Ceramer composition and composite comprising free radically curable fluorochemical component

• US 6,238,798 B1
• Filed: 02/22/1999
• Issued: 05/29/2001
• Est. Priority Date: 02/22/1999
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Moore, George G. I., Rambosek, Thomas W., Kang, Soonkun
• Primary Examiner(s): Chen, Vivian
• Application Number:
  US09/255,195
• Time in Patent Office: 827 Days
• Field of Search: 428/421, 428/422, 522/90, 522/99, 522/91, 522/93, 522/144, 522/172, 106/287.1, 106/287.13, 106/287.14, 106/287.16, 106/287.15, 427/487, 427/503, 427/515, 526/242, 526/243, 526/245, 526/247, 526/248, 526/279
• US Class Current: 428/421
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: C08F 222/185 the ester chains containing seven or more carbon atoms
• CPC Class Codes: Y10T 428/259 Silicic material
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated

Abstract

A ceramer composition is provided that comprises a plurality of colloidal inorganic oxide particles and a free-radically curable binder precursor. The free-radically curable binder precursor comprises a fluorochemical component that further comprises at least two free-radically curable moieties and at least one fluorinated moiety. By virtue of the inclusion of the fluorochemical component, the ceramer compositions of the present invention can be used to provide ceramer composites and ceramer composite structures with excellent stain, oil and/or water repellency characteristics as well as a high level of abrasion resistance and hardness.

Claims

1. A free-radically curable ceramer composition comprising:

(a) a plurality of colloidal inorganic oxide particles wherein said colloidal inorganic oxide particles are surface treated with a surface treatment agent comprising a curable silane component comprising a hydrolyzable silane moiety and a free-radically curable moiety, and

(b) a free-radically curable binder precursor, wherein said free-radically curable binder precursor comprises a free-radically curable fluorochemical component comprising at least two free-radically curable moieties and at least one fluorinated moiety.

2. The free-radically curable ceramer composition of claim 1 wherein the weight ratio of the colloidal inorganic oxide particles to the free-radically curable binder precursor is from about 1:

10 to about 1;

1.5.

3. The free-radically curable ceramer composition of claim 2, wherein the free-radically curable fluorochemical component is selected from the group consisting of

C₈F₁₇SO₂N[C₂H₄OCOCH═ CH₂]₂,

CH₂═

CH—

CO—

OCH₂(CF₂OCF₂)_nCH₂OCOCH═

CH₂, n=2-10

(CF₃)₂CFCH(OCOCH═

CH₂)(CF₂)₈CH(OCOCH═

CH₂)CF(CF₃)₂,

C₄F₉CF(C₂F₅)COOCH₂C(C₂H₅)(CH₂OCOCH═

CH₂)₂, C₄F₉SO₂N(C₂H₄OCOCH═

CH₂)₂,

and

C₆F₁₃SO₂N(C₂H₄OCOCH═

CH₂)₂.

4. The free-radically curable ceramer composition of claim 1, wherein the free-radically curable fluorochemical component is represented by the formula:

5. The composition of claim 4 wherein the free-radically curable fluorochemical component is represented by the formula:

wherein X′

is a divalent linking group capable of linking the R_A moieties to the nitrogen moiety.

6. The composition of claim 4 wherein each Rf is independently a mono- or divalent, linear or branched, cyclic or non-cylic perfluorinated moiety.

7. The composition of claim 3, wherein each R_f is independently selected from the group consisting of perfluoroalkyl, perfluoroalkylene, perfluoroalkoxy, perfluoroether and perfluoropolyether.

8. The composition of claim 4, wherein each R_f is defined by the formula C_nF_2n+1, where n is 3 to 20 and one or more non-adjacent —

CF₂—

groups may be replaced by oxygen.

9. The free-radically curable ceramer composition of claim 1, wherein the free-radically curable binder precursor further comprises one or more copolymerizable free-radically curable monomers, oligomers, polymers or combinations thereof.

10. The free-radically curable ceramer composition of claim 1, wherein the colloidal inorganic oxide particles comprise colloidal silica particles.

11. The free-radically curable ceramer composition of claim 1, wherein said surface treatment agent further comprises fluoro/silane component of the formula:

12. The surface treatment agent of claim 11 wherein the weight ratio of the curable silane component to the fluoro/silane component is from about 4:

1 to 20;

1.

13. The composition of claim 1 wherein 1.5 to 20 weight percent of said free-radically curable binder precursor is said free-radically curable fluorochemical component.

14. A free-radically cured ceramer composite, said composite being derived from ingredients comprising:

(a) a plurality of surface treated colloidal inorganic oxide particles, and

(b) a free-radically curable binder precursor, wherein said free-radically curable binder precursor comprises a free-radically curable fluorochemical component comprising at least two free-radically curable moieties and at least one fluorinated moiety wherein the weight ratio of the colloidal inorganic oxide particles to the free-radically curable binder precursor is from about 1;

10 to about 1;

1.5.

15. The free-radically cured ceramer composite of claim 14, wherein the free-radically curable fluorochemical component is represented by the formula:

16. The free-radically cured ceramer composite of claim 15, wherein the free-radically curable fluorochemical component is selected from the group consisting of

C₈F₁₇SO₂N[C₂H₄OCOCH═

CH₂]₂,

CH₂═

CH—

CO—

OCH₂(CF₂OCF₂)_nCH₂OCOCH═

CH₂, n=2-10

(CF₃)₂CFCH(OCOCH═

CH₂)(CF₂)₈CH(OCOCH═

CH₂)CF(CF₃)₂,

C₄F₉CF(C₂F₅)COOCH₂C(C₂H₅)(CH₂OCOCH═

CH₂)₂, C₄F₉SO₂N(C₂H₄OCOCH═

CH₂)₂,

and

C₆F₁₃SO₂N(C₂H₄OCOCH═

CH₂)₂.

17. The free-radically cured ceramer composite of claim 14, wherein the colloidal inorganic oxide particles comprise colloidal silica particles.

18. A ceramer composite structure, comprising:

(a) a polymeric substrate having a coatable surface;

(b) a free-radically cured ceramer composite provided on the surface of the substrate, said composite being derived from ingredients comprising;

(i) a plurality of colloidal inorganic oxide particles, and

(ii) a free-radically curable binder precursor, wherein said free-radically curable binder precursor comprises a free-radically curable fluorochemical component comprising at least two free-radically curable moieties and at least one fluorinated moiety, wherein the weight ratio of the colloidal inorganic oxide particles to the free-radically curable binder precursor is from about 1;

0 to about 1;

1.5.

19. The ceramer composite structure of claim 18, wherein the free-radically curable fluorochemical component is represented by the formula:

20. The ceramer composite structure of claim 19, wherein the free-radically curable fluorochemical component is selected from the group consisting of

C₈F₁₇SO₂N[C₂H₄OCOCH═

CH₂]₂,

CH₂═

CH—

CO—

OCH₂(CF₂OCF₂)_nCH₂OCOCH═

CH₂, n=2-10

(CF₃)₂CFCH(OCOCH═

CH₂)(CF₂)₈CH(OCOCH═

CH₂)CF(CF₃)₂,

C₄F₉CF(C₂F₅)COOCH₂C(C₂H₅)(CH₂OCOCH═

CH₂)₂, C₄F₉SO₂N(C₂H₄OCOCH═

CH₂)₂,

and

C₆F₁₃SO₂N(C₂H₄OCOCH═

CH₂)₂.

21. The ceramer composite structure of claim 18, wherein the free-radically curable binder precursor further comprises one or more copolymerizable free-radically curable monomers, oligomers, polymers or combinations thereof.

22. A method of making a ceramer composite structure, comprising the steps of:

(a) coating at least a portion of a substrate surface with a free-radically curable ceramer composition, wherein the free-radically curable ceramer composition comprises;

(i) a plurality of colloidal inorganic oxide particles, and

(ii) a free-radically curable binder precursor, wherein said free-radically curable binder precursor comprises a free-radically curable fluorochemical component comprising at least two free-radically curable moieties and at least one fluorinated moiety, wherein the weight ratio of the colloidal inorganic oxide particles to the free-radically curable binder precursor is from about 1;

10 to about 1;

1.5.

(b) irradiating the coated substrate with an amount of curing energy under conditions effective to at least partially cure the coated free-radically curable ceramer composition, whereby the ceramer composite is formed on the substrate.

23. The method of claim 22, wherein the at least a portion of the substrate surface is coated at a thickness of from about 1 micron to about 100 microns of the ceramer composition.

24. The method of claim 22, wherein the ceramer composition is coated onto the at least a portion of substrate surface by spin coating, gravure coating, flow coating, spray coating, coating with a brush or roller, screen printing, knife coating, curtain coating, slide curtain coating, extrusion, squeegee coating, or a combination thereof.