JP2023104892A - Antifouling article - Google Patents

Abstract

To provide an article comprising a surface treatment layer having high frictional durability.SOLUTION: The present invention provides an article comprising a substrate, an intermediate layer positioned on the substrate, and a surface treatment layer which is positioned on the intermediate layer and formed from a surface treatment agent including a fluorine-containing silane compound, the intermediate layer including a Ce-containing layer.SELECTED DRAWING: None

Description

The present disclosure relates to antifouling articles.

Certain fluorine-containing silane compounds are known to provide excellent water repellency, oil repellency, and antifouling properties when used for surface treatment of substrates. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a "surface treatment layer") can be used as a so-called functional thin film on various substrates such as glass, plastic, fiber, sanitary goods, and building materials. (Patent Documents 1 and 2).

JP 2014-218639 A JP 2017-082194 A

Although the fluorine-containing silane compound described in Patent Document 1 or Patent Document 2 can provide a surface treatment layer having excellent functions, there is a demand for an article having a surface treatment layer with higher friction durability.

An object of the present disclosure is to provide an article having a surface treatment layer with higher friction durability.

The present disclosure includes the following aspects.
[1] a substrate;
an intermediate layer located on the substrate;
a surface treatment layer positioned on the intermediate layer and formed of a surface treatment agent containing a fluorine-containing silane compound;
The article, wherein the intermediate layer comprises a Ce-containing layer.
[2] The article according to [1] above, wherein the Ce-containing layer further contains Si.
[3] The article according to [1] or [2] above, wherein the Ce-containing layer includes a composite oxide containing Si and Ce.
[4] The article according to [2] or [3] above, wherein the Ce-containing layer has a molar ratio of Si to Ce of 10:90 to 99.99:0.01.
[5] The article according to any one of [1] to [4] above, wherein the intermediate layer further contains an alkali metal or alkaline earth metal.
[6] The article according to [5] above, wherein the concentration of the alkali metal and alkaline earth metal in the intermediate layer is 0.1 to 30 mol %.
[7] The article according to any one of [1] to [6] above, wherein the Ce-containing layer has a thickness of 0.1 to 100 nm.
[8] The article according to any one of [1] to [7] above, wherein the intermediate layer comprises a Ce-containing layer.
[9] The article according to any one of [1] to [7] above, wherein the intermediate layer further includes a silicon oxide layer on the Ce-containing layer.
[10] The article according to [9] above, wherein the silicon oxide layer has a thickness of 0.1 nm to 100 nm.
[11] The fluorine-containing silane compound has the following formula (1) or (2):
[In the formula:
each R ^F1 is independently Rf ¹ —R ^F —O _q —;
R ^F2 is -Rf ² _p -R ^F -O _q -;
each Rf ¹ is independently a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
each R ^F is independently a divalent fluoropolyether group;
p is 0 or 1;
each q is independently 0 or 1;
R ^Si is each independently 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;
at least one R ^Si is a monovalent group comprising a Si atom to which a hydroxyl or hydrolyzable group is attached;
each X ^A is independently a single bond or a divalent to decavalent organic group;
α is an integer from 1 to 9;
β is an integer from 1 to 9;
Each γ is independently an integer of 1-9. ]
The article according to any one of [1] to [10] above, which is at least one fluoropolyether group-containing compound represented by
[12] R ^F is each independently represented by the formula:
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ R ^Fa ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f -
[Wherein, each R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom,
a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more; The order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula. ]
The article according to [11] above, which is a group represented by
[13] each Rf ¹ is independently a C _1-16 perfluoroalkyl group;
each Rf ² is independently a C _1-6 perfluoroalkylene group;
The article according to [12] above, wherein R ^Fa is a fluorine atom.
[14] R ^F is, at each occurrence independently, the following formula (f1), (f2), (f3), (f4), (f5) or (f6):
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, d is an integer of 1 to 200, and e is 0 or 1. ],
-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)
[Wherein, c and d are each independently an integer of 0 to 30;
e and f are each independently an integer from 1 to 200;
the sum of c, d, e and f is an integer from 10 to 200;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ],
-(R ⁶ -R ⁷ ) _g - (f3)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or two or three groups selected from these groups. is a combination of groups;
g is an integer from 2 to 100; ],
—(R ⁶ —R ⁷ ) _g —R ^r —(R ^7′ —R ^6′ ) _g′ − (f4)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or 2 independently selected from these groups or a combination of three groups,
R ^6' is OCF ₂ or OC ₂ F ₄ ;
R ^7′ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
^Rr is
(In the formula, * indicates the binding position.)
is. ];
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f5)
[Wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and a, b, c, d, The order of existence of each repeating unit bracketed with e or f is arbitrary in the formula. ]
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f6)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d, The order of existence of each repeating unit bracketed with e or f is arbitrary in the formula. ]
The article according to any one of [11] to [13] above, which is a group represented by
[15] R ^Si is represented by the following formula (S1), (S2), (S3), (S4) or (S5):
[In the formula:
R ¹¹ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ¹² is independently at each occurrence a hydrogen atom or a monovalent organic group;
n1 is an integer of 0 to 3 independently for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit;
X ¹¹ is independently at each occurrence a single bond or a divalent organic group;
R ¹³ is independently at each occurrence a hydrogen atom or a monovalent organic group;
t is independently at each occurrence an integer greater than or equal to 2;
R ¹⁴ is independently at each occurrence a hydrogen atom, a halogen atom or —X ¹¹ —SiR ¹¹ _n1 R ¹² _3-n1 ;
each occurrence of R ¹⁵ is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms;
R ^a1 is independently at each occurrence -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ;
Z ¹ is independently at each occurrence an oxygen atom or a divalent organic group;
R ²¹ is independently at each occurrence -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ;
R ²² is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ²³ is independently at each occurrence a hydrogen atom or a monovalent organic group;
p1 is independently at each occurrence an integer from 0 to 3;
q1 is independently at each occurrence an integer from 0 to 3;
r1 is independently at each occurrence an integer from 0 to 3;
the sum of p1, q1, and r1 is 3 in the ^SiR21 _p1 ^R22 _q1 ^R23 _r1 unit;
the sum of p1, q1 and r1 is 3;
Z ^1′ is independently at each occurrence an oxygen atom or a divalent organic group;
R ^21′ is independently at each occurrence —Z ^1″ —SiR ^22″ _q1″ R ^23″ _r1″ ;
R ^22′ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ^23′ at each occurrence is independently a hydrogen atom or a monovalent organic group;
p1′ is independently at each occurrence an integer from 0 to 3;
q' is independently at each occurrence an integer from 0 to 3;
r' is independently at each occurrence an integer from 0 to 3;
the sum of p1′, q1′ and r1′ is 3 in the SiR ^21′ _p1′ R ^22′ _q1′ R ^23′ _r1′ unit;
Z ^1″ is independently at each occurrence an oxygen atom or a divalent organic group;
R ^22″ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ^23″ at each occurrence is independently a hydrogen atom or a monovalent organic group;
q1″ is independently at each occurrence an integer from 0 to 3;
r1″ is independently at each occurrence an integer from 0 to 3;
the sum of q1″ and r1″ is 3 in SiR ^22″ _q1″ R ^23″ _r1″ units;
each occurrence of R ^b1 is independently a hydroxyl group or a hydrolyzable group;
R ^c1 is independently at each occurrence a hydrogen atom or a monovalent organic group;
k1 is independently at each occurrence an integer from 0 to 3;
l1 is independently at each occurrence an integer from 0 to 3;
m1 is independently at each occurrence an integer from 0 to 3;
the sum of k1, l1 and m1 is 3 in SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 units;
R ^d1 is independently at each occurrence -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ;
Z ² is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
R ³¹ is independently at each occurrence -Z ^2' -CR ^32' _q2' R ^33' _r2' ;
R ³² is independently at each occurrence -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;
each occurrence of R ³³ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group;
p2 is independently at each occurrence an integer from 0 to 3;
q2 is independently at each occurrence an integer from 0 to 3;
r2 is independently at each occurrence an integer from 0 to 3;
The sum of p2, q2, and r2 is 3 in the SiR ³¹ _p2 R ³² _q2 R ³³ _r2 unit, and Z ^2′ is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group. can be;
R ^32′ is independently at each occurrence —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ^33′ is independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group;
q2' is independently at each occurrence an integer from 0 to 3;
r2' is independently at each occurrence an integer from 0 to 3;
the sum of q2' and r2' is 3 in the SiR ^32' _q2' R ^33' _r2' unit;
Z ³ is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
R ³⁴ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ³⁵ is independently at each occurrence a hydrogen atom or a monovalent organic group;
n2 is independently at each occurrence an integer from 0 to 3;
R ^e1 is independently at each occurrence —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ^f1 is independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group;
k2 is independently at each occurrence an integer from 0 to 3;
l2 is independently at each occurrence an integer from 0 to 3;
m2 is independently at each occurrence an integer from 0 to 3;
the sum of k2, l2 and m2 is 3 in CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 units;
R ^g1 and R ^h1 are each independently at each occurrence -Z ⁴ -SiR ¹¹ _n1 R ¹² _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ;
Z ⁴ is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
However, in formulas (S1), (S2), (S3), (S4) and (S5), there is at least one Si atom to which a hydroxyl group or hydrolyzable group is bonded. ]
The article according to any one of [11] to [14] above, which is a group represented by
[16] X ^A is each independently a single bond or a divalent organic group,
The article according to any one of [11] to [15] above, wherein α, β, and γ are 1.
[17] X ^A is each independently a trivalent organic group,
α is 1 and β is 2, or α is 2 and β is 1,
γ is 2;
The article according to any one of [11] to [15] above.
[18] The article according to any one of [1] to [17] above, wherein the substrate is a glass substrate.
[19] A film-forming material containing silicon oxide and cerium oxide, wherein the molar ratio of silicon atoms to cerium atoms is from 10:90 to 99.99:0.01.
[20] The above-described [19], further comprising 0.1 to 30 mol% of an alkali metal or alkaline earth metal relative to the total amount of silicon atoms, cerium atoms, and alkali metals and alkaline earth metals. deposition material.

According to the present disclosure, it is possible to provide an article having a surface treatment layer with higher friction durability.

Articles of the present disclosure comprise a substrate,
an intermediate layer positioned on the substrate;
a surface treatment layer formed from a surface treatment agent containing a fluorine-containing silane compound located on the intermediate layer;
The intermediate layer includes a Ce-containing layer.

Substrates that can be used in the present disclosure include, for example, glass, resins (natural or synthetic resins, such as common plastic materials), metals, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, non-woven fabrics etc.), fur, leather, wood, ceramics, stone, etc., construction members, etc., sanitary products, and any suitable material.

For example, when the article to be manufactured is an optical member, the material forming the surface of the substrate may be a material for optical members, such as glass or transparent plastic.

In one aspect, some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate. The antireflection layer may be either a single antireflection layer or a multi-layer antireflection layer. Examples of inorganic materials _that can be used for the antireflection layer include _SiO2 , SiO, _ZrO2 , _TiO2 , _TiO , _{Ti2O3 , Ti2O5} , _Al2O3 , _{Ta2O5 , Ta3O5 .} , Nb ₂ O ₅ , HfO ₂ , Si ₃ N ₄ , 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 (for example, as a mixture). In the case of a multi-layer antireflection layer, it is preferable to use SiO ₂ and/or SiO for the outermost layer. When the article to be manufactured is an optical member, particularly an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is applied to one surface of the substrate (glass). You may have it in the department. In addition, depending on the specific specifications of the base material, an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase retardation film, and a liquid crystal display module.

In another embodiment, the surface of the substrate does not have any layers as described above. That is, the intermediate layer is provided in direct contact with the substrate.

The shape of the substrate is not particularly limited, and may be, for example, plate-like, film, or other shapes. Moreover, the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the application and specific specifications of the article to be manufactured.

In one embodiment, such a substrate may consist of a material that originally has hydroxyl groups, at least at its surface portion. Examples of such materials include glass, metals (particularly base metals), ceramics, and semiconductors on which a natural oxide film or thermal oxide film is formed. In the case where it is not sufficient to have hydroxyl groups, such as resins, etc., or when it does not originally have hydroxyl groups, hydroxyl groups can be introduced into the surface of the base material by subjecting the base material to some kind of pretreatment. , can be increased. Examples of such pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign matter and the like). Further, as another example of such a pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is preliminarily formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method), a chemical adsorption method, or the like. A method in which the unsaturated bond is cleaved in an atmosphere containing oxygen, nitrogen, or the like is exemplified.

Alternatively, such a substrate may comprise, at least a portion of its surface, another reactive group, such as a silicone compound having one or more Si—H groups, or a material comprising an alkoxysilane. .

In a preferred embodiment, the substrate is glass. As such glass, sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, and chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glasses are particularly preferred.

The intermediate layer is located on the substrate.

By providing the intermediate layer, the durability of the surface treatment layer can be improved. Durability means weather resistance, abrasion resistance, and the like.

The intermediate layer may be formed in contact with the base material, or may be formed on the base material via another layer. In a preferred embodiment, the intermediate layer is formed in contact with the substrate.

The intermediate layer includes a Ce-containing layer. A Ce-containing layer means a layer containing cerium (Ce) atoms.

The Ce is preferably contained in the Ce-containing layer as an oxide. The oxide may be a composite oxide with other metal atoms.

Here, the composite oxide includes oxides of a plurality of elements forming a homogeneous phase, so-called solid solutions, as well as oxides of a plurality of elements forming a heterogeneous phase. The composite oxide is preferably composed of a solid solution forming a homogeneous phase.

In one aspect, the Ce-containing layer consists of cerium oxide. Here, "the Ce-containing layer is composed of cerium oxide" means that the Ce-containing layer contains other components, such as metal atoms, as unavoidable trace components, in the form of simple substances, ions, salts, oxides, and the like. allowed to be included in the state of

The cerium oxide may contain those with different oxidation states. For example, cerium oxide may include different oxidation states, such as CeO _x (x=1-2). In a preferred embodiment, the cerium oxide is _CeO2 .

In another aspect, the Ce-containing layer may further contain other metal atoms. These metal atoms may exist as individual oxides, or may exist as composite oxides with Ce or as composite oxides containing no Ce.

In this specification, metal atoms also include metalloid atoms such as B, Si, Ge, Sb, As and Te.

The other metal atoms may be, for example, one or more atoms selected from transition metals of Groups 3 to 11 and typical metal elements of Groups 12 to 15 of the periodic table. The other metal atoms are preferably group 3 to group 11 transition metal atoms, more preferably group 3 to group 7 transition metal atoms, and still more preferably group 4 to 6 transition metal atoms.

In one aspect, the other metal atoms are Si, Y, Ru, In, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Bi It may be one or more metal atoms selected from the group consisting of

In a preferred embodiment, the Ce-containing layer further contains Si.

In a preferred embodiment, Ce and Si are contained in the Ce-containing layer as composite oxides. That is, the Ce-containing layer contains a composite oxide containing Ce and Si.

In another aspect, the Ce and Si are included in the Ce-containing layer as separate oxides.

The oxides may include those with different oxidation states. For example, cerium oxide may include CeO _x (x=1 to 2), silicon oxide may include SiO _y (y=1 to 2), and the like. In a preferred embodiment, the cerium oxide is _CeO2 and the silicon oxide is _SiO2 .

In a preferred embodiment, metal atoms contained in the Ce-containing layer are substantially only Si and Ce. Here, "the metal atoms contained in the Ce-containing layer are substantially only Si and Ce" allow the Ce-containing layer to contain other metal atoms as unavoidable minor components.

In one embodiment, the molar ratio of Si to Ce in the Ce-containing layer is from 10:90 to 99.99:0.01 (Si:Ce), preferably from 40:60 to 99.99:0.01 , more preferably 60:40 to 99:1, still more preferably 90:10 to 99:1, particularly preferably 90:10 to 98:2. By setting the molar ratio of Si to Ce within this range, the durability of the surface treatment layer is improved. In addition, when the molar ratio of Si and Ce differs depending on the depth, the molar ratio of Si and Ce in the Ce-containing layer may be the average value.

The composition and ratio of the intermediate layer such as the Ce-containing layer can be determined by surface analysis. As a surface analysis method, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, or the like can be used. Typically, X-ray photoelectron spectroscopy is used.

XPS, PHI5000 VersaProbe II manufactured by ULVAC-PHI, Inc. can be used as an apparatus for performing X-ray photoelectron spectroscopy for measuring the composition and ratio of the intermediate layer. The measurement conditions for the XPS analysis are as follows: monochromatic AlKα rays of 25 W for the X-ray source, a photoelectron detection area of 1400 μm × 300 μm, and a photoelectron detection angle in the range of 20 degrees to 90 degrees (eg, 20 degrees, 45 degrees, 90 degrees). , a pass energy of 23.5 eV, and Ar ions can be used as sputtering ions. Observing the peak areas of C1s, O1s, F1s, Si2p orbitals, and appropriate orbitals of other metals using the above equipment and measurement conditions, and calculating the atomic ratios of carbon, oxygen, fluorine, silicon, and other metals. The composition of the laminate can be determined by Suitable orbitals of other metals include, for example, 1s orbitals for atomic number 5 (B), 2p orbitals for atomic numbers 13-14, 21-31 (Al-Si, Sc-Ga), 32-33 atomic numbers, 39-52 and 58 (Ge-As, Y-Te, Ce) are 3d orbitals, and atomic numbers 72-83 (Hf-Bi) are 4f orbitals.

It is also possible to perform a depth analysis of the intermediate layer. The measurement conditions for the XPS analysis are as follows: monochromatic AlKα rays at 25 W are used as the X-ray source, the photoelectron detection area is 1400 μm × 300 μm, and the photoelectron detection angle is in the range of 20 degrees to 90 degrees (eg, 20 degrees, 45 degrees, 90 degrees degree), a pass energy of 23.5 eV, and Ar ions can be used as sputtering ions. The _intermediate layer was etched 1 to 100 nm in terms of SiO by sputtering with Ar ions, and the peak areas of O1s, Si2p orbitals, and appropriate orbitals of other metals were observed at each depth after etching, and oxygen, silicon , and other metals, the composition inside the intermediate layer can be determined. Suitable orbitals of other metals include, for example, 1s orbitals for atomic number 5 (B), 2p orbitals for atomic numbers 13-14, 21-31 (Al-Si, Sc-Ga), 32-33 atomic numbers, 39-52 and 58 (Ge-As, Y-Te, Ce) are 3d orbitals, and atomic numbers 72-83 (Hf-Bi) are 4f orbitals.

By adjusting the photoelectron detection angle of the XPS analysis described above, the detection depth can be adjusted as appropriate. For example, a shallow angle close to 20 degrees allows the detection depth to be about 3 nm, while a deep angle close to 90 degrees allows the detection depth to be about 10 and several nm. can.

In the composition analysis by XPS analysis, when Si or the like is detected in the base material, specific atoms in the base material, for example, when the base material is glass, metal atoms contained in trace amounts (e.g., Al, Na, K, B, Ca, Mg, Sn, etc.) is calculated from the detected amount of Si in the base material, and subtracted from the measurement result to calculate the composition of the intermediate layer.

In one aspect, the intermediate layer may further contain an alkali metal or an alkaline earth metal, preferably an alkali metal. By including an alkali metal in the intermediate layer, the friction durability, weather resistance, etc. of the surface treatment layer are improved. The alkali metal and alkaline earth metal contained in the intermediate layer may be contained in the Ce-containing layer, may be contained in another layer, or may be contained in both of these layers. good too.

Alkali metals and alkaline earth metals in the intermediate layer may be uniformly present, or may be segregated on the surface of the intermediate layer (surface treatment layer side). Preferably, the alkali metal and alkaline earth metal in the intermediate layer are segregated on the surface of the intermediate layer.

Examples of the alkali metals include Li, Na, K, Rb, Cs, and Fr. The alkali metal is preferably Na or K, more preferably Na.

The alkaline earth metals include Be, Mg, Ca, Sr, Ba, and Ra. The alkali metal is preferably Mg or Ca.

The content of alkali metals and alkaline earth metals in the intermediate layer (the total content when multiple types are present) is not particularly limited, but is preferably 0.00 to the total of all metal atoms contained in the intermediate layer. 1 to 30 mol%, more preferably 0.1 to 20 mol%, still more preferably 0.1 to 15 mol%, still more preferably 0.5 to 15 mol%, for example 1.0 to 15 mol% or 1 .0 to 10 mol %. By setting the concentration of the alkali metal and alkaline earth metal in the intermediate layer within the above range, the friction durability, weather resistance, etc. of the surface treatment layer are improved. In addition, the concentration of the alkali metal and alkaline earth metal in the intermediate layer is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 15 mol% or less, thereby improving the friction durability of the surface treatment layer. is better.

The intermediate layer may be a single layer or multiple layers. The boundary between layers in the intermediate layer is a portion where the composition clearly differs in the thickness direction, and the layers above and below the boundary are regarded as different layers. A portion where the composition gradually changes with a gradient in the thickness direction is not a boundary, but is regarded as one layer.

In one embodiment, the intermediate layer is a single layer.

When the intermediate layer is a single layer, the intermediate layer is a Ce-containing layer.

If the intermediate layer is a single layer, the Ce-containing layer preferably contains Si and Ce. In such a Ce-containing layer, Si atoms are preferably present on the surface in contact with the surface treatment layer. By allowing Si atoms to exist on the surface of the Ce-containing layer on the side of the surface treatment layer, the surface treatment layer is improved in friction durability, weather resistance, and the like.

In one aspect, in the Ce-containing layer containing Si and Ce, it is preferable that the Si concentration gradient gradually increases toward the surface treatment layer side. By gradually increasing the concentration gradient of Si toward the surface treatment layer side, the friction durability, weather resistance, etc. of the surface treatment layer are improved.

In another aspect, the intermediate layer is multilayer.

When the intermediate layer is multilayer, the intermediate layer includes a Ce-containing layer and a Si-containing layer.

In one aspect, the intermediate layer consists of a Ce-containing layer and a Si-containing layer.

In a preferred embodiment, the intermediate layer further comprises a Si-containing layer on the Ce-containing layer. That is, the intermediate layer includes a Ce-containing layer located on the substrate side and a Si-containing layer located on the Ce-containing layer and in contact with the surface treatment layer. By arranging the Ce-containing layer and the Si-containing layer in the above order, the friction durability, weather resistance, etc. of the surface treatment layer are improved.

In a preferred embodiment, the intermediate layer consists of a Ce-containing layer located on the substrate and a Si-containing layer located directly on the Ce-containing layer.

The thickness of the intermediate layer (in the case of multiple layers, the total thickness of all layers) is not particularly limited, but may be, for example, 1.0 nm or more, preferably 2.0 nm or more, and more preferably 3.0 nm or more. . By setting the thickness of the intermediate layer to 1.0 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably. In addition, the thickness of the intermediate layer (in the case of multiple layers, the total thickness of all layers) is not particularly limited. Particularly preferably, it may be 10 nm or less. By setting the thickness of the intermediate layer to 120 nm or less, the transparency of the article can be further enhanced. The thickness of the intermediate layer (in the case of multiple layers, the total thickness of all layers) is preferably 1.0 to 120 nm, more preferably 2.0 to 60 nm, even more preferably 2.0 to 25 nm, and even more preferably can be from 3.0 nm to 10 nm.

The thickness of the Ce-containing layer is not particularly limited. By setting the thickness of the Ce-containing layer to 0.1 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably. The thickness of the Ce-containing layer is not particularly limited, but may be, for example, 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less. By setting the thickness of the Ce-containing layer to 100 nm or less, the transparency of the article can be further enhanced. The Ce-containing layer may preferably have a thickness of 0.1 to 100 nm, more preferably 1.0 to 50 nm, even more preferably 2.0 to 20 nm, still more preferably 3.0 nm to 10 nm.

When present, the thickness of the layer containing other metals is not particularly limited, but is, for example, 0.1 nm or more, preferably 1.0 nm or more, more preferably 2.0 nm or more, and still more preferably 3.0 nm or more. could be. By setting the thickness of the layer containing the other metal to 0.1 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably. The thickness of the layer containing the other metal is not particularly limited, but may be, for example, 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less. By setting the thickness of the layer containing the other metal to 100 nm or less, the transparency of the article can be further enhanced. The thickness of the layer containing the other metal may be preferably 0.1 to 100 nm, more preferably 1.0 to 50 nm, still more preferably 2.0 to 20 nm, still more preferably 3.0 nm to 10 nm. .

In particular, the thickness of the Si-containing layer, if present, is not particularly limited, but can be, for example, 0.1 nm or greater, preferably 1.0 nm or greater, more preferably 2.0 nm or greater, and even more preferably 3.0 nm or greater. . By setting the thickness of the Si-containing layer to 1.0 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably. The thickness of the Si-containing layer is not particularly limited, but may be, for example, 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less. By setting the thickness of the Si-containing layer to 100 nm or less, the transparency of the article can be further enhanced. The thickness of the Si-containing layer can be preferably 0.1-100 nm, more preferably 1.0-50 nm, even more preferably 2.0-20 nm, still more preferably 3.0-10 nm.

In a preferred embodiment, the intermediate layer comprises a Ce-containing layer positioned on the substrate and a Si-containing layer positioned in direct contact with the Ce-containing layer, and the Ce-containing layer has a thickness of 0.1 to 20 nm, preferably is 1.0 to 10 nm, and the thickness of the Si-containing layer is 0.1 to 20 nm, preferably 1.0 to 10 nm.

The thickness of each layer can be measured by a combination of XPS analysis and sputtering. Specifically, the thickness of the layer can be measured by analyzing the depth direction and measuring the depth of the sputtering ring with the location where the composition clearly changes as the boundary of each layer.

The method for forming the intermediate layer is not particularly limited, but for example, sputtering, ion beam assist, vacuum deposition (preferably electron beam heating method), CVD (chemical vapor deposition), atomic layer deposition, etc. can be used. Vacuum deposition or sputtering is preferably used.

As the sputtering method, a sputtering method using a DC (direct current) sputtering method, an AC (alternating current) sputtering method, an RF (radio frequency) sputtering method, an RAS (radical assist) sputtering method, or the like can be used. These sputtering methods may be bipolar sputtering or magnetron sputtering.

When forming a film by a sputtering method, the substrate is placed in a chamber having a mixed gas atmosphere of an inert gas and an oxygen gas, and a target is selected so as to have a desired composition as an intermediate layer forming material to form a film. do. At this time, the type of inert gas in the chamber is not particularly limited, and various inert gases such as argon and helium can be used.

The pressure in the chamber due to the mixed gas of the inert gas and the oxygen gas is not particularly limited, but the surface roughness of the film to be formed is kept in the preferable range by setting it in the range of 0.5 Pa or less. is easy. This is considered to be due to the reason shown below. That is, when the pressure in the chamber due to the mixed gas of the inert gas and the oxygen gas is 0.5 Pa or less, the mean free path of the film-forming molecules is ensured, and the film-forming molecules reach the substrate with more energy. . Therefore, rearrangement of the film-forming molecules is promoted, and it is considered that a film having a relatively dense and smooth surface can be formed. The lower limit of the pressure in the chamber due to the mixed gas of inert gas and oxygen gas is not particularly limited, but is preferably 0.1 Pa or more, for example.

In the method for forming the intermediate layer, a film forming material containing cerium oxide is used.

In a preferred embodiment, the film-forming material comprises silicon oxide and cerium oxide.

In the film-forming material containing silicon oxide and cerium oxide, the molar ratio of silicon atoms to cerium atoms is preferably 10:90 to 99.99:0.01 (Si:Ce), more preferably 10 :90 to 99:1, more preferably 10:90 to 95:5, still more preferably 20:80 to 90:10, particularly preferably 40:60 to 80:20. By setting the molar ratio of Si and Ce in the film forming material to such a range, the durability of the surface treatment layer is improved.

(Preparation of film-forming material)
Specific examples of the form of the film-forming material include powder, melt, sintered body, granules, and crushed bodies, and from the viewpoint of handleability, melts, sintered bodies, and granules are preferable.

Here, the melt means a solid obtained by melting the powder of the film-forming material at a high temperature and then cooling and solidifying it. A sintered body means a solid obtained by firing the powder of the film-forming material, and if necessary, instead of the powder of the film-forming material, the powder is pressed to form a compact. may be used. A granule means a solid obtained by kneading a powder of a film-forming material and a liquid medium (for example, water or an organic solvent) to obtain particles, and then drying the particles.

A film-forming material can be manufactured by the following method, for example.
- A method of mixing silicon oxide powder and cerium oxide powder to obtain a film-forming material powder.
- A method of obtaining granules of the film-forming material by kneading the powder of the film-forming material and water to obtain particles, followed by drying the particles.
・Powder containing silicon (for example, powder made of silicon oxide, silica sand, silica gel) and powder containing cerium oxide (for example, cerium oxide powder, carbonate, sulfate, nitrate, oxalate) , hydroxide) and water are dried, and then the dried mixture or a compact obtained by press-molding the dried mixture is fired to obtain a sintered body.
・Powder containing silicon (for example, powder made of silicon oxide, silica sand, silica gel) and powder containing cerium (for example, cerium oxide powder, carbonate, sulfate, nitrate, oxalate, hydroxide) and are melted at a high temperature, and then the melt is cooled and solidified to obtain a melt.
・An oxide obtained by reacting an alkoxide or chloride containing silicon (e.g. tetramethoxysilane, tetraethoxysilane, tetraisopropylsilane, tetrachlorosilane) with an alkoxide containing cerium (e.g. cerium isopropoxide) and water A method of obtaining a sintered body by drying a solid, press-molding it, and then sintering it.
- A method of obtaining a sintered body by reacting either one of silicon and cerium with an oxide in the case of using the above alkoxide, drying the resulting oxide solid, press-molding it, and then sintering it.
etc. can be considered.

In a preferred embodiment, the film-forming material further contains an alkali metal or alkaline earth metal, preferably an alkali metal, in addition to silicon oxide and cerium oxide.

The alkali metals and alkaline earth metals are contained in the form of ions, oxides, or salts.

The alkali metal and alkaline earth metal are preferably 0.1 to 30 mol%, more preferably 0.1 to 20 mol%, based on the total amount of silicon atoms, cerium atoms, alkali metals and alkaline earth metals, More preferably 0.1 to 15 mol %, still more preferably 0.5 to 15 mol %, for example 1.0 to 15 mol % or 1.0 to 10 mol %. By setting the concentration of the alkali metal in the film forming material within the above range, the friction durability, weather resistance, etc. of the surface treatment layer are improved.

In one aspect, the film-forming material is a vapor deposition material.

The surface treatment layer is located on the intermediate layer. Preferably, the surface treatment layer is positioned directly above the intermediate layer, that is, in contact with the intermediate layer.

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

As used herein, "monovalent organic radical" means a monovalent radical containing carbon. Although the monovalent organic group is not particularly limited, it may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group is a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. means In addition, when it shows simply as an "organic group", it means a monovalent organic group. Further, the “divalent to decavalent organic group” means a divalent to decavalent group containing carbon. Such a divalent to decavalent organic group is not particularly limited, but includes a divalent to decavalent group in which 1 to 9 hydrogen atoms are further eliminated from an organic group. For example, the divalent organic group is not particularly limited, but includes a divalent group in which one hydrogen atom is further eliminated from the organic group.

As used herein, "hydrocarbon group" means a group containing carbon and hydrogen from which one hydrogen atom has been removed from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C _1-20 hydrocarbon groups optionally substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic A hydrocarbon group etc. are mentioned. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Hydrocarbon groups may also contain one or more ring structures.

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

As used herein, "hydrolyzable group" means a group capable of undergoing a hydrolysis reaction, ie, a group capable of being detached from the backbone of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, halogen (wherein R ^j is a substituted or represents an unsubstituted C _1-4 alkyl group).

The fluorine-containing silane compound is represented by the following formula (1) or (2):
[In the formula:
R ^F1 is independently at each occurrence Rf ¹ -R ^F -O _q -;
R ^F2 is -Rf ² _p -R ^F -O _q -;
Rf ¹ is independently at each occurrence a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
R ^F is independently at each occurrence a divalent fluoropolyether group;
p is 0 or 1;
q is independently 0 or 1 at each occurrence;
R ^Si is independently at each occurrence a monovalent group comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group;
at least one R ^Si is a monovalent group comprising a Si atom to which a hydroxyl group or a hydrolyzable group is attached;
each X ^A is independently a single bond or a divalent to decavalent organic group;
α is an integer from 1 to 9;
β is an integer from 1 to 9;
Each γ is independently an integer of 1-9. ]
is at least one fluorine-containing silane compound represented by

In formula (1) above, each occurrence of R ^F1 is independently Rf ¹ —R ^F —O _q —.

In the above formula (2), R ^F2 is -Rf ² _p -R ^F -O _q -.

In the above formula, Rf ¹ at each occurrence is independently a C _1-16 alkyl group optionally substituted by one or more fluorine atoms.

The "C _1-16 alkyl group" in the C _1-16 alkyl group optionally substituted by one or more fluorine atoms may be linear or branched, preferably is a straight or branched C _1-6 alkyl group, especially a C _1-3 alkyl group, more preferably a straight chain C _1-6 alkyl group, especially a C _1-3 alkyl group.

Rf ¹ above is preferably a C _1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 perfluoroalkylene group, still more preferably is a C _1-16 perfluoroalkyl group.

The C _1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C _1-6 perfluoroalkyl group, especially C _{1- 3} perfluoroalkyl group, more preferably a linear C _1-6 perfluoroalkyl group, particularly a C _1-3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ .

In the above formula, Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms.

The "C _1-6 alkylene group" in the C _1-6 alkylene group optionally substituted by one or more fluorine atoms may be linear or branched, preferably is a linear or branched C _1-3 alkylene group, more preferably a linear C _1-3 alkylene group.

Rf ² above is preferably a C _1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C _1-6 perfluoroalkylene group, still more preferably C _{1- 3} is a perfluoroalkylene group.

The C _1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C _1-3 perfluoroalkylene group, more preferably is a linear C _1-3 perfluoroalkylene group, specifically -CF ₂ -, -CF ₂ CF ₂ -, or -CF ₂ CF ₂ CF ₂ -.

In the above formula, p is 0 or 1. In one aspect, p is zero. In another aspect, p is 1.

In the above formula, q is 0 or 1 independently at each occurrence. In one aspect, q is zero. In another aspect q is 1.

In formulas (1) and (2) above, each occurrence of ^RF is independently a divalent fluoropolyether group.

R ^F is preferably:
- (OC _h1 R ^Fa _2h1 ) _h3 - (OC _h2 R ^Fa _2h2-2 ) _h4 -
[In the formula:
R ^Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom;
h1 is an integer from 1 to 6,
h2 is an integer from 4 to 8,
h3 is an integer of 0 or more,
h4 is an integer of 0 or more,
However, the composition of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of existence of each repeating unit bracketed with h3 and h4 is Optional. ]
It may contain a group represented by

In one aspect, R ^F can be linear or branched. R ^F preferably has the formula:
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ R ^Fa ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f -
[In the formula:
R ^Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom;
a, b, c, d, e and f are each independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit bracketed with a, b, c, d, e or f is arbitrary in the formula. However, when all ^RFa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more. ]
is a group represented by

^RFa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, when all ^RFa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.

a, b, c, d, e and f may preferably each independently be an integer from 0 to 100.

The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

These repeating units may be linear or branched. _For example, -( _{OC6F12 ) - is} -( _{OCF2CF2CF2CF2CF2CF2} ) _{- ,} -( _OCF ( _CF3 ) _{CF2CF2CF2CF2 )} -, - ₍ OCF ₂ CF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-, - (OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-, - (OCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ )- , -(OCF ₂ CF ₂ CF ₂ CF ₂ CF(CF ₃ ))- and the like. -( _OC5F10 )- is -( _{OCF2CF2CF2CF2CF2 ) - ,} -( _{OCF ( CF3} ) _CF2CF2CF2 )-, _{- ( OCF2CF} ( _CF3 ) CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))- and the like. -( _OC4F8 )- is -( _{OCF2CF2CF2CF2 ) -} , -( _OCF ( _CF3 ) _CF2CF2 )- _, -( _OCF2CF ( _CF3 ) _CF2 ) _- , -( _OCF2CF2CF ( _CF3 ))-, - ₍ OC( _CF3 ) _2CF2 )-, -( _OCF2C ( _CF3 ) ₂ ) _- , -(OCF( _CF3 )CF( CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-. -(OC ₃ F ₆ )- (that is, in the above formula, R 3 ^Fa is a fluorine atom) is represented by -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -( OCF ₂ CF(CF ₃ ))—. -(OC ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- or -(OCF(CF ₃ ))-.

In one aspect, the repeating unit is linear. By making the repeating unit linear, it is possible to improve the surface lubricity, abrasion resistance, etc. of the surface treatment layer.

In one aspect, the repeat unit is branched. By branching the repeating unit, the dynamic friction coefficient of the surface treatment layer can be increased.

In one aspect, R ^F can include a ring structure.

The ring structure may be the following three-membered ring, four-membered ring, five-membered ring, or six-membered ring.
[In the formula, * indicates a binding position. ]

The ring structure can be preferably a four-, five- or six-membered ring, more preferably a four- or six-membered ring.

The repeating unit having a ring structure can preferably be the following units.
[In the formula, * indicates a binding position. ]

In one embodiment, each occurrence of R 1 ^F is independently a group represented by any one of the following formulas (f1) to (f6).
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, d is an integer of 1 to 200, and e is 0 or 1. ];
-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)
[Wherein, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less,
the sum of c, d, e and f is greater than or equal to 2;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ];
-(R ⁶ -R ⁷ ) _g - (f3)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or 2 independently selected from these groups or a combination of three groups,
g is an integer from 2 to 100; ];
—(R ⁶ —R ⁷ ) _g —R ^r —(R ^7′ —R ^6′ ) _g′ − (f4)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or 2 independently selected from these groups or a combination of three groups,
R ^6' is OCF ₂ or OC ₂ F ₄ ;
R ^7′ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
^Rr is
(In the formula, * indicates the binding position.)
is. ];
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f5)
[Wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and a, b, c, d , e or f in parentheses may be present in any order in the formula. ]
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f6)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d , e or f in parentheses may be present in any order in the formula. ]

In the above formula (f1), d is preferably an integer of 5-200, more preferably 10-100, still more preferably 15-50, for example 25-35. OC ₃ F ₆ in the above formula (f1) is preferably (OCF ₂ CF ₂ CF ₂ ), (OCF(CF ₃ )CF ₂ ) or (OCF ₂ CF(CF ₃ )), more preferably _{( OCF2CF2CF2 )} . In one aspect, e is zero. In another aspect, e is 1. (OC ₂ F ₄ ) in the above formula (f1) is preferably (OCF ₂ CF ₂ ) or (OCF(CF ₃ )), more preferably (OCF ₂ CF ₂ ).

In the above formula (f2), e and f are each independently an integer of preferably 5-200, more preferably 10-200. Also, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the above formula (f2) is preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _c -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) It is a group represented by _f- . In another embodiment, formula (f2) may be a group represented by -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

In formula (f3) above, R ⁶ is preferably OC ₂ F ₄ . In (f3) above, R ⁷ is preferably a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or 2 independently selected from these groups, or A combination of three groups, more preferably a group selected from OC ₃ F ₆ and OC ₄ F ₈ . The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but for example -OC ₂ F ₄ OC ₃ F ₆ -, -OC _{2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F _ _ _ _ _ _ _ _ _ _ 8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC _ _ _ _ _ _ _ _ _ _ 4F8- , -OC2F4OC3F6OC2F4- , -OC2F4OC3F6OC3F6- , -OC2F4OC4F8OC2F4- , _ _ _ _ _ _ _ _ _ _ _ _ -OC3F6OC2F4OC2F4- , -OC3F6OC2F4OC3F6- , -OC3F6OC3F6OC2F4- , and -OC4F _ _ _ _ _ _ _ _ _ _ _ 8} OC ₂ F ₄ OC ₂ F ₄ - and the like. In the above formula (f3), g is an integer of preferably 3 or more, more preferably 5 or more. Said g is preferably an integer of 50 or less. In formula (f3) above, OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be linear or branched, preferably linear. is a chain. In this aspect, the above formula (f3) is preferably -(OC ₂ F ₄ -OC ₃ F ₆ ) _g - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _g -.

In formula (f4) above, R ⁶ , R ⁷ and g have the same meanings as in formula (f3) above, and have the same aspects. R ^6′ , R ^7′ and g′ have the same meanings as R ⁶ , R ⁷ and g in formula (f3) above, respectively, and have the same aspects. R ^r is preferably
[In the formula, * indicates a binding position. ]
and more preferably
[In the formula, * indicates a binding position. ]
is.

In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

In one aspect, R ^F is a group represented by the formula (f1).

In one aspect, R ^F is a group represented by the formula (f2).

In one aspect, R ^F is a group represented by the formula (f3) or (f4).

In one aspect, R ^F is a group represented by the formula (f3).

In one aspect, R ^F is a group represented by the formula (f4).

In one aspect, R ^F is a group represented by the formula (f5).

In one aspect, R ^F is a group represented by the formula (f6).

In the above ^RF , the ratio of e to f (hereinafter referred to as “e/f ratio”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2. Yes, more preferably 0.2 to 1.5, still more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, the slipperiness, wear resistance and chemical resistance (for example, durability against artificial perspiration) of the surface treatment layer obtained from this compound are further improved. The smaller the e/f ratio, the more improved the sliding property and abrasion resistance of the surface treatment layer. On the other hand, by setting the e/f ratio to 0.1 or more, the stability of the compound can be further enhanced. The higher the e/f ratio, the more stable the compound.

In the fluorine-containing silane compound, the number average molecular weights of the R ^{1 F1} and R ^{2 F2} moieties are not particularly limited, but are for example 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000. 000 to 10,000. In this specification, the number average molecular weights of R ^F1 and R ^F2 are values measured by ¹⁹ F-NMR.

In another embodiment, the R ^F1 and R ^F2 moieties have a number average molecular weight of 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000. 000 to 10,000, such as 3,000 to 6,000.

In another aspect, the number average molecular weight of the R ^F1 and R ^F2 moieties can be from 4,000 to 30,000, preferably from 5,000 to 10,000, more preferably from 6,000 to 10,000.

In the above formulas (1) and (2), each occurrence of R ^Si is independently 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 R ^Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is attached.

As used herein, the term "hydrolyzable group" means a group capable of undergoing a hydrolysis reaction, that is, a group capable of being eliminated from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, halogen (wherein R ^j is a substituted or represents an unsubstituted C _1-4 alkyl group).

In a preferred embodiment, R 3 ^Si is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is attached.

In preferred embodiments, R ^Si is represented by the following formula (S1), (S2), (S3), (S4), or (S5):
is a group represented by

In the above formula, each occurrence of R ¹¹ is independently a hydroxyl group or a hydrolyzable group.

R ¹¹ is preferably independently at each occurrence a hydrolyzable group.

R ¹¹ is preferably independently at each occurrence -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (wherein , R ^j represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^j (ie, an alkoxy group). Examples of R ^j 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 an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is a methyl group, and in another aspect R ^j is an ethyl group.

In the above formula, each occurrence of R ¹² is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ¹² , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, even more preferably a methyl group.

In the above formula, n1 is an integer of 0 to 3 independently for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit. However, when R ^Si is a group represented by formula (S1) or (S2), the terminal R ^Si portion of formula (1) and formula (2) (hereinafter simply formula (1) and formula (2) (also referred to as the “terminal portion” of), there is at least one (SiR ¹¹ _n1 R ¹² _3-n1 ) unit where n1 is 1-3. That is, not all n1's are 0 at the same time. In other words, there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is attached at the terminal portion of formulas (1) and (2).

n1 is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit.

In the above formula, X ¹¹ at each occurrence is independently a single bond or a divalent organic group. Such divalent organic groups are preferably —R ²⁸ —O _x —R ²⁹ —, wherein R ²⁸ and R ²⁹ are each independently at each occurrence a single bond or a C _1-20 alkylene group. , x is 0 or 1.). Such C _1-20 alkylene groups may be straight chain or branched, but are preferably straight chain. Such C _1-20 alkylene groups are preferably C _1-10 alkylene groups, more preferably C _1-6 alkylene groups, still more preferably C _1-3 alkylene groups.

In one aspect, X ¹¹ is independently at each occurrence -C _1-6 alkylene-O-C _1-6 alkylene- or -O-C _1-6 alkylene-.

In preferred embodiments, each occurrence of X ¹¹ is independently a single bond or a straight-chain C _1-6 alkylene group, preferably a single bond or a straight-chain C _1-3 alkylene group, more preferably a single It is a bond or straight chain C _1-2 alkylene group, more preferably a straight chain C _1-2 alkylene group.

In the above formula, each occurrence of R ¹³ is independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are preferably C _1-20 alkyl groups. Such C _1-20 alkyl groups may be straight chain or branched, but are preferably straight chain.

In preferred embodiments, R ¹³ is independently at each occurrence a hydrogen atom or a linear C _1-6 alkyl group, preferably a hydrogen atom or a linear C _1-3 alkyl group, preferably a hydrogen atom or a methyl group.

In the above formula, each occurrence of t is independently an integer of 2 or more.

In preferred embodiments, t is independently at each occurrence an integer from 2 to 10, preferably an integer from 2 to 6.

In the above formula, each occurrence of R ¹⁴ is independently a hydrogen atom, a halogen atom, or —X ¹¹ —SiR ¹¹ _n1 R ¹² _3-n1 . Such a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom. In preferred embodiments, R ¹⁴ is a hydrogen atom.

In the above formula, each occurrence of R ¹⁵ is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.

In one embodiment, each occurrence of R ¹⁵ is independently an oxygen atom, a C 1-6 alkylene group, or a C 1-6 alkyleneoxy group.

In a preferred embodiment R ¹⁵ is a single bond.

In one aspect, formula (S1) is the following formula (S1-a).
[In the formula,
R ¹¹ , R ¹² , R ¹³ , X ¹¹ , and n1 have the same meanings as described in formula (S1) above;
t1 and t2 are each independently at each occurrence an integer of 1 or greater, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, such as an integer of 1 to 5 or an integer of 2 to 5;
The order of existence of each repeating unit bracketed with t1 and t2 is arbitrary in the formula. ]

In a preferred embodiment, formula (S1) is the following formula (S1-b).
[Wherein, R ¹¹ , R ¹² , R ¹³ , X ¹¹ , n1 and t have the same meanings as described in formula (S1) above]

In the above formula, each occurrence of R ^a1 is independently —Z ¹ —SiR ²¹ _p1 R ²² _q1 R ²³ _r1 .

Each occurrence of Z ¹ above is independently an oxygen atom or a divalent organic group. In the structure described below as Z ¹ , the right side is bound to (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ).

In preferred embodiments, Z ¹ is a divalent organic group.

In a preferred embodiment, Z ¹ does not include those that form a siloxane bond with the Si atom to which Z ¹ is bonded. Preferably, (Si—Z ¹ —Si) in formula (S3) does not contain a siloxane bond.

The above Z ¹ is preferably a C _1-6 alkylene group, —(CH ₂ ) _z1 —O—(CH ₂ ) _z2 — (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6 and z2 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -, wherein z3 is an integer of 0 to 6, For example, it is an integer from 1 to 6, and z4 is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. is preferably unsubstituted.

In a preferred embodiment, Z ¹ is a C _1-6 alkylene group or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -, preferably -phenylene-(CH ₂ ) _z4 -. When Z ¹ is such a group, higher light resistance, especially UV resistance, can be obtained.

In another preferred embodiment, Z ¹ above is a C _1-3 alkylene group. In one aspect, Z ¹ can be -CH ₂ CH ₂ CH ₂ -. In another aspect, Z ¹ can be -CH ₂ CH ₂ -.

R ²¹ above is independently at each occurrence —Z ^1′ —SiR ^21′ _p1′ R ^22′ _q1′ R ^23′ _r1′ .

Each occurrence of Z ^1′ above is independently an oxygen atom or a divalent organic group. In the structure described as Z ^1′ below, the right side is bound to (SiR ^21′ _p1′ R ^22′ _q1′ R ^23′ _r1′ ).

In a preferred embodiment, Z ^1' is a divalent organic group.

In a preferred embodiment, Z ^1' does not include those that form a siloxane bond with the Si atom to which Z ^1' is bonded. Preferably, (Si—Z ^1′ —Si) in formula (S3) does not contain a siloxane bond.

The above Z ^1′ is preferably a C _1-6 alkylene group, —(CH ₂ ) _z1′ —O—(CH ₂ ) _z2′ — (wherein z1′ is an integer of 0 to 6, for example 1 to is an integer of 6 and z2' is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH ₂ ) _z3' -phenylene-(CH ₂ ) _z4' - (wherein z3' is an integer from 0 to 6, such as an integer from 1 to 6, and z4' is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. is preferably unsubstituted.

In a preferred embodiment, Z ^1' is a C _1-6 alkylene group or -(CH ₂ ) _z3' -phenylene-(CH ₂ ) _z4' -, preferably -phenylene-(CH ₂ ) _z4' -. When Z ^1′ is such a group, it can have higher light resistance, especially UV resistance.

In another preferred embodiment, Z ^1′ above is a C _1-3 alkylene group. In one aspect, Z ^1' can be -CH ₂ CH ₂ CH ₂ -. In another aspect, Z ^1' can be -CH ₂ CH ₂ -.

R ^21′ above is independently at each occurrence —Z ^1″ —SiR ^22″ _q1″ R ^23″ _r1″ .

Each occurrence of Z ^{1″ above} _is independently an oxygen atom or _a ^divalent organic group ^. ).

In preferred embodiments, Z ^1″ is a divalent organic group.

In a preferred embodiment, Z ^1″ does not include those that form a siloxane bond with the Si atom to which Z ^1″ is bonded. Preferably, in formula (S3), (Si—Z ^1″ —Si) does not contain a siloxane bond.

The above Z ^1″ is preferably a C _1-6 alkylene group, —(CH ₂ ) _z1″ —O—(CH ₂ ) _z2″ — (wherein z1″ is an integer of 0 to 6, for example 1 to is an integer of 6, and z2″ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH ₂ ) _z3″ —phenylene-(CH ₂ ) _z4″ —, wherein z3″ is an integer from 0 to 6, such as an integer from 1 to 6, and z4″ is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups are linear or branched, but preferably straight-chain, these groups are, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2- It may be substituted with one or more substituents selected from ₆ alkynyl groups, but is preferably unsubstituted.

In a preferred embodiment, Z ^1″ is a C _1-6 alkylene group or -(CH ₂ ) _z3″ -phenylene-(CH ₂ ) _z4″ -, preferably -phenylene-(CH ₂ ) _z4″ -. When Z ^1″ is such a group, it can be more light-resistant, especially UV-resistant.

In another preferred aspect, Z ^1″ is a C _1-3 alkylene group. In one aspect, Z ^1″ can be —CH ₂ CH ₂ CH ₂ —. In another aspect, Z ^1″ can be —CH ₂ CH ₂ —.

Each occurrence of R ^22″ above is independently a hydroxyl group or a hydrolyzable group.

R ^{22 ″} above is preferably independently at each occurrence a hydrolyzable group.

The above R ^22″ is preferably independently at each occurrence -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (these In the formula, R ^j represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^j (that is, an alkoxy group) R ^j includes a methyl group, an ethyl group, unsubstituted alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group; Ethyl groups are more preferred, hi one aspect R ^j is a methyl group, and in another aspect R ^j is an ethyl group.

Each occurrence of R ^{23 ″} above is independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above hydrolyzable groups.

In R ^23″ above, the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

The above q1″ is independently at each occurrence an integer from 0 to 3, and the at least one r1″ is independently at each occurrence an integer from 0 to 3. The sum of q1″ and r1″ is 3 in units of (SiR ^22″ _q1″ R ^23″ _r1″ ).

The above q1″ is an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR ^22″ _q1″ R ^23″ _r1″ ) unit.

Each occurrence of R ^22′ above is independently a hydroxyl group or a hydrolyzable group.

R ^22' is preferably independently at each occurrence a hydrolyzable group.

R ^22′ is preferably independently at each occurrence -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen ( wherein R ^j represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^j (ie, an alkoxy group). Examples of R ^j 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 an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is a methyl group, and in another aspect R ^j is an ethyl group.

Each occurrence of R ^23′ above is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ^23′ , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, even more preferably a methyl group.

The above p1' is independently an integer of 0 to 3 at each occurrence, q1' is independently an integer from 0 to 3 at each occurrence, and r1' is independently at each occurrence. , and is an integer from 0 to 3. The sum of p', q1' and r1' is 3 in the unit of (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ).

In one aspect, p1' is zero.

In one embodiment, p1' is an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ) unit. may In a preferred embodiment, p1' is 3.

In one embodiment, q1' is an integer of 1 to 3, preferably an integer of 2 to 3, each independently for each (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ) unit, 3 is more preferable.

In one aspect, p1' is 0 and q1' is an integer of 1 to 3 independently for each (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ) unit, preferably is an integer of 2-3, more preferably 3.

Each occurrence of R ²² above is independently a hydroxyl group or a hydrolyzable group.

R ²² is preferably independently at each occurrence a hydrolyzable group.

R ²² is preferably independently at each occurrence -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (wherein , R ^j represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^j (ie, an alkoxy group). Examples of R ^j 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 an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is a methyl group, and in another aspect R ^j is an ethyl group.

Each occurrence of R ²³ above is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ²³ , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, even more preferably a methyl group.

p1 above independently at each occurrence is an integer of 0 to 3, q1 is independently at each occurrence an integer from 0 to 3, r1 is independently at each occurrence, An integer from 0 to 3. The sum of p1, q1 and r1 is 3 in units of (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ).

In one aspect, p1 is zero.

In one aspect, p1 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) unit. In a preferred embodiment, p1 is 3.

In one aspect, q1 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3, independently for each (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) unit.

In one embodiment, p1 is 0 and q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, for each (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) unit. 3 is preferred.

In the above formula, each occurrence of R ^b1 is independently a hydroxyl group or a hydrolyzable group.

R ^b1 above is preferably independently at each occurrence a hydrolyzable group.

Preferably, each occurrence of R ^b1 is independently —OR ^j , —OCOR ^j , —ON=CR ^j ₂ , —NR ^j ₂ , —NHR ^j , —NCO, or halogen ( wherein R ^j represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^j (ie, an alkoxy group). Examples of R ^j 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 an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is a methyl group, and in another aspect R ^j is an ethyl group.

In the above formula, each occurrence of R ^c1 is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ^c1 above, the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, still more preferably a methyl group.

k1 above independently at each occurrence is an integer of 0 to 3, l1 is independently at each occurrence an integer from 0 to 3, m1 is independently at each occurrence, An integer from 0 to 3. The sum of k1, l1 and m1 is 3 in units of (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ).

In one aspect, k1 is independently an integer of 1 to 3, preferably 2 or 3, more preferably 3 for each (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ) unit. In a preferred embodiment, k1 is 3.

In the above formulas (1) and (2), when R ^Si is a group represented by formula (S3), preferably at the terminal portion of formulas (1) and (2), a hydroxyl group or a hydrolyzable group There are at least two Si atoms to which are bonded.

In a preferred embodiment, the group represented by formula (S3) is —Z ¹ —SiR ²² _q1 R ²³ _r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 and r1 is an integer of 0 to 2.), —Z ^1′ —SiR ^22′ _q1′ R ^23′ _r1′ (wherein q1′ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1′ is an integer of 0 to 2), or —Z ^1″ —SiR ^22″ _q1″ R ^23″ _r1″ (wherein q1″ is 1 to is an integer of 3, preferably 2 or 3, more preferably 3, and r1″ is an integer of 0 to 2.) Z ¹ , Z ^1′ , Z ^1″ , R ²² , R ²³ , R ^22′ , R ^23′ , R ^22″ , and R ^23″ are as defined above.

In a preferred embodiment, in formula (S3), if R ^21′ is present, at least one, preferably all R ^21′ , q1″ is an integer from 1 to 3, preferably 2 or 3, or more 3 is preferred.

In a preferred embodiment, in formula (S3), if R ²¹ is present, at least one, preferably all R ²¹ , p1′ is 0 and q1′ is an integer of 1 to 3, preferably is 2 or 3, more preferably 3.

In a preferred embodiment, in formula (S3), if R ^a1 is present, at least one, preferably all R ^a1 , p1 is 0, q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3.

In a preferred embodiment, k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3, in formula (S3).

R ^d1 is independently at each occurrence -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 .

Z ² is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group. In the structure described below as Z ² , the right side is bound to (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ).

In preferred embodiments, Z ² is a divalent organic group.

The above Z ² is preferably a C _1-6 alkylene group, —(CH ₂ ) _z5 —O—(CH ₂ ) _z6 — (wherein z5 is an integer of 0 to 6, for example an integer of 1 to 6 and z6 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -, wherein z7 is an integer of 0 to 6, For example, an integer from 1 to 6, and z8 is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. is preferably unsubstituted.

In a preferred embodiment, Z ² is a C _1-6 alkylene group or -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -, preferably -phenylene-(CH ₂ ) _z8 -. When ^Z2 is such a group, it can be more light-resistant, especially UV-resistant.

In another preferred embodiment, Z ² above is a C _1-3 alkylene group. In one aspect, Z ² can be -CH ₂ CH ₂ CH ₂ -. In another aspect, Z ² can be -CH ₂ CH ₂ -.

R ³¹ is independently at each occurrence -Z ^2' -CR ^32' _q2' R ^33' _r2' .

Z ^2' at each occurrence is independently a single bond, an oxygen atom or a divalent organic group. In the structure described as Z ^2′ below, the right side is bound to (CR ^32′ _q2′ R ^33′ _r2′ ).

The above Z ^2′ is preferably a C _1-6 alkylene group, —(CH ₂ ) _z5′ —O—(CH ₂ ) _z6′ — (wherein z5′ is an integer of 0 to 6, for example 1 to is an integer of 6 and z6' is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH ₂ ) _z7' -phenylene-(CH ₂ ) _z8' - (wherein z7' is an integer from 0 to 6, such as an integer from 1 to 6, and z8' is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. is preferably unsubstituted.

In a preferred embodiment, Z ^2' is a C _1-6 alkylene group or -(CH ₂ ) _z7' -phenylene-(CH ₂ ) _z8' -, preferably -phenylene-(CH ₂ ) _z8' -. When Z ^2' is such a group, it can be more light-resistant, especially UV-resistant.

In another preferred embodiment, Z ^2′ above is a C _1-3 alkylene group. In one aspect, Z ^2' can be -CH ₂ CH ₂ CH ₂ -. In another aspect, Z ^2' can be -CH ₂ CH ₂ -.

Each occurrence of R ^32′ above is independently —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 .

Each occurrence of Z ³ above is independently a single bond, an oxygen atom, or a divalent organic group. In the structure described below as Z ³ , the right side is bound to (SiR ³⁴ _n2 R ³⁵ _3-n2 ).

In one aspect, ^Z3 is an oxygen atom.

In one aspect, Z ³ is a divalent organic group.

The above Z ³ is preferably a C _1-6 alkylene group, —(CH ₂ ) _z5″ —O—(CH ₂ ) _z6″ — (wherein z5″ is an integer of 0 to 6, such as 1 to 6 and z6″ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH ₂ ) _z7″ —phenylene-(CH ₂ ) _z8″ — (wherein z7″ is , an integer from 0 to 6, such as an integer from 1 to 6, and z8″ is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. is preferably unsubstituted.

In a preferred embodiment, Z ³ is a C _1-6 alkylene group or —(CH ₂ ) _z7″ -phenylene-(CH ₂ ) _z8″ -, preferably -phenylene-(CH ₂ ) _z8″ - ^. When is such a group, higher light resistance, especially UV resistance, can be obtained.

In another preferred embodiment, Z ³ above is a C _1-3 alkylene group. In one aspect, Z ³ can be -CH ₂ CH ₂ CH ₂ -. In another aspect, Z ³ can be -CH ₂ CH ₂ -.

Each occurrence of R ³⁴ above is independently a hydroxyl group or a hydrolyzable group.

R ³⁴ is preferably independently at each occurrence a hydrolyzable group.

R ³⁴ is preferably independently at each occurrence -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (wherein , R ^j represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^j (ie, an alkoxy group). Examples of R ^j 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 an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is a methyl group, and in another aspect R ^j is an ethyl group.

Each occurrence of R ³⁵ above is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ³⁵ above, the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, still more preferably a methyl group.

In the above formula, n2 is an integer of 0 to 3 independently for each (SiR ³⁴ _n2 R ³⁵ _3-n2 ) unit. However, when R ^Si is a group represented by formula (S4), in the terminal portion of formula (1) and formula (2), (SiR ³⁴ _n2 R ³⁵ _3-n2 ) units in which n2 is 1 to 3 there is at least one That is, not all n2 are 0 at the same time. In other words, there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is attached at the terminal portion of formulas (1) and (2).

n2 is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR ³⁴ _n2 R ³⁵ _3-n2 ) unit.

Each occurrence of R ^33′ above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ^33′ above, the monovalent organic group is preferably a C _1-20 alkyl group or —(C _s H _2s ) _t1 —(O—C _s H _2s ) _t2 (wherein s is 1 to 6 , preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C _1-20 alkyl group, still more preferably a C _1-6 alkyl group, and particularly preferably a methyl group.

In one aspect, R ^33' is a hydroxyl group.

In another aspect, R ^33' is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

Each occurrence of q2' is independently an integer from 0 to 3, and each occurrence of r2' is independently an integer from 0 to 3. The sum of q2' and r2' is 3 in the unit of (CR ^32' _q2' R ^33' _r2' ).

q2' is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (CR ^32' _q2' R ^33' _r2' ) unit.

R ³² is independently at each occurrence -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 . Such —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 has the same meaning as described for R ^32′ above.

Each occurrence of R ³³ above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ³³ above, the monovalent organic group is preferably a C _1-20 alkyl group or —(C _s H _2s ) _t1 —(O—C _s H _2s ) _t2 (wherein s is 1 to 6 an integer, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C _1-20 alkyl group, still more preferably a C _1-6 alkyl group, and most preferably a methyl group.

In one aspect, R ³³ is a hydroxyl group.

In another aspect, R ³³ is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

p2 above independently at each occurrence is an integer of 0 to 3, q2 is independently at each occurrence an integer from 0 to 3, r2 is independently at each occurrence, An integer from 0 to 3. The sum of p2, q2 and r2 is 3 in the unit of (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ).

In one aspect, p2 is zero.

In one aspect, p2 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ) unit. In preferred embodiments, p2 is three.

In one aspect, q2 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ) unit.

In one embodiment, p2 is 0 and q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, for each (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ) unit. 3 is preferred.

Each occurrence of R ^e1 above is independently —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 . Such —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 has the same meaning as described for R ^32′ above.

Each occurrence of R ^f1 above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ^f1 above, the monovalent organic group is preferably a C _1-20 alkyl group or —(C _s H _2s ) _t1 —(O—C _s H _2s ) _t2 (wherein s is 1 to 6 an integer, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C _1-20 alkyl group, still more preferably a C _1-6 alkyl group, and most preferably a methyl group.

In one aspect, R ^f1 is a hydroxyl group.

In another aspect, R ^f1 is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

k2 above independently at each occurrence is an integer of 0 to 3, l2 is independently at each occurrence an integer from 0 to 3, m2 is independently at each occurrence, An integer from 0 to 3. The sum of k2, l2 and m2 is 3 in units of (CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ).

In the above formulas (1) and (2), when R ^Si is a group represented by formula (S4), preferably at the terminal portion of formulas (1) and (2), a hydroxyl group or a hydrolyzable group There are at least two Si atoms to which are bonded.

In one embodiment, when R ^Si is a group represented by formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR ³⁴ _n2 R ³⁵ _3-n2 ) units is 2 or more, for example 2 to 27, preferably 2 to 9, more preferably 2 to 6, still more preferably 2 to 3, at each terminal portion of formula (1) and formula (2), Especially preferably, there are three.

In a preferred embodiment, in formula (S4), at least one, preferably all R ^{32 '} , if present, n2 is an integer from 1 to 3, preferably 2 or 3, more preferably is 3.

In a preferred embodiment, in formula (S4), at least one, preferably all R ³² , if present ^, n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3 is.

In a preferred embodiment, in formula (S4), if R ^e1 is present, at least one, preferably all R ^a1 , n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3 is.

In a preferred embodiment, k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3, in formula (S4).

R ^g1 and R ^h1 are each independently at each occurrence -Z ⁴ -SiR ¹¹ _n1 R ¹² _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 . Here, R ¹¹ , R ¹² , R ^a1 , R ^b2 , R ^c1 , R ^d1 , R ^e1 , R ^f1 , n1, k1, l1, m1, k2, l2, and m2 have the same meanings as above.

In preferred embodiments, R ^g1 and R ^h1 are each independently —Z ⁴ —SiR ¹¹ _n1 R ¹² _3-n1 .

Each occurrence of Z ⁴ above is independently a single bond, an oxygen atom, or a divalent organic group. In the structure described below as Z ⁴ , the right side is bound to (SiR ¹¹ _n1 R ¹² _3-n1 ).

In one aspect, Z ⁴ is an oxygen atom.

In one aspect, Z ⁴ is a divalent organic group.

The above Z ⁴ is preferably a C _1-6 alkylene group, —(CH ₂ ) _z5″ —O—(CH ₂ ) _z6″ — (wherein z5″ is an integer of 0 to 6, such as 1 to 6 and z6″ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH ₂ ) _z7″ —phenylene-(CH ₂ ) _z8″ — (wherein z7″ is , an integer from 0 to 6, such as an integer from 1 to 6, and z8″ is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. is preferably unsubstituted.

In a preferred embodiment, Z ⁴ is a C _1-6 alkylene group or —(CH ₂ ) _z7″ -phenylene-(CH ₂ ) _z8″ -, preferably -phenylene-(CH ₂ ) _z8″ -. ^{Z 3} When is such a group, higher light resistance, especially UV resistance, can be obtained.

In another preferred embodiment, Z ⁴ above is a C _1-3 alkylene group. In one aspect, Z ⁴ can be -CH ₂ CH ₂ CH ₂ -. In another aspect, Z ⁴ can be -CH ₂ CH ₂ -.

In one aspect, R ^Si is a group represented by formula (S2), (S3), (S4) or (S5). These compounds can form a surface treatment layer having high surface lubricity.

In one aspect, R ^Si is a group represented by formula (S3), (S4) or (S5). Since these compounds have a plurality of hydrolyzable groups at one end, they can form a surface treatment layer that strongly adheres to a substrate and has high abrasion resistance.

In one aspect, R ^Si is a group represented by formula (S3) or (S4). Since these compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at one end, they can form a surface treatment layer with even higher abrasion resistance.

In one aspect, R ^Si is a group represented by formula (S1).

In one aspect, R ^Si is a group represented by formula (S2).

In one aspect, R ^Si is a group represented by formula (S3).

In one aspect, R ^Si is a group represented by formula (S4).

In one aspect, R ^Si is a group represented by formula (S5).

In the above formulas (1) and (2), X ^A is the fluoropolyether portion (R ^F1 and R ^F2 ) that mainly provides water repellency, surface slipperiness, etc., and the portion that provides bonding ability with the substrate ( R ^Si ) and the linker. Therefore, ^XA may be a single bond or any group as long as the compounds represented by formulas (1) and (2) can exist stably.

In the above formula (1), α is an integer of 1-9, and β is an integer of 1-9. These α and β can vary depending on the valence of ^XA . The sum of α and β is the same as the valence of ^XA . For example, if X ^A is a decavalent organic group, the sum of α and β is 10, such as α being 9 and β being 1, α being 5 and β being 5, or α being 1 and β being 9. obtain. Also, α and β are 1 when X ^A is a divalent organic group.

In the above formula (2), γ is an integer of 1-9. γ can vary depending on the valence of X ^A. That is, γ is the value obtained by subtracting 1 from the valence of ^XA .

each X ^A is independently a single bond or a divalent to decavalent organic group;

The divalent to decavalent organic group in X ^A above is preferably a divalent to octavalent organic group. In one aspect, such divalent to decavalent organic groups are preferably divalent to tetravalent organic groups, more preferably divalent organic groups. In another aspect, such divalent to decavalent organic groups are preferably trivalent to octavalent organic groups, more preferably trivalent to hexavalent organic groups.

In one aspect, X ^A is a single bond or a divalent organic group, α is 1 and β is 1.

In one aspect, X ^A is a single bond or a divalent organic group and γ is one.

In one embodiment, X ^A is a tri- to hexavalent organic group, α is 1 and β is 2-5.

In one embodiment, X ^A is a 3-6 valent organic group and γ is 2-5.

In one aspect, X ^A is a trivalent organic group, α is 1 and β is 2.

In one aspect, X ^A is a trivalent organic group and γ is two.

When X ^A is a single bond or a divalent organic group, formulas (1) and (2) are represented by formulas (1') and (2') below.

In one aspect, X ^A is a single bond.

In another aspect, X ^A is a divalent organic group.

In one aspect, X ^A is, for example, a single bond or the following formula:
-(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -
[In the formula:
R ⁵¹ represents a single bond, —(CH ₂ ) _s5 — or an o-, m- or p-phenylene group, preferably —(CH ₂ ) _s5 —,
s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, even more preferably 1 or 2;
X ⁵¹ represents -(X ⁵² ) _l5 -,
X ⁵² is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R ⁵³ ) ₂ -, -( a group selected from the group consisting of Si(R ⁵³ ) ₂ O) _m5 -Si(R ⁵³ ) ₂ -, -CONR ⁵⁴ -, -O-CONR ⁵⁴ -, -NR ⁵⁴ - and -(CH ₂ ) _n5 - represents
R ⁵³ at 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 and
each occurrence of R ⁵⁴ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group);
m5 at each occurrence is independently an integer from 1 to 100, preferably an integer from 1 to 20;
n5 at each occurrence is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3;
l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3;
p5 is 0 or 1;
q5 is 0 or 1;
Here, at least one of p5 and q5 is 1, and the order of existence of each repeating unit bracketed with p5 or q5 is arbitrary.]
A divalent organic group represented by is mentioned. Here, X ^A (typically the hydrogen atom of X ^A ) is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. may be In preferred embodiments, X ^A is not substituted by these groups.

In a preferred embodiment, each X ^A above is independently -(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -R ⁵² -. R ⁵² represents a single bond, -(CH ₂ ) _t5 - or an o-, m- or p-phenylene group, preferably -(CH ₂ ) _t5 -. t5 is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. wherein R ⁵² (typically the hydrogen atom of R ⁵² ) is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group; may be In preferred embodiments, R ⁵⁶ is not substituted by these groups.

Preferably, the above X ^A are each independently
single bond,
a C _1-20 alkylene group,
—R ⁵¹ —X ⁵³ —R ⁵² —, or —X ⁵⁴ —R ⁵ —
[Wherein, R ⁵¹ and R ⁵² have the same meanings as above,
^X53 is
-O-,
-S-,
-C(O)O-,
-CONR ^54- ,
-O-CONR ^54- ,
—Si(R ⁵³ ) ₂ —,
—(Si(R ⁵³ ) ₂ O) _m5 —Si(R ⁵³ ) ₂ —,
—O—(CH ₂ ) _u5 —(Si(R ⁵³ ) ₂ O) _m5 —Si(R ⁵³ ) ₂ —,
—O—(CH ₂ ) _u5 —Si(R ⁵³ ) ₂ —O—Si(R ⁵³ ) ₂ —CH ₂ CH ₂ —Si(R ⁵³ ) ₂ —O—Si(R ⁵³ ) ₂ —,
—O—(CH ₂ ) _u5 —Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ —,
—CONR ⁵⁴ —(CH ₂ ) _u5 —(Si(R ⁵³ ) ₂ O) _m5 —Si(R ⁵³ ) ₂ —,
-CONR ⁵⁴ -(CH ₂ ) _u5 -N(R ⁵⁴ )-, or -CONR ⁵⁴ -(o-, m- or p-phenylene)-Si(R ⁵³ ) ₂ -
(Wherein, R ⁵³ , R ⁵⁴ and m5 have the same meanings as above,
u5 is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. ),
^X54 is
-S-,
-C(O)O-,
-CONR ^54- ,
-O-CONR ^54- ,
—CONR ⁵⁴ —(CH ₂ ) _u5 —(Si(R ⁵⁴ ) ₂ O) _m5 —Si(R ⁵⁴ ) ₂ —,
-CONR ⁵⁴ -(CH ₂ ) _u5 -N(R ⁵⁴ )-, or -CONR ⁵⁴ -(o-, m- or p-phenylene)-Si(R ⁵⁴ ) ₂ -
(In the formula, each symbol has the same meaning as above.)
represents ]
can be

More preferably, the above X ^A are each independently
single bond,
a C _1-20 alkylene group,
—(CH ₂ ) _s5 —X ⁵³ —,
—(CH ₂ ) _s5 —X ⁵³ —(CH ₂ ) _t5 —
-X ⁵⁴ -, or -X ⁵⁴ -(CH ₂ ) _t5 -
[In the formula, X ⁵³ , X ⁵⁴ , s5 and t5 have the same meanings as above. ]
is.

More preferably, the above X ^A are each independently
single bond,
a C _1-20 alkylene group,
—(CH ₂ ) _s5 —X ⁵³ —(CH ₂ ) _t5 —, or —X ⁵⁴ —(CH ₂ ) _t5 —
[In the formula, each symbol has the same meaning as described above. ]
can be

In a preferred embodiment, each of the above X ^A is independently
a single bond C _1-20 alkylene group,
—(CH ₂ ) _s5 —X ⁵³ —, or —(CH ₂ ) _s5 —X ⁵³ —(CH ₂ ) _t5 —
[In the formula,
X ⁵³ is -O-, -CONR ⁵⁴ -, or -O-CONR ⁵⁴ -;
R ⁵⁴ at each occurrence independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
s5 is an integer from 1 to 20,
t5 is an integer from 1 to 20; ]
can be

In a preferred embodiment, each of the above X ^A is independently
—(CH ₂ ) _s5 —O—(CH ₂ ) _t5 —
^-CONR54- ( _CH2 ) _t5-
[In the formula,
R ⁵⁴ at each occurrence independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
s5 is an integer from 1 to 20,
t5 is an integer from 1 to 20; ]
can be

In one aspect, each of the X ^A is independently
single bond,
a C _1-20 alkylene group,
—(CH ₂ ) _s5 —O—(CH ₂ ) _t5 —,
—(CH ₂ ) _s5 —(Si(R ⁵³ ) ₂ O) _m5 —Si(R ⁵³ ) ₂ —(CH ₂ ) _t5 —,
—(CH ₂ ) _s5 —O—(CH ₂ ) _u5 —(Si(R ⁵³ ) ₂ O) _m5 —Si(R ⁵³ ) ₂ —(CH ₂ ) _t5 — or —(CH ₂ ) _s5 —O— (CH ₂ ) _t5 —Si(R ⁵³ ) ₂ —(CH ₂ ) _u5 —Si(R ⁵³ ) ₂ —(C _v H _2v )—
[In the formula, R ⁵³ , m5, s5, t5 and u5 have the same meanings as above, and v5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ]
is.

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

X ^A is each independently one or more 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). It may be substituted by a substituent. In one aspect, X ^A is unsubstituted.

In addition, X ^A is bonded to R ^F1 or R ^F2 on the left side of each formula, and is bonded to R ^Si on the right side.

In one aspect, each X ^A can independently be other than a —O—C _1-6 alkylene group.

In another aspect, X ^A includes, for example, the following groups:
[wherein each R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
D is
—CH ₂ O(CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ —,
—CF ₂ O(CH ₂ ) ₃ —,
-(CH ₂ ) ₂ -,
-(CH ₂ ) ₃ -,
-(CH ₂ ) ₄ -,
—CONH—(CH ₂ ) ₃ —,
-CON(CH ₃ )-(CH ₂ ) ₃ -,
-CON(Ph)-(CH ₂ ) ₃ -, where Ph means phenyl, and
(In the formula, each R ⁴² independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.)
is a group selected from
E is -(CH ₂ ) _n - (n is an integer of 2 to 6),
D is attached to R ^F1 or R ^F2 of the molecular backbone and E is attached to R ^Si . ]

Specific examples of X ^A above include:
single bond,
—CH ₂ OCH ₂ —,
—CH ₂ O(CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ —,
—CH ₂ O(CH ₂ ) ₄ —,
—CH ₂ O(CH ₂ ) ₅ —,
—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 —,
_{-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 -} C ₍ O)NH _{- CH2- ,
-CH2OCH2} ( _{CH2 ) 7CH2Si} ( _OCH3 ) _2OSi ( _OCH3 ) _{2 ( CH2} ) _2Si ( _OCH3 ) _2OSi ( _OCH3 ) ₂ ( _CH2 ) _2- ,
_{-CH2OCH2CH2CH2Si} ( _{OCH3 ) 2OSi ( OCH3} ) _{2 ( CH2} ) _3- ,
_{-CH2OCH2CH2CH2Si ( OCH2CH3} ) _{2OSi ( OCH2CH3 ) 2} ( _{CH2 ) 3- ,
-CH2OCH2CH2CH2Si} ( _{OCH3 ) 2OSi ( OCH3} ) _{2 ( CH2} ) _2- ,
_{-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi} ( _{OCH2CH3 ) 2} ( _{CH2 ) 2- ,}
—(CH ₂ ) ₂ —Si(CH ₃ ) ₂ —(CH ₂ ) ₂ —,
_-CH2- ,
-(CH ₂ ) ₂ -,
-(CH ₂ ) ₃ -,
-(CH ₂ ) ₄ -,
-(CH ₂ ) ₅ -,
-( _CH2 ) _6- ,
-CO-,
-CONH-,
-CONH- _CH2- ,
—CONH—(CH ₂ ) ₂ —,
—CONH—(CH ₂ ) ₃ —,
—CONH—(CH ₂ ) ₄ —,
—CONH—(CH ₂ ) ₅ —,
—CONH—(CH ₂ ) ₆ —,
-CON( _CH3 ) _-CH2- ,
-CON(CH ₃ )-(CH ₂ ) ₂ -,
-CON(CH ₃ )-(CH ₂ ) ₃ -,
-CON(CH ₃ )-(CH ₂ ) ₄ -,
-CON(CH ₃ )-(CH ₂ ) ₅ -,
-CON(CH ₃ )-(CH ₂ ) ₆ -,
-CON(Ph)-CH ₂ - (where Ph means phenyl),
-CON(Ph)-(CH ₂ ) ₂ - (wherein Ph means phenyl),
-CON(Ph)-(CH ₂ ) ₃ - (wherein Ph means phenyl),
-CON(Ph)-(CH ₂ ) ₄ - (wherein Ph means phenyl),
-CON(Ph)-(CH ₂ ) ₅ - (where Ph means phenyl),
-CON(Ph)-(CH ₂ ) ₆ - (wherein Ph means phenyl),
-CONH-(CH ₂ ) ₂ NH(CH ₂ ) ₃ -,
-CONH-( _CH2 ) _6NH ( _CH2 ) _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 —,
_-OCH2- ,
—O(CH ₂ ) ₃ —,
_-OCFHCF2- ,

etc.

In yet another aspect, each X ^A is independently a group of the formula: -(R ¹⁶ ) _x1 -(CFR ¹⁷ ) _y1 -(CH ₂ ) _z1 -. In the formula, x1, y1 and z1 are each independently an integer of 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of existence of each parenthesized repeating unit is is optional in

In the above formula, each occurrence of R ¹⁶ is independently an oxygen atom, phenylene, carbazolylene, —NR ¹⁸ — (wherein R ¹⁸ represents a hydrogen atom or an organic group) or a divalent organic group. be. Preferably, R ¹⁸ is an oxygen atom or a divalent polar group.

The above-mentioned "divalent polar group" is not particularly limited, but -C(O)-, -C(=NR ¹⁹ )-, and -C(O)NR ¹⁹ - (in these formulas, R ¹⁹ is , represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.

In the above formula, each occurrence of R ¹⁷ 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 a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, It is a pentafluoroethyl group, more preferably a trifluoromethyl group.

In yet another aspect, examples of X ^A include the groups:
[In the formula,
each R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
In each X ^A group any one of the T's are attached to R ^F1 or R ^F2 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 - (where Ph means phenyl), or
[In the formula, each R ⁴² independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
and some of the other T's are attached to R ^Si of the molecular backbone and, if present, the remaining T's are each independently a methyl group, a phenyl group, a C _1-6 alkoxy group or a radical scavenging group group or UV-absorbing group.

The radical scavenging group is not particularly limited as long as it can scavenge radicals generated by light irradiation. , hindered amines, hindered phenols, or triazines.

The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. Examples include residues of oxanilides, benzoxazinones, and benzoxazoles.

In a preferred embodiment, preferred radical-scavenging groups or UV-absorbing groups include:
is mentioned.

In this aspect, each X ^A can independently be a trivalent to decavalent organic group.

In yet another aspect, examples of X ^A include the groups:
[wherein R ²⁵ , R ²⁶ and R ²⁷ are each independently a divalent to hexavalent organic group,
R ²⁵ is bound to at least one R ^{2 F1} and R ²⁶ and R ²⁷ are each bound to at least one R 2 ^Si . ]

In one embodiment, R ²⁵ above is a single bond, a C _1-20 alkylene group, a C _3-20 cycloalkylene group, a C _5-20 arylene group, -R ⁵⁷ -X ⁵⁸ -R ⁵⁹ -, -X ⁵⁸ - R ⁵⁹ -, or -R ⁵⁷ -X ⁵⁸ -. R ⁵⁷ and R ⁵⁹ above are each independently a single bond, a C _1-20 alkylene group, a C _3-20 cycloalkylene group, or a C _5-20 arylene group. X ⁵⁸ above is -O-, -S-, -CO-, -O-CO- or -COO-.

In one embodiment, R ²⁶ and R ²⁷ are each independently a hydrocarbon or a group having at least one atom selected from N, O and S in the end or main chain of the hydrocarbon, Preferred are C _1-6 alkyl group, —R ³⁶ —R ³⁷ —R ³⁶ —, —R ³⁶ —CHR ³⁸ ₂ — and the like. Here, each R ³⁶ is independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R ³⁷ is N, O or S, preferably N or O. R ³⁸ is -R ⁴⁵ -R ⁴⁶ -R ⁴⁵ -, -R ⁴⁶ -R ⁴⁵ - or -R ⁴⁵ -R ⁴⁶ -. Here, each R ⁴⁵ is independently an alkyl group having 1 to 6 carbon atoms. R ⁴⁶ is N, O or S, preferably O.

In this aspect, each X ^A can independently be a trivalent to decavalent organic group.

In yet another aspect, examples of X ^A include:
[In the formula, X ^a is a single bond or a divalent organic group. ]
A group represented by

X ^a above is a single bond or a divalent linking group that directly bonds to the isocyanuric ring. X ^a is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a sulfide bond, and An alkylene group of 1 to 10, or a divalent hydrocarbon group of 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a sulfide bond is more preferred.

X ^a is represented by the following formula:
-(CX ¹²¹ X ¹²² ) _x1 -(X ^a1 ) _y1 -(CX ¹²³ X ¹²⁴ ) _z1 -
(Wherein, X ¹²¹ to X ¹²⁴ are each independently H, F, OH, or —OSi(OR ¹²¹ ) ₃ (Wherein, three R ¹²¹ each independently have 1 to is an alkyl group of 4.),
X ^a1 above is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O -, or -NHC(=O)NH- (the left side of each bond is attached to CX ¹²¹ X ¹²² ),
x1 is an integer of 0-10, y1 is 0 or 1, and z1 is an integer of 1-10. )
A group represented by is more preferable.

The above X ^a1 is preferably -O- or -C(=O)O-.

As the above X ^a , the following formula:
-(CF ₂ ) _m11 -(CH ₂ ) _m12 -O-(CH ₂ ) _m13 -
(Wherein, m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3.)
A group represented by
-(CF ₂ ) _m14 -(CH ₂ ) _m15 -O-CH ₂ CH(OH)-(CH ₂ ) _m16 -
(Wherein, m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3.)
A group represented by
-(CF ₂ ) _m17 -(CH ₂ ) _m18 -
(Wherein, m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3.)
A group represented by
-(CF ₂ ) _m19 -(CH ₂ ) _m20 -O-CH ₂ CH(OSi(OCH ₃ ) ₃ )-(CH ₂ ) _m21 -
(Wherein, m19 is an integer of 1 to 3, m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3.)
or a group represented by
-( _CH2 ) _m22-
(Wherein, m22 is an integer of 1 to 3.)
A group represented by is particularly preferred.

The above X ^a is not particularly limited, but specifically,
—CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₄ H ₈ —O—CH ₂ —, —CO—O—CH ₂ —CH(OH) —CH ₂ —, —(CF ₂ ) _n5 — (n5 is an integer of 0 to 4), —(CF ₂ ) _n5 —(CH ₂ ) _m5 — (n5 and m5 are each independently 0 4), —CF ₂ CF ₂ CH ₂ OCH ₂ CH(OH)CH ₂ —, —CF ₂ CF ₂ CH 2 _{OCH 2} CH(OSi(OCH ₃ ) ₃ )CH ₂ —
etc.

In this aspect, each X ^A can independently be a divalent or trivalent organic group.

The fluorine-containing silane compound represented by formula (1) or formula (2) is not particularly limited, but may have an average molecular weight of 5×10 ² to 1×10 ⁵ . Among these ranges, from the viewpoint of wear resistance, it is preferable to have an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000. The "average molecular weight" refers to the number average molecular weight, and the "average molecular weight" is a value measured by ¹⁹ F-NMR.

In one aspect, the fluorine-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by Formula (1).

In another aspect, the fluorine-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by Formula (2).

In another aspect, the fluorine-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by formula (1) and a compound represented by formula (2).

In the surface treatment agent of the present disclosure, the compound represented by formula (2) is preferably 0.1 with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) It is mol % or more and 35 mol % or less. The lower limit of the content of the compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol%, more preferably It can be 0.2 mol %, more preferably 0.5 mol %, even more preferably 1 mol %, particularly preferably 2 mol %, especially 5 mol %. The upper limit of the content of the compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 35 mol%, more preferably 30 mol %, more preferably 20 mol %, even more preferably 15 mol % or 10 mol %. The compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.2 mol% or more and 10 mol% or less, even more preferably 0.5 mol% or more and 10 mol% or less, particularly preferably 1 mol% or more and 10 mol% or less Hereinafter, for example, it is 2 mol % or more and 10 mol % or less, or 5 mol % or more and 10 mol % or less. By setting the content of the compound represented by formula (2) within such a range, it is possible to further improve wear resistance.

In one aspect, the surface treatment agent of the present disclosure contains two or more fluorine-containing silane compounds represented by formula (1) or (2). By including a plurality of fluorine-containing silane compounds, friction durability can be further improved.

In one aspect, in the surface treatment agent of the present disclosure, R ^Si is a group selected from formulas (S1), (S2), (S3), (S4) and (S5), and Certain fluorine-containing silane compounds represented by two or more types of formula (1) or (2) are included. Including fluorine-containing silane compounds having different R ^Si can further improve friction durability.

In one aspect, the surface treatment agent of the present disclosure includes a fluorine-containing silane compound represented by formula (1) or (2), wherein R ^Si is a group represented by formula (S1), and R ^Si is a group represented by formula A fluorine-containing silane compound represented by formula (1) or (2), which is a group selected from (S3), (S4) and (S5), is included. A fluorine-containing silane compound represented by formula (1) or (2), wherein R ^Si is a group represented by formula (S1), and R ^Si is selected from formulas (S3), (S4) and (S5). Combined use of the fluorine-containing silane compound represented by the formula (1) or (2), which is a group to be used, can further improve the friction durability.

In one aspect, the surface treatment agent of the present disclosure includes a fluorine-containing silane compound represented by formula (1) or (2), wherein R ^Si is a group represented by formula (S1), and R ^Si is a group represented by formula A fluorine-containing silane compound represented by formula (1) or (2), which is a group selected from (S3) and (S4), is included. A fluorine-containing silane compound represented by formula (1) or (2), wherein R ^Si is a group represented by formula (S1), and R ^Si is a group selected from formulas (S3) and (S4). Combined use of a certain fluorine-containing silane compound represented by formula (1) or (2) can further improve friction durability.

In one aspect, the surface treatment agent of the present disclosure includes a fluorine-containing silane compound represented by formula (1) or (2), wherein R ^Si is a group represented by formula (S1), and R ^Si is a group represented by formula A fluorine-containing silane compound represented by formula (1) or (2), which is a group represented by (S3), is included. A fluorine-containing silane compound represented by formula (1) or (2), wherein R ^Si is a group represented by formula (S1), and formula (1), wherein R ^Si is a group represented by formula (S3) Alternatively, by using the fluorine-containing silane compound represented by (2) in combination, the friction durability can be further improved.

In one aspect, the surface treatment agent of the present disclosure includes a fluorine-containing silane compound represented by formula (1) or (2), wherein R ^Si is a group represented by formula (S1), and R ^Si is a group represented by formula A fluorine-containing silane compound represented by formula (1) or (2), which is a group represented by (S4), is included. A fluorine-containing silane compound represented by formula (1) or (2), wherein R ^Si is a group represented by formula (S1), and formula (1), wherein R ^Si is a group represented by formula (S4) Alternatively, by using the fluorine-containing silane compound represented by (2) in combination, the friction durability can be further improved.

The compound represented by the above formula (1) or (2), for example, a method known per se, for example, International Publication No. WO 97/07155, JP 2008-534696, JP 2014-218639, JP 2017 It can be obtained by the method described in JP-82194 and the like.

The content of the compound represented by the above formula (1) or (2) is preferably 0.01 to 50.0% by mass, more preferably 0.1 to 30.0% by mass, based on the total surface treatment agent. % by weight, more preferably 1.0 to 25.0% by weight, particularly preferably 5.0 to 20.0% by weight. By setting the content of the fluorine-containing silane compound within the above range, higher water and oil repellency can be obtained.

The surface treatment agent of the present disclosure is a solvent, a (non-reactive) fluoropolyether compound, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorine-containing oil"), which can be understood as a fluorine-containing oil. , a (non-reactive) silicone compound that can be understood as silicone oil (hereinafter referred to as "silicone oil"), alcohols, compatibilizers, catalysts, surfactants, polymerization inhibitors, sensitizers, etc. .

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. ; 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-2-hydroxybutyrate , ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate and other esters; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Glycol ethers such as monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol monoalkyl ether; methanol, ethanol, iso-propanol, n-butanol, alcohols such as isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; tetrahydrofuran, tetrahydro Cyclic ethers such as pyran 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; 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethylsulfoxide, 1,1-dichloro-1,2 , 2,3,3-pentafluoropropane (HCFC225), Zeorola H, HFE7100, HFE7200, HFE7300 and other fluorine-containing solvents. Alternatively, a mixed solvent of two or more of these may be used.

Examples of the fluorine-containing oil include, but are not limited to, compounds represented by the following general formula (3) (perfluoro(poly)ether compounds).
^Rf5- ( _OC4F8 ) _a' -( _OC3F6 ) _b' -( _OC2F4 ) _{c '} -( _OCF2 ) _d'- ^Rf6 _{( 3} )
In the formula, Rf ⁵ represents a C 1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) optionally substituted with one or more fluorine atoms, and Rf ⁶ is represents a C 1-16 alkyl group optionally substituted with one or more fluorine atoms (preferably a C _1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and Rf ⁵ and Rf ⁶ , more preferably each independently a C _1-3 perfluoroalkyl group.
a', b', c' and d' each represent the number of four types of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 or more and 300 or less, , a′, b′, c′ and d′ are at least 1, preferably 1-300, more preferably 20-300. The order of existence of each repeating unit enclosed in parentheses with subscript a', b', c' or d' is arbitrary in the formula. Among 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 ))-, preferably - (OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- may be any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and (OCF ₂ CF(CF ₃ ))- , preferably -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- or (OCF(CF ₃ ))-, but is preferably -(OCF ₂ CF ₂ )-.

Examples of perfluoro(poly)ether compounds represented by the general formula (3) include compounds represented by any of the following general formulas (3a) and (3b) (one or a mixture of two or more) may be used).
Rf ⁵ -(OCF ₂ CF ₂ CF ₂ ) _b″ -Rf ⁶ (3a)
^Rf5- ( _{OCF2CF2CF2CF2 ) a"} -( _{OCF2CF2CF2 ) b" -} ( _{OCF2CF2 ) c "} -( _OCF2 ) _{d" -Rf6} ^... (3b )
In these formulas, Rf ⁵ and Rf ⁶ are as described above; in formula (3a), b″ is an integer of 1 or more and 100 or less; is an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The order of existence of each repeating unit is arbitrary in the formula.

From another point of view, the fluorine-containing oil may be a compound represented by the general formula Rf ³ —F (wherein Rf ³ is a C _5-16 perfluoroalkyl group). It may also be a chlorotrifluoroethylene oligomer.

The fluorine-containing oil may have an average molecular weight of 500-10,000. The molecular weight of the fluorine-containing oil can be measured using GPC.

The fluorine-containing oil may be included in an amount of, for example, 0.01 to 50% by mass, preferably 0.1 to 30% by mass, for example 1 to 15% by mass, based on the surface treatment agent of the present disclosure.

In one aspect, the surface treatment agent of the present disclosure is substantially free of fluorine-containing oil. “Substantially free of fluorine-containing oil” means that it does not contain fluorine-containing oil at all, or may contain a very small amount of fluorine-containing oil.

In one aspect, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the fluorine-containing silane compound. With such an average molecular weight, particularly when the surface treatment layer is formed by a vacuum deposition method, it is possible to obtain more excellent abrasion resistance and surface lubricity.

In one aspect, 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 an average molecular weight, it is possible to form a cured product having high abrasion resistance and high surface slipperiness while suppressing deterioration in the transparency of the surface treatment layer obtained from such a compound.

The fluorine-containing oil contributes to improving the surface lubricity of the layer formed by the surface treatment agent of the present disclosure.

As the silicone oil, for example, linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil. Modified silicone oils include those obtained by modifying straight silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil.

In the surface treatment agent of the present disclosure, the amount of such silicone oil is, for example, 0 to 300 parts per 100 parts by mass of the fluorine-containing silane compound of the present disclosure (the sum of these when two or more are used, the same shall apply hereinafter). It can be included in parts by weight, preferably 50 to 200 parts by weight.

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

Examples of the alcohols include non-fluorine alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, iso-propanol and tert-butanol. By adding these alcohols to the surface treating agent, the stability of the surface treating agent is improved and the compatibility between the perfluorinated silane compound and the solvent is improved.

As the compatibilizer, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol or 2,2,3,3,4,4,5,5- fluorine-substituted alcohols such as octafluoro-1-pentanol, preferably fluorine-substituted alcohols having CF ₂ H at the terminal, fluorine-substituted aryls such as 1,3-bis(trifluoromethyl)benzene, preferably fluorine-substituted benzene, and the like; mentioned.

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

The catalyst promotes hydrolysis and dehydration condensation of the fluorine-containing silane compound of the present disclosure, and promotes formation of the layer formed by the surface treatment agent of the present disclosure.

Other components include, in addition to the above, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.

The surface treatment agent of the present disclosure can be formed into pellets by impregnating a porous material such as a porous ceramic material, metal fiber such as steel wool into a flocculated material. The pellet can be used, for example, for vacuum deposition.

In addition to the components described above, the surface treatment agent of the present disclosure contains trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates. obtain.

The thickness of the surface treatment layer is not particularly limited. In the case of optical members, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, friction durability and antifouling properties. .

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

Layer formation of the surface treatment agent can be carried out by applying the surface treatment agent to the surface of the intermediate layer so as to coat the surface. A coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.

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

Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD and similar methods. Specific examples of vapor deposition methods (usually vacuum vapor deposition methods) include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods. Examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

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

When using a wet coating method, the surface treatment may be diluted with a solvent before being applied to the intermediate layer. From the viewpoint of the stability of the surface treatment agent and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoromethylcyclohexane); fluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg, bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (eg, C ₆ F ₁₃ CH ₂ CH ₃ (eg, Asahi Glass Co., Ltd.); company Asahiklin (registered trademark) AC-6000), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Nippon Zeon Co., Ltd. Zeorora (registered trademark) H); Fluoroethers ( _HFE ) (e.g. perfluoropropyl methyl ether ( _{C3F7OCH3 )} (e.g. Novec™ 7000 from Sumitomo 3M ₎ , perfluorobutyl methyl ether ( _{C4F9OCH3 )} (e.g. Novec™ 7100 _manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether ( _C4F9OC2H5 ) (e.g. _Novec ™ ₇₂₀₀ manufactured by Sumitomo 3M Limited), perfluorohexyl _Alkyl perfluoroalkyl ethers ( _{perfluoroalkyl} groups _and alkyl _{groups are} linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc. These solvents may be used alone, or It can be _{used as a mixture of} two or _more of them _. ) is particularly preferred.

When the dry coating method is used, the above surface treatment agent may be subjected to the dry coating method as it is, or may be subjected to the dry coating method after being diluted with the above solvent.

Layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, when the wet coating method is used, the catalyst may be added to the diluted solution of the surface treatment agent immediately before the surface treatment agent is diluted with a solvent and applied to the surface of the intermediate layer. When the dry coating method is used, the surface treatment agent added with the catalyst is vapor-deposited (usually, vacuum vapor deposition) as it is, or a metal porous body such as iron or copper is impregnated with the surface treatment agent added with the catalyst. Vapor deposition (usually vacuum deposition) processing may be performed using a pellet-shaped material.

Any suitable acid or base can be used for the catalyst. Examples of acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid. Moreover, as a basic catalyst, for example, ammonia, organic amines, and the like can be used.

As described above, a layer derived from the surface treatment agent is formed on the surface of the intermediate layer to produce the article of the present disclosure. The surface treatment layer thus obtained has high friction durability. In addition to high friction durability, the layer has water repellency, oil repellency, antifouling properties (for example, to prevent the adhesion of stains such as fingerprints), and waterproof properties, depending on the composition of the surface treatment agent used. (prevents water from penetrating into electronic parts, etc.), surface lubricity (or lubricity, e.g., wiping off of fingerprints and other stains, excellent tactile sensation on fingers), etc., and is suitable as a functional thin film can be utilized.

The article of the present disclosure may further be an optical material having the surface treatment layer as the outermost layer.

The article of the present disclosure is not particularly limited, but may be an optical member. Examples of optical members include the following: lenses for eyeglasses; front protective plates, antireflection plates, polarizing plates, anti-glare plates for displays such as PDP and LCD; touch panel sheets; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers;

Articles of the present disclosure may also be medical devices or medical materials.

The article of the present disclosure has, on a substrate, an intermediate layer containing a Ce-containing layer, and a surface treatment layer formed thereon from a surface treatment agent containing a fluorine-containing silane compound, thereby achieving high friction durability and high weather resistance. have sex.

The articles of the present disclosure have been described above in detail. Note that the article, the method for manufacturing the article, and the like of the present disclosure are not limited to the examples given above.

The articles of the present disclosure will be described below in Examples, but the present disclosure is not limited to the following Examples. In the present examples, the chemical formulas shown below all represent average compositions, and repeating units ((CF ₂ CF ₂ CF ₂ O), (CF (CF 3 ) CF 2 O), (CF (CF ₃ ) CF ₂ O), ( CF ₂ CF ₂ O), (CF ₂ O), etc.) can be present in any order.

As a glass substrate, Gorilla Glass 5 (manufactured by Corning Incorporated) having a thickness of 0.8 mm and a size of 66.0 mm×142.0 mm and having undergone chemical strengthening and surface polishing was used. After forming an intermediate layer on a glass substrate, a surface treatment layer was formed on the intermediate layer to obtain a glass substrate with a surface treatment layer. Details are as follows.

(Vapor deposition material)
As for the vapor deposition material of the single composition of SiO ₂ and Ta ₂ O ₅ , the vapor deposition material manufactured by Canon Optron was purchased and used as the CeO ₂ vapor deposition material manufactured by Sanwa Abrasive Industry Co., Ltd. Separately, vapor deposition materials having Si and Ce molar ratios of 95:5 and 90:10 were prepared and used. The molar ratio of Si and Ce was determined by X-ray fluorescence (XRF) analysis.

(Formation of intermediate layer)
The intermediate layer was deposited by electron beam evaporation (Examples 1-7, Comparative Examples 1, 3, and 4) or sputtering (Comparative Example 2).

Electron beam evaporation was performed as follows.
SiO ₂ alone, CeO ₂ alone, Ta ₂ O ₅ alone, or both SiO ₂ and CeO ₂ were placed in the vacuum deposition apparatus, and the vacuum deposition apparatus was evacuated to a pressure of 3.0×10 ⁻³ Pa or less. Next, on Gorilla Glass 5 (manufactured by Corning), the conditions are set for each example, and a single layer of film-forming material 1 shown in Table 1 below is formed, or film-forming material 1 and film-forming material An intermediate layer was formed by stacking two layers.

The sputtering method was performed as follows.
A silicon target and a tantalum target were set in a DC sputtering apparatus, and while introducing a mixed gas of argon and oxygen into the chamber, the film formation rate ratio (Si/Ta) was set to 9/1, and a thickness of 40 nm was obtained. An intermediate layer composed of a composite oxide of silicon and tantalum was deposited.

(Preparation of surface treatment agent)
The following fluoropolyether group-containing compound (A) or (B) was diluted with HFE7200 to 20% by mass. In Examples 1 to 4, 6 and 7, and Comparative Examples 1 to 3, the fluoropolyether group-containing compound (A) was used, and in Example 5 and Comparative Example 4, the fluoropolyether group-containing compound (B) was used.

- Fluoropolyether group-containing compound (A)
_{CF3CF2CF2O ( CF2CF2CF2O ) 23CF2CF2CONHCH2C ( CH2CH2CH2Si ( OCH3 ) 3 ) 3 _ _ _}

- Fluoropolyether group-containing compound (B)

(Formation of surface treatment layer)
The surface treatment layer was formed using an apparatus capable of resistance heating vapor deposition. Specifically, 0.09 g of the surface treatment agent was filled in a resistance heating boat in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was evacuated to a pressure of 3.0×10 ⁻³ Pa or less. Then, by raising the temperature of the resistance heating boat, a vapor deposition film was formed on the glass on which the intermediate layer was formed. Next, the glass with a vapor deposition film was allowed to stand in an atmosphere at a temperature of 150° C. for 30 minutes, and then allowed to cool to room temperature to form a surface treatment layer on the glass, Examples 1 to 7 and Comparative Examples 1 to 4. to obtain a glass substrate with a surface treatment layer.

(friction test)
(Friction test A)
Using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.), the static contact angle (°) of water was measured every 2,500 times of rubbing against the surfaces of the glass substrates of Examples 1 to 9 and Comparative Examples 1 to 4 under the following conditions. It was measured. The test was stopped when the measured value of the static contact angle of water became less than 100° or when the number of times of abrasion changed 20000 times. The test environmental conditions were 25° C. and 40% RH. The static contact angle of water was measured by the following method. The results are shown in Table 1 below.

Eraser: Rubber Eraser (manufactured by Minoan)
Contact area: 6mmφ
Travel distance (one way): 30mm
Moving speed: 2,400mm/min Load: 1kg/6mmφ

(Friction test B)
The glass substrates of Examples 1 to 9 and Comparative Examples 1 to 4 were placed horizontally, the following friction element was brought into contact with the surface of the surface treatment layer (the contact surface is a circle with a diameter of 1 cm), and a load of 5 N was applied thereon. After that, the friction element was reciprocated at a speed of 40 mm/sec while a load was applied. The static contact angle (°) of water was measured every 1000 times of friction. The test was stopped when the static contact angle of water measured less than 90°. The static contact angle of water was measured by the following method.

Friction element A surface (1 cm in diameter) of the silicone rubber product shown below was covered with cotton immersed in artificial sweat having the composition shown below, and this was used as a friction element.
Composition of artificial sweat:
Anhydrous disodium hydrogen phosphate: 2 g
Sodium chloride: 20g
85% lactic acid: 2g
Histidine hydrochloride: 5g
Distilled water: 1 kg
Silicone rubber products:
A silicone rubber plug SR-51 manufactured by Tigers Polymer was processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.

(Accelerated weather resistance test evaluation)
The glass substrates of Example 5 and Comparative Example 4 were subjected to an accelerated weather resistance test by xenon lamp irradiation. The xenon irradiation was performed using a xenon lamp (manufactured by Suga Test Instruments Co., Ltd., irradiance of 180 W/m ² at 300 to 400 nm), and the temperature of the plate on which the glass substrate was placed was 63°C. Xenon irradiation is carried out continuously, but when measuring the static contact angle of water, the glass substrate is once taken out, and the surface treatment layer is wiped with a Kimwipe (trade name, manufactured by Jujo Kimberly Co., Ltd.) sufficiently soaked with pure water and then reciprocated 5 times. After wiping, another Kimwipe was sufficiently impregnated with ethanol, wiped 5 reciprocations, and dried. The static contact angle of water was measured immediately thereafter.

First, as an initial evaluation, the static contact angle of water was measured on the glass substrate after the formation of the surface treatment layer before xenon irradiation (irradiation time: 0 hour). After that, the static contact angle of water was measured for each of the surface treatment layers after being irradiated with xenon for a predetermined time. The evaluation was performed from the start of xenon irradiation until the static contact angle of water fell below 90 degrees, or until the cumulative irradiation time was 1858 hours. Table 2 shows the results.

(static contact angle measurement)
In both friction tests A and B, the static contact angle of water was measured by applying a 2 μL pure water droplet and using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.: automatic contact angle meter DropMaster 701). The contact angle to water was measured and reported as the average value.

Articles of the present disclosure can be suitably used in a wide variety of applications, such as optical members.

Claims (20)

a substrate;
an intermediate layer located on the substrate;
a surface treatment layer positioned on the intermediate layer and formed of a surface treatment agent containing a fluorine-containing silane compound;
The article, wherein the intermediate layer comprises a Ce-containing layer. 2. The article of claim 1, wherein said Ce-containing layer further comprises Si. 2. The article of claim 1, wherein the Ce-containing layer comprises a complex oxide containing Si and Ce. 3. The article of claim 2, wherein the Ce-containing layer has a molar ratio of Si to Ce of 10:90 to 99.99:0.01. 2. The article of claim 1, wherein the intermediate layer further comprises an alkali metal or alkaline earth metal. 6. The article of claim 5, wherein the concentration of said alkali metals and alkaline earth metals in said intermediate layer is from 0.1 to 30 mol %. The article according to claim 1, wherein the Ce-containing layer has a thickness of 0.1 to 100 nm. 2. The article of claim 1, wherein said intermediate layer comprises a Ce-containing layer. 2. The article of claim 1, wherein the intermediate layer further comprises a silicon oxide layer over the Ce-containing layer. 10. The article of claim 9, wherein the silicon oxide layer has a thickness of 0.1 nm to 100 nm. The fluorine-containing silane compound has the following formula (1) or (2):
[In the formula:
each R ^F1 is independently Rf ¹ —R ^F —O _q —;
R ^F2 is -Rf ² _p -R ^F -O _q -;
each Rf ¹ is independently a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
each R ^F is independently a divalent fluoropolyether group;
p is 0 or 1;
each q is independently 0 or 1;
R ^Si is each independently 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;
at least one R ^Si is a monovalent group comprising a Si atom to which a hydroxyl or hydrolyzable group is attached;
each X ^A is independently a single bond or a divalent to decavalent organic group;
α is an integer from 1 to 9;
β is an integer from 1 to 9;
Each γ is independently an integer of 1-9. ]
2. The article according to claim 1, which is at least one fluoropolyether group-containing compound represented by: Each R ^F is independently of the formula:
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ R ^Fa ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f -
[Wherein, each R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom,
a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more; The order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula. ]
12. The article according to claim 11, which is a group represented by each Rf ¹ is independently a C _1-16 perfluoroalkyl group;
each Rf ² is independently a C _1-6 perfluoroalkylene group;
13. The article of claim 12, wherein ^RFa is a fluorine atom. R ^F is independently at each occurrence the following formula (f1), (f2), (f3), (f4), (f5) or (f6):
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, d is an integer of 1 to 200, and e is 0 or 1. ],
-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)
[Wherein, c and d are each independently an integer of 0 to 30;
e and f are each independently an integer from 1 to 200;
the sum of c, d, e and f is an integer from 10 to 200;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ],
-(R ⁶ -R ⁷ ) _g - (f3)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or two or three groups selected from these groups. is a combination of groups;
g is an integer from 2 to 100; ],
—(R ⁶ —R ⁷ ) _g —R ^r —(R ^7′ —R ^6′ ) _g′ − (f4)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or 2 independently selected from these groups or a combination of three groups,
R ^6' is OCF ₂ or OC ₂ F ₄ ;
R ^7′ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
^Rr is
(In the formula, * indicates the binding position.)
is. ];
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f5)
[Wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and a, b, c, d, The order of existence of each repeating unit bracketed with e or f is arbitrary in the formula. ]
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f6)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d, The order of existence of each repeating unit bracketed with e or f is arbitrary in the formula. ]
12. The article according to claim 11, which is a group represented by R ^Si is represented by the following formula (S1), (S2), (S3), (S4) or (S5):
[In the formula:
R ¹¹ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ¹² is independently at each occurrence a hydrogen atom or a monovalent organic group;
n1 is an integer of 0 to 3 independently for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit;
X ¹¹ is independently at each occurrence a single bond or a divalent organic group;
R ¹³ is independently at each occurrence a hydrogen atom or a monovalent organic group;
t is independently at each occurrence an integer greater than or equal to 2;
R ¹⁴ is independently at each occurrence a hydrogen atom, a halogen atom or —X ¹¹ —SiR ¹¹ _n1 R ¹² _3-n1 ;
each occurrence of R ¹⁵ is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms;
R ^a1 is independently at each occurrence -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ;
Z ¹ is independently at each occurrence an oxygen atom or a divalent organic group;
R ²¹ is independently at each occurrence -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ;
R ²² is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ²³ is independently at each occurrence a hydrogen atom or a monovalent organic group;
p1 is independently at each occurrence an integer from 0 to 3;
q1 is independently at each occurrence an integer from 0 to 3;
r1 is independently at each occurrence an integer from 0 to 3;
the sum of p1, q1, and r1 is 3 in the ^SiR21 _p1 ^R22 _q1 ^R23 _r1 unit;
Z ^1′ is independently at each occurrence an oxygen atom or a divalent organic group;
R ^21′ is independently at each occurrence —Z ^1″ —SiR ^22″ _q1″ R ^23″ _r1″ ;
R ^22′ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ^23′ at each occurrence is independently a hydrogen atom or a monovalent organic group;
p1′ is independently at each occurrence an integer from 0 to 3;
q' is independently at each occurrence an integer from 0 to 3;
r' is independently at each occurrence an integer from 0 to 3;
the sum of p1′, q1′ and r1′ is 3 in the SiR ^21′ _p1′ R ^22′ _q1′ R ^23′ _r1′ unit;
Z ^1″ is independently at each occurrence an oxygen atom or a divalent organic group;
R ^22″ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ^23″ at each occurrence is independently a hydrogen atom or a monovalent organic group;
q1″ is independently at each occurrence an integer from 0 to 3;
r1″ is independently at each occurrence an integer from 0 to 3;
the sum of q1″ and r1″ is 3 in SiR ^22″ _q1″ R ^23″ _r1″ units;
each occurrence of R ^b1 is independently a hydroxyl group or a hydrolyzable group;
R ^c1 is independently at each occurrence a hydrogen atom or a monovalent organic group;
k1 is independently at each occurrence an integer from 0 to 3;
l1 is independently at each occurrence an integer from 0 to 3;
m1 is independently at each occurrence an integer from 0 to 3;
the sum of k1, l1 and m1 is 3 in SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 units;
R ^d1 is independently at each occurrence -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ;
Z ² is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
R ³¹ is independently at each occurrence -Z ^2' -CR ^32' _q2' R ^33' _r2' ;
R ³² is independently at each occurrence -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;
each occurrence of R ³³ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group;
p2 is independently at each occurrence an integer from 0 to 3;
q2 is independently at each occurrence an integer from 0 to 3;
r2 is independently at each occurrence an integer from 0 to 3;
The sum of p2, q2, and r2 is 3 in the SiR ³¹ _p2 R ³² _q2 R ³³ _r2 unit, and Z ^2′ is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group can be;
R ^32′ is independently at each occurrence —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ^33′ is independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group;
q2' is independently at each occurrence an integer from 0 to 3;
r2' is independently at each occurrence an integer from 0 to 3;
the sum of q2' and r2' is 3 in the SiR ^32' _q2' R ^33' _r2' unit;
Z ³ is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
R ³⁴ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ³⁵ is independently at each occurrence a hydrogen atom or a monovalent organic group;
n2 is independently at each occurrence an integer from 0 to 3;
R ^e1 is independently at each occurrence —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ^f1 is independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group;
k2 is independently at each occurrence an integer from 0 to 3;
l2 is independently at each occurrence an integer from 0 to 3;
m2 is independently at each occurrence an integer from 0 to 3;
the sum of k2, l2 and m2 is 3 in CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 units;
R ^g1 and R ^h1 are each independently at each occurrence -Z ⁴ -SiR ¹¹ _n1 R ¹² _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ;
Z ⁴ is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
However, in formulas (S1), (S2), (S3), (S4) and (S5), there is at least one Si atom to which a hydroxyl group or hydrolyzable group is bonded. ]
12. The article according to claim 11, which is a group represented by X ^A is each independently a single bond or a divalent organic group,
12. The article of claim 11, wherein [alpha], [beta], and [gamma] are unity. X ^A is each independently a trivalent organic group,
α is 1 and β is 2, or α is 2 and β is 1,
γ is 2;
12. The article of claim 11. 2. The article of claim 1, wherein said substrate is a glass substrate. A film-forming material comprising silicon oxide and cerium oxide, wherein the molar ratio of silicon atoms to cerium atoms is from 10:90 to 99.99:0.01. 20. The film-forming material according to claim 19, further comprising an alkali metal or an alkaline earth metal in an amount of 0.1 to 30 mol % based on the total amount of silicon atoms, cerium atoms, alkali metals and alkaline earth metals.