCH<NUM>)<NUM>]<NUM>.

[(CH<NUM>O)<NUM>SiCH<NUM>CH<NUM>CH<NUM>]<NUM>CCH<NUM>NHCOCF<NUM>O(CF<NUM>CF<NUM>O)<NUM>(CF<NUM>O)<NUM>CF<NUM>CONH CH<NUM>C[CH<NUM>CH<NUM>CH<NUM>Si(OCH<NUM>)<NUM>]<NUM>.

[(CH<NUM>O)<NUM>SiCH<NUM>CH<NUM>CH<NUM>]<NUM>CCH<NUM>NHCOCF<NUM>O(CF<NUM>CF<NUM>O)<NUM>(CF<NUM>O)<NUM>CF<NUM>CONHC H<NUM>C[CH<NUM>CH<NUM>CH<NUM>Si(OCH<NUM>)<NUM>]<NUM>.

[(CH<NUM>O)<NUM>SiCH<NUM>CH<NUM>CH<NUM>]<NUM>CCH<NUM>NHCOCF<NUM>CF<NUM>O(CF<NUM>CF<NUM>CF<NUM>O)<NUM>CF<NUM>CF<NUM>CON HCH<NUM>C[CH<NUM>CH<NUM>CH<NUM>Si(OCH<NUM>)<NUM>]<NUM>.

CF<NUM>CF<NUM>CF<NUM>O[CF(CF<NUM>)CF<NUM>O]<NUM>CFCONHCH<NUM>C[CH<NUM>CH<NUM>CH<NUM>Si(OCH<NUM>)<NUM>]<NUM>.

The glass substrate with the surface-treating layer obtained above was each subjected to measurement of the water contact angle, alkali test, and evaluation of friction durability as follows.

PTFE O-rings <NUM> in diameter were placed on the surfaces of the substrates surface-treated in Examples <NUM>, <NUM>, <NUM>, <NUM>-<NUM>, and <NUM> and Comparative Examples <NUM>, <NUM>-<NUM>, and <NUM>, and 8N NaOH solutions (aqueous alkali solutions) were dropped into the O-rings, the surfaces of the surface-treating layers were brought into contact with the aqueous alkali solutions, and alkali immersion tests were performed. After <NUM>-<NUM> minutes of the alkali immersion test, the aqueous alkali solution was wiped off and washed with pure water and ethanol, and then the contact angle with water was measured. The static contact angles of water were measured by dropping <NUM>µL of a water droplet of pure water on the surfaces of the glass substrates after the alkali immersion test and using a contact-angle meter (automatic contact-angle meter DropMaster701 manufactured by Kyowa Interface Science Co. The static contact angle of water after the alkali immersion test was measured at five points. When the measured value of the static contact angle of water was lowered within <NUM> minutes, the alkali immersion test was stopped on the way. The relationship between the immersion time and the average value of the contact angles at five points is shown in Table <NUM> below (wherein CE = Comparative Example).

The sample article on which the surface-treating layer was formed was horizontally disposed, the following friction element was brought into contact with the surface-treating layer (the contact surface was a circle having a <NUM> diameter), a 5N load was applied thereon, and then the friction block was reciprocated at a speed of <NUM>/sec in a state in which the load was applied. The friction block was reciprocated up to <NUM> times for Examples <NUM> and <NUM> and Comparative Example <NUM>, or up to <NUM>,<NUM> times for Examples <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM>, and Comparative Examples <NUM>-<NUM>, and the static contact angle (°) of water was measured for each reciprocation frequency (friction frequency) of <NUM> or <NUM>,<NUM> times. The test was stopped when the measured value of the static contact angle of water was less than <NUM>°. The static contact angle of water was measured in the same manner as in the alkali test. The results are shown in Table <NUM> below for Examples <NUM> and <NUM> and Comparative Example <NUM> using RAS, in Table <NUM> below for Examples <NUM>-<NUM>, <NUM>-<NUM> and <NUM>-<NUM> using DC, and in Table <NUM> below for Comparative Examples <NUM>-<NUM>.

The surfaces (<NUM> diameter) of the silicone rubber processed products shown below were covered with cotton soaked in artificial sweat having the compositional features shown below, and the products were used as friction blocks.

Compositional feature of artificial sweat:.

The compositional feature of the treated surfaces of the above treated glass substrates (analyzed in the depth direction) was analyzed using an X-ray photoelectron spectrometer (XPS, PHI <NUM> VersaProbe II manufactured by ULVAC-PHI, Inc. The measurement conditions for XPS analysis were as follows.

For the glass substrates with the surface-treating layer of Examples <NUM> and <NUM>, the peak areas of C1s, O1s, F1s, Si2p, and Ta4f orbitals were observed by XPS, and the atomic ratios and area ratios of carbon, oxygen, fluorine, silicon, and tantalum were calculated to obtain the compositional features of the treated surface including the surface-treating antifouling layer. The results are shown in Table <NUM> below for Examples <NUM> and <NUM> using RAS.

For the glass substrate with the surface-treating layer of Examples <NUM>-<NUM>, the layers (the surface-treating layer and the intermediate layer) on the substrate were etched gradually in the depth direction by sputtering with Ar ions for a predetermined time, and after each predetermined time, the peak areas of the O1s, Si2p, and Ta4f orbitals were observed by XPS, and the atomic ratio and the area ratio of oxygen and silicon were calculated to obtain the compositional features of the layer on the substrate surface. The etching rate in the sputtering was set to <NUM>/min. The results of Examples <NUM>-<NUM> are shown in Table <NUM> below.

From the above analysis results, it was confirmed that Examples in which the Si/Ta ratio was <NUM>-<NUM> (Si:Ta = (<NUM>:<NUM>)-(<NUM>:<NUM>)) had high alkali resistance and friction durability.

As understood from the above results, in Examples <NUM>-<NUM> in which the intermediate layer made of Si, Ta, and O or the intermediate layer made of Si, Nb, and O was formed between the substrate and the surface-treating layer, it was confirmed that a decrease in the contact angle in the alkali immersion test was suppressed and the alkali durability was excellent as compared with Comparative Examples <NUM>-<NUM> in which such an intermediate layer was not formed. Further, it was confirmed that in Examples <NUM>-<NUM>, a decrease in the contact angle in the abrasion durability test was suppressed, and the friction durability using artificial sweat was excellent.

Claim 1:
An article, comprising:
- a substrate;
- an intermediate layer located on the substrate and comprising a composite oxide which (i) is a composite oxide of Si and Ta or of Si and Nb, and (ii) constitutes a homogeneous phase; and
- a surface-treating layer located directly on the intermediate layer and formed from a surface-treating agent containing at least one fluorine-containing silane compound of formula (<NUM>) or (<NUM>):

        RF1α-XA-RSiβ     (<NUM>)

        RSiγ-XA-RF2-XA-RSiγ     (<NUM>)

wherein, each independently at each occurrence,
RF1 is Rf<NUM>-RF-Oq-, wherein Rf<NUM> is C<NUM>-<NUM>-alkyl optionally substituted with F, RF is a divalent fluoropolyether group, and q is <NUM> or <NUM>;
RF2 is -Rf<NUM>p-RF-Oq-, wherein RF and q are as defined above, Rf<NUM> each independently is C<NUM>-<NUM>-alkylene optionally substituted with F, and p is <NUM> or <NUM>;
RSi is a monovalent group containing a Si atom to which H, OH, a hydrolyzable group, or a monovalent organic group is bonded; and at least one RSi containing a Si atom to which OH or a hydrolyzable group is bonded;
XA is a single bond or a di- to decavalent organic group;
α is an integer of <NUM>-<NUM>;
β is an integer of <NUM>-<NUM>; and
γ each independently is an integer of <NUM>-<NUM>.