Water/oil-repellent treatment agent having heat resistance, method of preparation, and treated article

Patent metadata

Field	Value
Publication number	US-9850399-B2
Application number	US-201514920082-A
Country	US
Kind code	B2
Filing date	Oct 22, 2015
Priority date	Nov 17, 2014
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

A water/oil repellent treatment agent which includes a specific polymer-modified silane having a fluorooxyalkylene structure on the main chain and a hydrolyzable group at the end of the molecular chain, and/or a partial (co)hydrolyzate/condensate thereof, has a percent weight loss following one hour of exposure at 250° C. of 10% or less. The treatment forms a layer having excellent water and oil repellency, scuff resistance and mold release properties even when heated to 250° C. or more.

First claim

The invention claimed is:

1. A water/oil repellent treatment agent comprising at least one compound selected from the group consisting of fluorooxyalkylene group-containing polymer-modified silanes of general formulas (1) to (4) below
A-Rf-QZW α   (1)

Rf-(QZW α ) 2   (2)

A-Rf-Q-(Y) β B  (3)

Rf-(Q-(Y) β B) 2   (4),

wherein Rf is —(CF 2 ) d —(OCF 2 ) p (OCF 2 CF 2 ) q (OCF 2 CF 2 CF 2 ) r (OCF 2 CF 2 CF 2 CF 2 ) s (OCF(CF 3 )CF 2 ) t —O(CF 2 ) d —, each d being independently an integer from 0 to 5, p, q, r, s and t being each independently an integer from 0 to 500, with the proviso that the sum p+q+r+s+t=40 to 500, and each unit shown in parentheses being randomly bondable;
A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal —CF 3 group, —CF 2 H group or —CH 2 F group;
Q is independently a single bond or a divalent organic group which may be fluorine-substituted and does not contain a hydrocarbon ether bond;
Z is independently a group selected from the group consisting of a single bond, the divalent group -J 2 C— (where J is independently an alkyl group, a hydroxyl group or the silyl ether group K 3 SiO— (K being independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group), the divalent group -L 2 Si— (where L is independently an alkyl group, an alkenyl group, an alkoxy group or a chloro group), the trivalent group -JC═ (where J is as defined above), the trivalent group -LSi═ (where L is as defined above), the tetravalent group —C≡, the tetravalent group —Si≡, and siloxane residues having a valence of 2 to 8;
W is independently a hydrolyzable group-bearing moiety of any of general formulas (5a) to (5e) below

R being independently an alkyl group of 1 to 4 carbon atoms or a phenyl group, X being independently a hydrolyzable group, the letter “a” being 2 or 3, the letter “l” being an integer from 0 to 10, each m being independently an integer from 1 to 10, D being a single bond or a divalent organic group of 1 to 20 carbon atoms which may be fluorine-substituted, b being an integer from 2 to 6, c being an integer from 1 to 50, and Me being a methyl group;
α is an integer from 1 to 7;
Y is independently a divalent group having a hydrolyzable group;
β is in each instance an integer from 1 to 10; and
B is independently a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or a halogen atom,
and partial (co)hydrolyzates/condensates thereof in an amount of at least 50% of the total weight exclusive of diluting solvent, wherein the treatment has a percent weight loss after one hour of exposure at 250° C. that is not more than 10% of the total weight exclusive of diluting solvent.

2. The treatment agent of claim 1 , wherein Y is selected from the group consisting of groups of general formulas (6) to (8) below

wherein R, X, the letter “a” and D are as defined above, D′ is a divalent organic group of 1 to 10 carbon atoms that may be fluorine-substituted, R 1 is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and e is 1 or 2.

3. The treatment agent of claim 1 , wherein Q is selected from the group consisting of a single bond and divalent groups of the following formulas

wherein f is an integer from 2 to 4, g is an integer from 1 to 4, h is an integer from 1 to 50, and Me is a methyl group.

4. The treatment agent of claim 1 , wherein the hydrolyzable group X is selected from the group consisting of alkoxy groups of 1 to 10 carbon atoms, alkoxyalkoxy groups of 2 to 10 carbon atoms, acyloxy groups of 1 to 10 carbon atoms, alkenyloxy groups of 2 to 10 carbon atoms, halogen groups, and silazane groups.

5. The treatment agent of claim 1 , further comprising a fluorooxyalkylene group-containing polymer of general formula (9) below
A-Rf-A  (9),

wherein Rf and A are as defined above, which fluorooxyalkylene group-containing polymer accounts for at least 0.1 wt % and not more than 50 wt % of the combined amount of the fluorooxyalkylene group-containing polymer-modified silane and/or the partial (co)hydrolyzate/condensate thereof and the fluorooxyalkylene group-containing polymer.

6. An article treated with the water/oil repellent treatment agent of claim 1 .

7. An optical article treated with the water/oil repellent treatment agent of claim 1 .

8. Glass, chemically toughened glass, physically toughened glass, SiO 2 -treated glass, sapphire glass, SiO 2 -treated sapphire glass, a quartz substrate, a silicon wafer or a metal treated with the water/oil repellent treatment agent of claim 1 .

9. A touch panel, anti-reflective coating, wearable device, photovoltaic panel or transportation equipment window treated with the water/oil repellent treatment agent of claim 1 .

10. An imprinting mold treated with the water/oil repellent treatment agent of claim 1 .

11. A method of preparing the water/oil repellent treatment agent of claim 1 , comprising the step of:
thin-film distilling, in the temperature range of 150 to 400° C., the at least one compound selected from the group consisting of fluorooxyalkylene group-containing polymer-modified silanes of formulas (1) to (4) and partial (co)hydrolyzates/condensates thereof to remove low-boiling components.

12. A method of preparing the water/oil repellent treatment agent of claim 5 , comprising the step of:
thin-film distilling, in the temperature range of 150 to 400° C., a mixture of the at least one compound selected from the group consisting of fluorooxyalkylene group-containing polymer-modified silanes of formulas (1) to (4) and partial (co)hydrolyzates/condensates thereof with the fluorooxyalkylene group-containing polymer of formula (9) to remove low-boiling components.

13. A method of preparing the water/oil repellent treatment agent of claim 5 , comprising the steps of:
separately thin-film distilling, in the temperature range of 150 to 400° C., the at least one compound selected from the group consisting of fluorooxyalkylene group-containing polymer-modified silanes of formulas (1) to (4) and partial (co)hydrolyzates/condensates thereof and the fluorooxyalkylene group-containing polymer of formula (9) to remove low-boiling components; and
mixing together the residue from each distillation.

14. The treatment agent of claim 1 , wherein α is an integer of from 2 to 7 in general formula (1) or (2) and β is an integer of from 2 to 10 in general formula (3) or (4).

Assignees

• Shinetsu Chemical Co

Inventors

• Yamane Yuji
• Sakoh Ryusuke
• Matsuda Takashi

Classifications

• B32B17/10

  of synthetic resin · CPC title

• C08G77/46

  containing polyether sequences · CPC title

• C09D171/00 Primary

  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 · CPC title

• C08G65/007

  containing fluorine · CPC title

• C08G65/336 Primary

  containing silicon · CPC title