Fluorine-containing coating agent composition, surface treatment agent containing said composition, and article

Patent metadata

Field	Value
Publication number	US-12054637-B2
Application number	US-201816613924-A
Country	US
Kind code	B2
Filing date	Apr 19, 2018
Priority date	May 23, 2017
Publication date	Aug 6, 2024
Grant date	Aug 6, 2024

Abstract

This fluorine-containing coating agent composition contains: (A) an organic silicon compound containing a hydrolyzable group or a hydroxy group modified by a fluorooxyalkylene group-containing polymer residue, and/or a partial (hydrolyzed) condensate thereof; and (B) an organic silicon compound containing a polyether group and a hydrolyzable group or a hydroxy group modified by a fluorooxyalkylene group-containing polymer residue, and/or a partial (hydrolyzed) condensate thereof, wherein the mixture mass ratio of component (A) and component (B) is 15:85-85:15. When the composition is applied as a surface treatment agent, the surface treatment agent containing the fluorine-containing coating agent composition can form a cured coating film which has excellent water repellency and oil repellency, and which has both excellent steel wool abrasion resistance and eraser rubber abrasion resistance.

First claim

The invention claimed is:

1. A fluorochemical coating composition comprising
(A) an organosilicon compound containing a hydroxyl or hydrolyzable group, modified with a fluorooxyalkylene-containing polymer residue represented by (i) the general formula (1), (ii) a partial hydrolytic condensate of general formula (1), or (iii) a combination thereof:

wherein in the general formula (1):
Rf is a mono- or divalent fluorooxyalkylene-containing polymer residue,
A is independently a di- to heptavalent organic group,
R is independently C 1 -C 4 alkyl or phenyl,
X is independently a hydroxyl or hydrolyzable group for either or both of general formula (1) or the partial hydrolytic condensate,
n is an integer of 1 to 3,
m is an integer of 1 to 6, and
α is 1 or 2, and
(B) an organosilicon compound containing a hydroxyl or hydrolyzable group and a polyether group, wherein the organosilicon compound is further modified with a fluorooxyalkylene-containing polymer residue represented by general formula (2) or (3), and/or a partial hydrolytic condensate of the organosilicon compound:
Rf-[N(V) β (E) γ ] α   (2)

wherein in the general formula (2):
Rf is a mono- or divalent fluorooxyalkylene-containing polymer residue,
α is 1 or 2,
N is independently a tri- to octavalent organic group which may contain fluorine, oxygen, silicon or nitrogen,
V is independently a monovalent group terminated with a hydroxyl or hydrolyzable group,
E is independently a monovalent group containing oxyalkylene,
β is an integer of 1 to 6,
γ is an integer of 1 to 6,
β+γ is an integer of 2 to 7,
Rf-[Q-(G) δ -(E′) ε -B] α   (3)

wherein in the general formula (3):
Rf is a mono- or divalent fluorooxyalkylene-containing polymer residue,
α is 1 or 2,
Q is independently a single bond or divalent organic group,
G is independently a divalent group having a hydroxyl or hydrolyzable group,
E′ is independently an oxyalkylene-containing divalent group which may have a hydroxyl or hydrolyzable group,
B is independently hydrogen, C 1 -C 4 alkyl or halogen,
δ is independently an integer of 1 to 10,
ε is independently an integer of 1 to 10,
with the proviso that G and E′ are linearly linked, and G and E′ individually may be randomly arranged,
wherein components (A) and (B) are mixed in a weight ratio of from 15:85 to 85:15, provided that the total of components (A) and (B) is 100.

2. The fluorochemical coating composition of claim 1 wherein the hydrolyzable group-containing organosilicon compound modified with a fluorooxyalkylene-containing polymer residue, represented by the formula (1), is selected from compounds having the following formulae:

wherein p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1+q1 is an integer of 10 to 105, individual units in parentheses may be randomly bonded.

3. The fluorochemical coating composition of claim 1 wherein the hydrolyzable and polyether group-containing organosilicon compound modified with a fluorooxyalkylene-containing polymer residue, represented by the formula (2) or (3), is selected from compounds having the following formulae:

wherein p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1+q1 is an integer of 10 to 105, r1 is an integer of 1 to 100, s1 is an integer of 1 to 100, p1+q1+r1+s1 is an integer of 12 to 199, individual units in parentheses may be randomly bonded.

4. A surface treating agent comprising the fluorochemical coating composition of claim 1 .

5. An article having a surface treated with the surface treating agent of claim 4 .

6. A fluorochemical coating composition comprising
(A) an organosilicon compound containing a hydroxyl or hydrolyzable group, modified with a fluorooxyalkylene-containing polymer residue represented by (i) the general formula (4) or (5), (ii) a partial hydrolytic condensate of general formula (4) or (5), or (iii) a combination thereof:

wherein in the general formula (4):
Rf is a mono- or divalent fluorooxyalkylene-containing polymer residue,
Y is independently a di- to hexavalent hydrocarbon group which may have silicon and/or a siloxane bond,
R is independently C 1 -C 4 alkyl or phenyl,
X is independently a hydroxyl or hydrolyzable group for either or both of general formula (4) or the partial hydrolytic condensate,
a is an integer of 1 to 5,
α is 1 or 2, and
W is hydrogen or a group having the formula (4a):

wherein in the general formula (4a):
Y′ is a di- to hexavalent hydrocarbon group which may have silicon and/or a siloxane bond,
R is independently C 1 -C 4 alkyl or phenyl,
X is independently a hydroxyl or hydrolyzable group for either or both of general formula (4a) or the partial hydrolytic condensate,
n is an integer of 1 to 3, and
b is an integer of 1 to 5,

wherein in the general formula (5):
A 1 is a C 2 -C 6 divalent hydrocarbon group which may contain an ether bond,
B 1 is independently a C 1 -C 5 alkylene group which may contain at least one selected from oxygen atom, diorganosilylene group, and diorganosiloxane structure,
Rf is a mono- or divalent fluorooxyalkylene-containing polymer residue,
X is independently a hydroxyl or hydrolyzable group for either or both of general formula (5) or the partial hydrolytic condensate,
R is independently C 1 -C 4 alkyl or phenyl,
n is an integer of 1 to 3, and
α is 1 or 2,
and
(B) an organosilicon compound containing a hydroxyl or hydrolyzable group and a polyether group, modified with a fluorooxyalkylene-containing polymer residue represented by the general formula (6) and/or a partial hydrolytic condensate thereof of the organosilicon compound:

wherein in the general formula (6):
Rf is a mono- or divalent fluorooxyalkylene-containing polymer residue,
Y is independently a di- to hexavalent hydrocarbon group which may have silicon and/or a siloxane bond,
X is independently a hydroxyl or hydrolyzable group for either or both of general formula (6) or the partial hydrolytic condensate,
R is independently C 1 -C 4 alkyl or phenyl,
n is an integer of 1 to 3,
α is 1 or 2,
Z is independently a single bond, siloxane bond or silylene group,
L is independently C 1 -C 4 alkylene,
1 is an integer of 1 to 20, and
a1 is an integer of 1 to 5.

7. The fluorochemical coating composition of claim 6 wherein in the formulae (4) and (6), Y is selected from the group consisting of a C 3 -C 10 alkylene group, a C 2 -C 8 alkylene group containing C 6 -C 8 arylene, a diva

Assignees

• Shinetsu Chemical Co

Inventors

• Katayama Lisa
• Matsuda Takashi
• Yamane Yuji
• Sakoh Ryusuke

Classifications

• C09D171/00

  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 · CPC title

• C08K5/56

  Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond · CPC title

• C08G65/336

  containing silicon · CPC title

• C08L71/00

  Compositions of polyethers obtained by reactions forming an ether link in the main chain (of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06); Compositions of derivatives of such polymers · CPC title

• C08L83/06

  containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence) · CPC title