Treated article and method of making the same

Patent metadata

Field	Value
Publication number	US-10675658-B2
Application number	US-201515126655-A
Country	US
Kind code	B2
Filing date	Mar 17, 2015
Priority date	Mar 18, 2014
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

A method of making a treated article having a metal surface. The method includes treating the metal surface with a primer composition comprising a secondary or tertiary amino-functional compound having at least two independently selected silane groups to provide a primed metal surface and subsequently treating the primed metal surface with a treatment composition comprising a fluorinated compound represented by formula Rf{—X—[Si(Y)3−x(R)x]y}z. An article treated by such a method is also disclosed. The use of a secondary or tertiary amino-functional compound having at least two independently selected silane groups as a primer for a metal surface before treatment with the fluorinated silane and a method of treating a metal surface with a treatment composition including the secondary or tertiary amino-functional compound having at least two independently selected silane groups and certain fluorinated silanes are also disclosed.

First claim

What is claimed is:

1. A method of making a treated article having a metal surface, the method comprising:
treating the metal surface with a primer composition comprising a secondary or tertiary amino-functional compound having at least two independently selected silane groups to provide a primed metal surface; and
subsequently treating the primed metal surface with a treatment composition comprising a fluorinated compound represented by formula:
Rf{Q-X′—[Si(Y) 3−x (R) x ] y } z

wherein:
Rf is a polyfluoropolyether group;
Q is —C(O)—N(R′)—, —C(O)—O—, or —SO 2 N(R′)—, wherein R′ is hydrogen or alkyl having up to 4 carbon atoms; and
X′ is a divalent or trivalent organic linking group comprising at least one of alkylene or arylalkylene interrupted by at least one carbamate or urea;
each Y is independently halogen, alkoxy, hydroxyl, acyloxy, polyalkyleneoxy, or aryloxy;
R is an alkyl group having up to 8 carbon atoms or a phenyl group;
x is 0 or 1 or 2;
y is a value from 1 to 8; and
z is 1 or 2.

2. The method of claim 1 , wherein in the fluorinated compound represented by formula Rf{Q-X′—[Si(Y) 3−x (R) x ] y } z ,
Q is —C(O)—N(R′)—, wherein R′ is hydrogen or alkyl having up to 4 carbon atoms; and
X′ is a divalent or trivalent organic linking group comprising alkylene interrupted by at least one carbamate or urea.

3. The method of claim 2 , wherein Q is —C(O)—N(R′)—, and X′ is divalent or trivalent alkylene that is interrupted by at least one carbamate.

4. The method of claim 3 , wherein X′ is

5. The method of claim 1 , wherein the secondary or tertiary amino-functional compound is represented by formula
(R 3 ) 2 N—R 1 —[Si(Y) p (R 2 ) 3−p ] q

wherein
R 1 is a multivalent alkylene group or a multivalent alkylene group interrupted by one or more —O— groups or up to three —NR 3 — groups;
R 2 is alkyl or arylalkylenyl;
each R 3 is independently hydrogen, alkyl, arylalkylenyl, or —R 1 —[Si(Y) p (R 2 ) 3−p ];
Y is alkoxy, acyloxy, aryloxy, polyalkyleneoxy, halogen, or hydroxyl;
p is 1, 2, or 3; and
q is 1, 2, or 3,

with the provisos that at least two independently selected —Si(Y) p (R 2 ) 3−p groups are present and that both R 3 groups may not be hydrogen.

6. The method of claim 5 , wherein one R 3 is alkyl or hydrogen, and the other R 3 is —R 1 —[Si(Y) p (R 2 ) 3−p ].

7. The method of claim 1 , wherein the secondary or tertiary amino-functional compound is bis(3-trimethoxysilylpropyl)amine, N-methyl-bis(3-trimethoxysilylpropyl)amine, or N,N′-bis[3-trimethoxysilylpropyl]-ethylenediamine.

8. The method of claim 1 , wherein Rf comprises perfluorinated repeating units comprising at least one of —(C n F 2n O)—, —(CF(Z)O)—, —(CF(Z)C n F 2n O)—, or —(C n F 2n CF(Z)O)—; and wherein Z is a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoroalkyl group or a perfluoroalkoxy group interrupted by at least one ether linkage, and n is an integer from 1 to 12.

9. The method of claim 8 , wherein z is 2, and Rf is —CF 2 O(CF 2 O) m (C 2 F 4 O) b CF 2 —, —CF 2 O(C 2 F 4 O) b CF 2 —, —(CF 2 ) 3 O(C 4 F 8 O) b (CF 2 ) 3 —, or —CF(CF 3 )—(OCF 2 CF(CF 3 )) b O—Rf′—O(CF(CF 3 )CF 2 O) b CF(CF 3 )—, and wherein Rf′ is a perfluoroalkylene group or a perfluoroalkylene group interrupted by at least one ether or amine linkage, m is 1 to 50, and b is 3 to 40.

10. The method of claim 1 , wherein Rf is C 3 F 7 O(CF(CF 3 )CF 2 O) a CF(CF 3 )—, C 3 F 7 O(CF 2 CF 2 CF 2 O) a CF 2 CF 2 —, or CF 3 O(C 2 F 4 O) a CF 2 —, wherein “a” has an average value of 3 to 50, and wherein z is 1.

11. The method of claim 1 , wherein the fluorinated compound is present in the treatment composition in a range from 0.01 percent to 2 percent by weight, based on the total weight of the treatment composition, and wherein the treatment composition further comprises at least one of an organic solvent or an acid catalyst.

12. A treated article treated according to the method of claim 1 , the treated article comprising:
a metal surface, wherein a layer is formed on at least a portion of the metal surface, wherein the layer comprises a secondary or tertiary amino-functional compound including at least one siloxane and at least one other group selected from the group consisting of siloxane, silanol, and silane; and
a fluorinated compound bonded to the secondary or tertiary amino-functional compound, wherein the fluorinated compound is represented by formula:
Rf{Q-X′—[Si(Y′) 3−x (R) x ] y } z

wherein:
Rf is a polyfluoropolyether group;
Q is —C(O)—N(R′)—, —C(O)—O—, or —SO 2 N(R′)—, wherein R′ is hydrogen or alkyl having up to 4 carbon atoms; and
X′ is a divalent or trivalent organic linking group comprising at least one of alkylene or arylalkylene interrupted by at least one carbamate or urea;
each Y′ is independently halogen, alkoxy, hydroxyl, acyloxy, polyalkyleneoxy, aryloxy, or —O— bonded to the secondary or tertiary amino-functional compound, forming the at least one siloxane;
R is an alkyl group having up to 8 carbon atoms or a phenyl group;
x is 0 or 1 or 2;
y is a value from 1 to 8; and
z is 1 or 2.

13. A method of making a treated article having a metal surface, the method comprising treating the metal surface with a treatment composition comprising:
a secondary or tertiary amino-functional compound having at least two independently selected silane groups; and
a fluorinated compound represented by formula:
Rf{C(O)NR′—X″—[Si(Y) 3−x (R) x ] y } z

wherein:
Rf is a polyfluoropolyether group;
X″ is a divalent or trivalent organic linking group comprising at least one of alkylene or arylalkylene, each of which is interrupted by at least one carbamate or urea;
each Y is independently halogen, alkoxy, hydroxyl, acyloxy, polyalkyleneoxy, or aryloxy;
R is an alkyl group having up to 8 carbon atoms or a phenyl group;
R′ is hydrogen or alkyl having up to 4 carbon atoms;
x is 0 or 1 or 2;
y is a value from 1 to 8; and
z is 1 or 2.

14. The method of claim 1 , wherein the metal surface comprises at least one of chromium, a chromium alloy, iron, aluminum, copper, nickel, zinc, tin, stainless steel, or brass.

15. The treated article of claim 12 , wherein in the fluorinated compound represented by formula Rf{Q-X′—[Si(Y′) 3−x (R) x ] y } z ,
Q is —C(O)—N(R′)—, wherein R′ is hydrogen or alkyl having up to 4 carbon atoms; and
X′ is a divalent or trivalent organic linking group comprising alkylene interrupted by at least one carbamate or urea.

16. The treated article of claim 12 , wherein Q is —C(O)—N(R′)—, and X′ is divalent or trivalent alkylene that is interrupted by at least one carbamate.

17. The treated article of claim 12 , wherein the secondary or tertiary amino-functional compound is represented by formula
(R 3 ) 2 N—R 1 —[Si(Y 2 ) p (R 2 ) 3−p ] q

wherein
R 1 is a multivalent alkylene group optionally interrupted by one or more —O— groups or up to three —NR 3 — groups;
R 2 is alkyl or arylalkylenyl;
each R 3 is independently hydrogen, alkyl, arylalkylenyl, or —R 1 —[Si(Y 2 ) p (R 2 ) 3−p ];
each Y 2 is independently alkoxy, acyloxy, aryloxy, polyalkyleneoxy, halogen, hydroxyl, or —O— bonded to the fluorinated compound, forming the at least one siloxane;
p is 1, 2, or 3; and
q is 1, 2, or 3,

with the provisos that at least two independently selected —Si(Y 2 ) p (R 2 ) 3−p groups are present and that both R 3 groups may not be hydrogen.

18. The treated article of

Assignees

• 3M Innovative Properties Co

Inventors

• Audenaert Frans A

Classifications

• C23C22/58

  Treatment of other metallic material · CPC title

• C23C22/54

  Treatment of refractory metals or alloys based thereon · CPC title

• B05D7/52

  Two layers · CPC title

• C23C22/50

  Treatment of iron or alloys based thereon · CPC title

• C09D5/002 Primary

  Priming paints (C09D5/08 takes precedence) · CPC title