# US 10,870,729 B2 · Surface treatment agent

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- Number: US 10,870,729 B2
- Document ID: US10870729B2
- Status: Granted
- Kind: B2
- Application number: 16/072,697
- Filed: 2017-01-24
- Published: 2019-01-31
- Granted: 2020-12-22
- Earliest claimed: 2016-01-26
- Assignees: Daikin Industries, Ltd.
- Applicants: Daikin Industries, Ltd.
- Inventors: Daiki Ishii; Yoshiaki Honda; Takeshi Maehira; Nozomi Nakano
- Web page: https://patentgrep.com/patent/US10870729B2

## CPC

- C08G 65/336: containing silicon
- C08G 65/007: {containing fluorine}
- C09D 127/22: modified by chemical after-treatment
- C09D 171/00: Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain (based on polyacetals C09D159/00; based on epoxy resins C09D163/00; based on polythioether-ethers C09D181/02; based on polyethersulfones C09D181/06); Coating compositions based on derivatives of such polymers
- C09D 183/12: containing polyether sequences
- C09K 3/18: for application to surfaces to minimize adherence of ice, mist or water thereto (rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30); Thawing or antifreeze materials for application to surfaces (used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00)
- G02B 1/18: Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films (G02B1/16 takes precedence)
- C08G 2650/48: containing fluorine, e.g. perfluropolyethers
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

## Abstract

A surface-treating agent containing (1) at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2): and (2) a fluorine containing oil of the general formula (O): Rf1-PFPE′-Rf2 (O) wherein: each of the symbols are as defined herein. A content of the fluorine containing oil having a molecular weight of 2.0 or more times higher than the number average molecular weight of the fluorine-containing oils among the fluorine containing oil of the formula (O) is 10 mol % or less.

## Claims

### Claim 1

A surface-treating agent comprising
(1) at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):
wherein:
PFPE is each independently at each occurrence a group of the formula:
—(OC4F8)a—(OC3F6)b—(OC2F4)c—(OCF2)d—
wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula;
Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;
R1 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
R2 is each independently at each occurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms;
R11 is each independently at each occurrence a hydrogen atom or a halogen atom;
R12 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
n1 is, independently per a unit (—SiR1n1R23- n 1), an integer of 0-3;
at least one n1 is an integer of 1-3 in the formulae (A1), (A2), (B1) and (B2);
X1 is each independently a single bond or a 2-10 valent organic group;
X2 is each independently at each occurrence a single bond or a divalent organic group;
t is each independently at each occurrence an integer of 1-10;
α is each independently an integer of 1-9;
α′ is each independently an integer of 1-9;
X5 is each independently a single bond or a 2-10 valent organic group;
β is each independently an integer of 1-9;
β′ is each independently an integer of 1-9;
X7 is each independently a single bond or a 2-10 valent organic group;
γ is each independently an integer of 1-9;
γ′ is each independently an integer of 1-9;
Ra is each independently at each occurrence —Z1—SiR71p1R72q1R73r1;
Z1 is each independently at each occurrence an oxygen atom or a divalent organic group;
R71 is each independently at each occurrence Ra′;
Ra′ has the same definition as that of Ra;
in Ra, the number of Si atoms which are straightly linked via the Z1 group is up to five;
R72 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
R73 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
p1 is each independently at each occurrence an integer of 0-3;
q1 is each independently at each occurrence an integer of 0-3;
r1 is each independently at each occurrence an integer of 0-3;
at least one q1 is an integer of 1-3 in the formula (C1) and (C2);
Rb is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
Rc is each independently at each occurrence a hydrogen atom or a lower alkyl group;
k1 is each independently at each occurrence an integer of 1-3;
l1 is each independently at each occurrence an integer of 0-2;
m1 is each independently at each occurrence an integer of 0-2;
the sum of k1, l1 and m1 is 3 in each unit in parentheses with the subscript γ;
X9 is each independently a single bond or a 2-10 valent organic group;
δ is each independently an integer of 1-9;
δ′ is each independently an integer of 1-9;
Rd is each independently at each occurrence —Z2—CR81p2R82q2R83r2;
Z2 is each independently at each occurrence an oxygen atom or a divalent organic group;
R81 is each independently at each occurrence Rd′;
Rd′ has the same definition as that of Rd;
in Rd, the number of C atoms which are straightly linked via the Z2 group is up to five;
R82 is each independently at each occurrence —Y—SiR85n2R863-n2;
Y is each independently at each occurrence a divalent organic group;
R85 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
R86 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
n2 is an integer of 1-3 independently per unit (—Y—SiR85n2R863-n2);
in formulae (D1) and (D2), at least one n2 is an integer of 1-3;
R83 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
p2 is each independently at each occurrence an integer of 0-3;
q2 is each independently at each occurrence an integer of 0-3;
r2 is each independently at each occurrence an integer of 0-3;
Re is each independently at each occurrence —Y—SiR85n2R86n2;
Rf is each independently at each occurrence a hydrogen atom or a lower alkyl group;
k2 is each independently at each occurrence an integer of 0-3;
l2 is each independently at each occurrence an integer of 0-3; and
m2 is each independently at each occurrence an integer of 0-3;
in formulae (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3; and
(2) a fluorine containing oil of the general formula (0):
Rf1-PFPE′-Rf2 (O)
wherein:
Rf1 is each independently at each occurrence a C1-16 alkyl group which may be substituted by one or more fluorine atoms;
Rf2 is a C1-16 alkyl group which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom;
PFPE′ is —(OC4F8)a′—(OC3F6)b′(OC2F4)c′—(OCF2)d′—;
a′, b′, c′ and d′ are each independently an integer of 0 or more and 300 or less, the sum of a′, b′, c′ and d′ is at least 1, and the occurrence order of the respective repeating units in parentheses with the subscript a′, b′, c′ or d′ is not limited in the formula,
wherein a content of the fluorine containing oil having a molecular weight of 2.0 or more times higher than the number average molecular weight of the fluorine-containing oil among the fluorine containing oil of the formula (O) is 10 mol % or less; and
wherein a number average molecular weight of the fluorine containing oil is 1,500 or more and 30,000 or less.

### Claim 2 (depends on 1)

The surface-treating agent according to claim 1 wherein the content of the fluorine containing oil having a molecular weight of 2.0 or more times higher than the number average molecular weight of the fluorine-containing oil among the fluorine containing oil of the formula (O) is 5 mol % or less.

### Claim 3 (depends on 1)

The surface-treating agent according to claim 1 wherein a content of the fluorine containing oil having a molecular weight of 1.8 or more times higher than the number average molecular weight of the fluorine-containing oil among the fluorine containing oil of the formula (O) is 10 mol % or less.

### Claim 4 (depends on 3)

The surface-treating agent according to claim 3 wherein the content of the fluorine containing oil having a molecular weight of 1.8 or more times higher than the number average molecular weight of the fluorine-containing oil among the fluorine containing oil of the formula (O) is 5 mol % or less.

### Claim 5 (depends on 1)

The surface-treating agent according to claim 1 wherein the number average molecular weight of the fluorine containing oil is 2,000 or more and 10,000 or less.

### Claim 6

A surface-treating agent comprising
(1) at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):
wherein:
PFPE is each independently at each occurrence a group of the formula:
—(OC4F8)a—(OC3F6)b—(OC2F4)c—(OCF2)d—
wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula;
Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;
R1 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
R2 is each independently at each occurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms;
R11 is each independently at each occurrence a hydrogen atom or a halogen atom;
R12 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
n1 is, independently per a unit (—SiR1n 1 R2 3- n 1), an integer of 0-3;
at least one n1 is an integer of 1-3 in the formulae (A1), (A2), (B1) and (B2);
X1 is each independently a single bond or a 2-10 valent organic group;
X2 is each independently at each occurrence a single bond or a divalent organic group;
t is each independently at each occurrence an integer of 1-10;
α is each independently an integer of 1-9;
α′ is each independently an integer of 1-9;
X5 is each independently a single bond or a 2-10 valent organic group;
β is each independently an integer of 1-9;
β′ is each independently an integer of 1-9;
X7 is each independently a single bond or a 2-10 valent organic group;
γ is each independently an integer of 1-9;
γ′ is each independently an integer of 1-9;
Ra is each independently at each occurrence —Z1—SiR71p1R72q1R73r1;
Z1 is each independently at each occurrence an oxygen atom or a divalent organic group;
R71 is each independently at each occurrence Ra′;
Ra′ has the same definition as that of Ra;
in Ra, the number of Si atoms which are straightly linked via the Z1 group is up to five;
R72 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
R73 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
p1 is each independently at each occurrence an integer of 0-3;
q1 is each independently at each occurrence an integer of 0-3;
r1 is each independently at each occurrence an integer of 0-3;
at least one q1 is an integer of 1-3 in the formula (C1) and (C2);
Rb is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
Rc is each independently at each occurrence a hydrogen atom or a lower alkyl group;
k1 is each independently at each occurrence an integer of 1-3;
l1 is each independently at each occurrence an integer of 0-2;
m1 is each independently at each occurrence an integer of 0-2;
the sum of k1, l1 and m1 is 3 in each unit in parentheses with the subscript γ;
X9 is each independently a single bond or a 2-10 valent organic group;
δ is each independently an integer of 1-9;
δ′ is each independently an integer of 1-9;
Rd is each independently at each occurrence —Z2—CR81p2R82q2R83r2;
Z2 is each independently at each occurrence an oxygen atom or a divalent organic group;
R81 is each independently at each occurrence Rd′;
Rd′ has the same definition as that of Rd;
in Rd, the number of C atoms which are straightly linked via the Z2 group is up to five;
R82 is each independently at each occurrence —Y—SiR85n2R863-n2;
Y is each independently at each occurrence a divalent organic group;
R85 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
R86 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
n2 is an integer of 1-3 independently per unit (—Y—SiR85n2R863n2);
in formulae (D1) and (D2), at least one n2 is an integer of 1-3;
R83 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
p2 is each independently at each occurrence an integer of 0-3;
q2 is each independently at each occurrence an integer of 0-3;
r2 is each independently at each occurrence an integer of 0-3;
Re is each independently at each occurrence —Y—SiR85n2R86n2;
Rf is each independently at each occurrence a hydrogen atom or a lower alkyl group;
k2 is each independently at each occurrence an integer of 0-3;
l2 is each independently at each occurrence an integer of 0-3; and
m2 is each independently at each occurrence an integer of 0-3;
in formulae (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3; and
(2) a fluorine containing oil of the general formula (0):
Rf1-PFPE′-Rf2 (O)
wherein:
Rf1 is each independently at each occurrence a C1-16 alkyl group which may be substituted by one or more fluorine atoms;
Rf2 is a C1-16 alkyl group which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom;
PFPE′ is —(OC4F8)a′—(OC3F6)b′—(OC2F4)c′—(OCF2)d′—;
a′, b′, c′ and d′ are each independently an integer of 0 or more and 300 or less, the sum of a′, b′, c′ and d′ is at least 1, and the occurrence order of the respective repeating units in parentheses with the subscript a′, b′, c′ or d′ is not limited in the formula,
wherein a content of the fluorine containing oil having a molecular weight of 5,000 or more in the fluorine containing oil of the formula (O) is 10 mol % or less; and
wherein the number average molecular weight of the fluorine containing oil is 1,500 or more and 5,500 or less.

### Claim 7 (depends on 6)

The surface-treating agent according to claim 6 wherein the content of the fluorine containing oil having a molecular weight of 5,000 or more in the fluorine containing oil of the formula (O) is 5 mol % or less.

### Claim 8 (depends on 1)

The surface-treating agent according to claim 1 wherein a dispersity of the fluorine containing oil is 1.00 or more and 1.20 or less.

### Claim 9 (depends on 8)

The surface-treating agent according to claim 8 wherein the dispersity of the fluorine containing oil is 1.00 or more and 1.10 or less.

### Claim 10 (depends on 1)

The surface-treating agent according to claim 1 wherein the fluorine containing oil is one or more compounds of the formula (O1) or (O2):
R21—(OCF2CF2CF2)b″-R22 (01)
R21—(OCF2CF2CF2CF2)a″—(OCF2CF2CF2)b″—(OCF2CF2)c″—(OCF2)d″-R22 (O2)
R21 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;
R22 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom;
in the formula (O1), b″ is an integer of 1 or more and 100 or less;
in the formula (O2), a″ and b″ are each independently an integer of 0 or more and 30 or less, and c″ and d″ are each independently an integer of 1 or more and 300 or less; and
the occurrence order of the respective repeating units in parentheses with the subscript a″, b″, c″ or d″ is not limited in the formula.

### Claim 11 (depends on 10)

The surface-treating agent according to claim 10 wherein the fluorine containing oil is one or more fluorine containing oils of the formula (O2), and the number average molecular weight of the fluorine containing oil is 1,500-5,500.

### Claim 12 (depends on 1)

The surface-treating agent according to a claim 1 wherein Rf is a perfluoroalkyl group having 1-16 carbon atoms.

### Claim 13 (depends on 1)

The surface-treating agent according to claim 1 wherein PFPE is a group of any of the following formulas (i) to (iv):
—(OCF2CF2CF2)b— (i)
wherein b is an integer of 1-200;
—(OCF(CF3)CF2)b— (ii)
wherein b is an integer of 1-200;
—(OCF2CF2CF2CF2)a—(OCF2CF2CF2)b—(OCF2CF2)c—(OCF2)d— (iii)
wherein a and b are each independently 0 or an integer of 1-30, c and d are each independently an integer of 1-200, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula;
or
—(R7—R8)f— (iv)
wherein R7 is OCF2 or OC2F4,
R8 is a group selected from OC2 F4, OC3 F6 and OC4 F8; and
f is an integer of 2-100.

### Claim 14 (depends on 1)

The surface-treating agent according to claim 1 wherein X1, X5, X7 and X9 are each independently a 2-4 valent organic group, α, β, γ and δ are each independently 1-3, and α′, β′, γ′ and δ′ are 1.

### Claim 15 (depends on 1)

The surface-treating agent according to claim 1 wherein X1, X5, X7 and X9 are each independently a 2 valent organic group, α, β, γ and δ are 1, and α′, β′, γ′ and δ′ are 1.

### Claim 16 (depends on 15)

The surface-treating agent according to claim 15 wherein X1, X5, X7 and X9 are each independently —(R3 1)p′—(Xa)q′—
wherein:
R31 is each independently a single bond, —(CH2)s′— (wherein s′ is an integer of 1-20) or a o-, m- or p-phenylene group;
Xa is —(Xb)l′— wherein l′ is an integer of 1-10;
Xb is each independently at each occurrence selected from the group consisting of —O—, —S—, an o-, m- or p-phenylene group, —C(O)O—, —Si(R3 3)2 —, —(Si(R3 3)2 O)m′—Si(R3 3)2— (wherein m′ is an integer of 1-100), —CONR3 4 —, —O—CONR3 4 —, —NR3 4— and —(CH2)n′— (wherein n′ is an integer of 1-20);
R3 3 is each independently at each occurrence a phenyl group, a C1-6 alkyl group or a C1-6 alkoxy group;
R3 4 is each independently at each occurrence a hydrogen atom, a phenyl group or a C1-6 alkyl group;
p′ is 0, 1 or 2;
q′ is 0 or 1;
at least one of p′ and q′ is 1,
the occurrence order of the respective repeating units in parentheses with the subscript p′ or q′ is not limited in the formula; and
R31 and Xa is may be substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group and a C1-3 fluoroalkyl group.

### Claim 17 (depends on 1)

The surface-treating agent according to claim 1 wherein X1, X′, X′ and X9 are each independently selected from the group consisting of:
—CH2O(CH2)2—,
—CH2O(CH2)3—,
—CH2O(CH2)6—,
—CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2—,
—CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2—,
—CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2—,
—CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2—,
—CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2—,
—CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2—,
—CH2OCF2CHFOCF2—,
—CH2OCF2CHFOCF2CF2—,
—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—
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—,
—(CH2)2—,
—(CH2)3—,
—(CH2)4—,
—(CH2)5—,
—(CH2)6—,
—(CH2)2—Si(CH3)2—(CH2)2—
—CONH—(CH2)—,
—CONH—(CH2)2—,
—CONH—(CH2)3—,
—CON(CH3)—(CH2)3—,
—CON(Ph)—(CH2)3— wherein Ph is a phenyl group,
—CONH—(CH2)6—,
—CON(CH3)—(CH2)6—,
—CON(Ph)—(CH2)6— wherein Ph is a phenyl group,
—CONH—(CH2)2NH(CH2)3—,
—CONH—(CH2)6NH(CH2)3—,
—CH2O—CONH—(CH2)3—,
—CH2O—CONH—(CH2)6—,
—S—(CH2)3—,
—(CH2)2S(CH2)3—,
—CONH—(CH2)3Si(CH3)2OSi(CH3)2(CH2)2—,
—CONH—(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2—,
—CONH—(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2—,
—CONH—(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2—,
—CONH—(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2—,
—CONH—(CH2)3Si(CH3)2O(Si(CH3)2O)2OSi(CH3)2(CH2)2—,
—C(O)O—(CH2)3—,
—C(O)O—(CH2)6—,
-CH2−O—(CH2)3—Si(CH3)2—(CH2)2—Si(CH3)2—(CH2)2—,
—CH2—O—(CH2)3—Si(CH3)2—(CH2)2—Si(CH3)2—CH(CH3)—,
—CH2—O—(CH2)3—Si(CH3)2—(CH2)2—Si(CH3)2—(CH2)3—,
—CH2—O—(CH2)3—Si(CH3)2—(CH2)2—Si(CH3)2—CH(CH3)—CH2—,
—OCH2—,
—O(CH2)3—,
—OCFHCF2—,

### Claim 18 (depends on 1)

The surface-treating agent according to claim 1 wherein
X1 is —O—CFR1 3—(CF2)e—,
R13 is a fluorine atom or a lower fluoroalkyl group, and
e is 0 or 1.

### Claim 19 (depends on 1)

The surface-treating agent according to claim 1 wherein
X2 is —(CH2)s —, and
s is an integer of 0-2.

### Claim 20 (depends on 1)

The surface-treating agent according to claim 1 wherein k1 is 3, and q1 is 3 in Ra.

### Claim 21 (depends on 1)

The surface-treating agent according to claim 1 wherein l2 is 3, and n2 is 3.

### Claim 22 (depends on 1)

The surface-treating agent according to claim 1 wherein Y is a C1-6 alkylene group, —(CH2)g′—O—(CH2)h′— (wherein g′ is an integer of 0-6, and h′ is an integer of 0-6), or -phenylene-(CH2)i′— (wherein i′ is an integer of 0-6).

### Claim 23 (depends on 1)

The surface-treating agent according to claim 1 wherein X1, X5, X7 and X9 are each independently a 3-10 valent organic group.

### Claim 24 (depends on 23)

The surface-treating agent according to claim 23 wherein X1, X5, X7 and X9 are each independently selected from the group consisting of:
wherein in each group, at least one of T is the following group attached to PFPE in the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):
—CH2O(CH2)2—,
—CH2O(CH2)3—,
—CF2O(CH2)3—,
—(CH2)2—,
—(CH2)3—,
—(CH2)4—,
—CONH—(CH2)—,
—CONH—(CH2)2—,
—CONH—(CH2)3—,
—CON(CH3)—(CH2)3—,
—CON(Ph)—(CH2)3— wherein Ph is a phenyl group, and
at least one of the other T is —(CH2)n— (wherein n is an integer of 2-6) attached to the carbon atom or the Si atom in the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2), and if present, the others T are each independently a methyl group, a phenyl group, a alkoxy having 1-6 carbon atoms, or a radical scavenger group or an ultraviolet ray absorbing group,
R41 is each independently a hydrogen atom, a phenyl group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and
R4 2 is each independently a hydrogen atom, a C1-6 alkyl group or a C1-6 alkoxy group.

### Claim 25 (depends on 1)

The surface-treating agent according to claim 1 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (A1) and (A2).

### Claim 26 (depends on 1)

The surface-treating agent according to claim 1 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (B1) and (B2).

### Claim 27 (depends on 1)

The surface-treating agent according to claim 1 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (C1) and (C2).

### Claim 28 (depends on 1)

The surface-treating agent according to claim 1 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (D1) and (D2).

### Claim 29 (depends on 1)

The surface-treating agent according to claim 1 containing the fluorine containing oil at 5-95% by weight with respect to the total of the perfluoro(poly)ether group containing silane compound and the fluorine containing oil.

### Claim 30 (depends on 1)

The surface-treating agent according to claim 1 further comprising one or more other components selected form a silicone oil and a catalyst.

### Claim 31 (depends on 1)

The surface-treating agent according to claim 1 further comprising a solvent.

### Claim 32 (depends on 1)

The surface-treating agent according to claim 1 which is used as an antifouling-coating agent or a water-proof coating agent.

### Claim 33 (depends on 1)

The surface-treating agent according to claim 1 for vacuum deposition.

### Claim 34 (depends on 1)

A pellet comprising the surface-treating agent according to claim 1.

### Claim 35 (depends on 1)

An article comprising a base material and a layer which is formed on a surface of the base material from the surface-treating agent according to claim 1.

### Claim 36 (depends on 35)

The article according to claim 35 having a haze value of 0.3 or less.

### Claim 37 (depends on 35)

The article according to claim 35 wherein the base material is a glass or a sapphire glass.

### Claim 38 (depends on 37)

The article according to claim 37 wherein the glass is a glass selected from the group consisting of a soda-lime glass, an alkali aluminosilicate glass, a borosilicate glass, a non-alkaline glass, a crystal glass, and a quartz glass.

### Claim 39 (depends on 35)

The article according to claim 35 wherein the article is an optical member.

### Claim 40 (depends on 35)

The article according to claim 35 wherein the article is a display.

### Claim 41 (depends on 5)

The surface-treating agent according to claim 5 wherein the content of the fluorine containing oil in the surface treating agent is 5-90% by mass with respect to the total of the perfluoro(poly)ether group containing silane compound and the fluorine containing oil.