# US 10,865,312 B2 · Surface treatment agent

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- Number: US 10,865,312 B2
- Document ID: US10865312B2
- Status: Granted
- Kind: B2
- Application number: 15/546,319
- Filed: 2015-11-26
- Published: 2018-02-01
- Granted: 2020-12-15
- Earliest claimed: 2015-01-29
- Assignees: Daikin Industries, Ltd.
- Applicants: Daikin Industries, Ltd.
- Inventors: Hisashi Mitsuhashi; Kenichi Katsukawa
- Web page: https://patentgrep.com/patent/US10865312B2

## CPC

- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)}
- C08G 65/007: {containing fluorine}
- C08G 65/336: containing silicon
- C08G 77/24: halogen-containing groups
- C09D 5/00: Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes
- C09D 5/16: Antifouling paints; Underwater paints
- C09D 5/165: {containing hydrolysable groups (C09D5/1643 takes precedence)}
- C09D 5/1675: {Polyorganosiloxane-containing compositions}
- C09D 171/02: Polyalkylene oxides
- 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)
- 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)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

A surface-treating agent including at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1) and (C2): wherein, each of symbols is as defined in the specification, and wherein a proportion of the perfluoro(poly)ether group containing silane compound having a molecular weight of 3,000 or less in the perfluoro(poly)ether group containing silane compounds of any of the above general formulae is 9 mol % or less.

## Claims

### Claim 1

A surface-treating agent comprising at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1) and (C2):
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 1 or more, 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 hydrogen atom or an alkyl group having 1-22 carbon atoms;
R2 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
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;
n is, independently per a unit (—SiR1nR23-n), an integer of 0-3;
there is at least one R2 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 —Z—SiR71pR72qR73r;
Z 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 Z 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;
p is each independently at each occurrence an integer of 0-3;
q is each independently at each occurrence an integer of 0-3;
r is each independently at each occurrence an integer of 0-3;
in one Ra, the sum of p, q and r is 3, and there is at least one R72 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;
k is each independently at each occurrence an integer of 1-3;
l is each independently at each occurrence an integer of 0-2;
m is each independently at each occurrence an integer of 0-2;
the sum of k, l and m is 3 in each unit in parentheses with the subscript γ,
wherein a proportion of the perfluoro(poly)ether group containing silane compound having a molecular weight of 3,000 or less in the perfluoro(poly)ether group containing silane compounds of any of the above general formulae is 9 mol % or less; and
wherein the number average molecular weight of the perfluoro(poly)ether group containing silane compound of any of formulae (A1), (A2), (B1), (B2), (C1) and (C2) is 10,000 or less.

### Claim 2 (depends on 1)

The surface-treating agent according to claim 1 wherein the proportion of the perfluoro(poly)ether group containing silane compound having a molecular weight of 3,000 or less in the perfluoro(poly)ether group containing silane compounds of any of the above general formulae is 7 mol % or less.

### Claim 3 (depends on 1)

The surface-treating agent according to claim 1 wherein the proportion of the perfluoro(poly)ether group containing silane compound having a molecular weight of 3,000 or less in the perfluoro(poly)ether group containing silane compounds of any of the above general formulae is 5 mol % or less.

### Claim 4 (depends on 1)

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

### Claim 5 (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)n—(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
—(OC2F4—R8)f— (iv)
wherein R8 is a group selected from OC2F4, OC3F6 and OC4F8; and
f is an integer of 2-100.

### Claim 6 (depends on 1)

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

### Claim 7 (depends on 1)

The surface-treating agent according to claim 1 wherein X1, X5 and X7 are a divalent organic group, α, β and γ are 1, and α′, β′ and γ′ are 1.

### Claim 8 (depends on 7)

The surface-treating agent according to claim 7 wherein X1, X5 and X7 are each independently —(R31)p′—(Xa)q′—
wherein:
R31 is 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(R33)2—, —(Si(R33)2O)m′—Si(R33)2— (wherein m′ is an integer of 1-100), —CONR34—, —O—CONR34—, —NR34— and —(CH2)n′— (wherein n′ is an integer of 1-20);
R33 is each independently at each occurrence a phenyl group, a C1-6 alkyl group or a C1-6 alkoxy group;
R34 is each independently at each occurrence a hydrogen atom, a phenyl group or a C1-6 alkyl group;
p′ is 0 or 1;
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 9 (depends on 7)

The surface-treating agent according to claim 7 wherein X1, X5 and X7 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(CH2)2O(Si(CH3)2O)Si(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—,
—CH2OCH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2—,
—CH2OCH2CH2CH2Si(OCH2CH3)2Si(OCH2CH3)2(CH2)2—,
—(CH2)2—,
—(CH2)3—,
—(CH2)4—,
—(CH2)6—,
—(CH2)2—Si(CH3)2(CH2)2—,
—CONH—(CH2)3—,
—CON(CH3)—(CH2)3—,
—CON(Ph)-(CH2)3— (wherein Ph is phenyl),
—CONH—(CH2)6—,
—CON(CH3)—(CH2)6—,
—CON(Ph)-(CH2)6— (wherein Ph is phenyl),
—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)20Si(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)—(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—,

### Claim 10 (depends on 1)

The surface-treating agent according to claim 1 wherein
X1 is —O—CFR13—(CF2)e—,
R13 is a fluorine atom or a lower fluoroalkyl group, and
e is 0 or 1.

### Claim 11 (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 12 (depends on 1)

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

### Claim 13 (depends on 1)

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

### Claim 14 (depends on 13)

The surface-treating agent according to claim 13 wherein X1, X5 and X7 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) and (C2):
—CH2O(CH2)2—,
—CH2O(CH2)3—,
—CF2O(CH2)3—,
—(CH2)2—,
—(CH2)3—,
—(CH2)4—,
—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) and (C2) and the others 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
R42 is each independently a hydrogen atom, a C1-6 alkyl group or a C1-6 alkoxy group.

### Claim 15 (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 16 (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 17 (depends on 1)

The surface-treating agent a 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 18 (depends on 1)

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

### Claim 19 (depends on 18)

The surface-treating agent according to claim 18 wherein the fluorine-containing oil is one or more compounds of the formula (3):
R21—(OC4F8)a′—(OC3F6)b′—(OC2F4)c′—(OCF2)d′—R22 (3)
wherein:
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; and
a′, b′, c′ and d′ are the repeating number of each of four repeating units of perfluoro(poly)ether which constitute a main backbone of the polymer, and are each independently an integer of 0 or more and 300 or less, the sum of a′, b′, c′ and d′ is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a′, b′, c′ and d′ is not limited in the formula.

### Claim 20 (depends on 18)

The surface-treating agent according to claim 18 wherein the fluorine-containing oil is one or more compounds of the formula (3a) or (3b):
R21—(OCF2CF2CF2)b″—R22 (3a)
R21—(OCF2CF2CF2)a″—(OCF2CF2CF2)b″—(OCF2CF2)c″—(OCF2)d″—R22 (3b)
wherein:
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 (3a), b″ is an integer of 1 or more and 100 or less;
in the formula (3b), a″ and b″ are each independently an integer of 0 or more and 30 or less, and c″ and d″ are each independently an integer of 1 or more and 300 or less; 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 21 (depends on 20)

The surface-treating agent according to claim 20 wherein a mass ratio of the perfluoro(poly)ether group containing silane compound and the compound of the formula (3b) is 10:1-1:10.

### Claim 22 (depends on 20)

The surface-treating agent according to claim 20 wherein a mass ratio of the perfluoro(poly)ether group containing silane compound and the compound of the formula (3b) is 4:1-1:4.

### Claim 23 (depends on 20)

The surface-treating agent according to claim 20 wherein the compound of the formula (3a) has a number average molecular weight of 2,000-8,000.

### Claim 24 (depends on 20)

The surface-treating agent according to claim 20 wherein the compound of the formula (3b) has a number average molecular weight of 8,000-30,000.

### Claim 25 (depends on 20)

The surface-treating agent according to claim 20 wherein the compound of the formula (3b) has a number average molecular weight of 3,000-8,000.

### Claim 26 (depends on 1)

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

### Claim 27 (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 28 (depends on 1)

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

### Claim 29 (depends on 1)

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

### Claim 30 (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 31 (depends on 30)

The article according to claim 30 wherein the base material is a glass or a sapphire glass.

### Claim 32 (depends on 31)

The article according to claim 31 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 33 (depends on 30)

The article according to claim 30 wherein the article is an optical member.

### Claim 34 (depends on 30)

The article according to claim 30 wherein the article is a display.