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

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 divalent group having C 2 -C 8 alkylene groups bonded via a C 1 -C 4 silalkylene structure or C 6 -C 10 silarylene structure, and a di- to tetravalent group in which a C 2 -C 10 alkylene group is bonded to the valence bond of a di- to tetravalent linear organopolysiloxane residue of 2 to 10 silicon atoms or a di- to tetravalent branched or cyclic organopolysiloxane residue of 3 to 10 silicon atoms.

8. The fluorochemical coating composition of claim 6 wherein in the formula (4a), Y′ is selected from the group consisting of a C 2 -C 10 alkylene group, a C 2 -C 8 alkylene group containing C 6 -C 8 arylene, a C 2 -C 6 alkylene group containing diorganosilylene, a divalent group having C 2 -C 8 alkylene groups bonded via a C 1 -C 4 silalkylene structure or C 6 -C 10 silarylene structure, a C 2 -C 6 alkylene group containing divalent linear organopolysiloxane residue of 2 to 10 silicon atoms, and a di- to tetravalent group in which a C 2 -C 10 alkylene group is bonded to the valence bond of a di- to tetravalent linear organopolysiloxane residue of 2 to 10 silicon atoms or a di- to tetravalent branched or cyclic organopolysiloxane residue of 3 to 10 silicon atoms.

9. The fluorochemical coating composition of claim 6 wherein in the formula (6), Z is selected from the group consisting of a single bond, a di- to tetravalent linear organopolysiloxane residue of 2 to 10 silicon atoms or a di- to tetravalent branched or cyclic organopolysiloxane residue of 3 to 10 silicon atoms, and a linear silalkylene residue or silarylene residue of 2 to 10 silicon atoms.

10. The fluorochemical coating composition of claim 1 or 6 wherein in the formulae (1) to (6), α=1 and Rf is a monovalent fluorooxyalkylene-containing polymer residue having the general formula (7):

wherein p, q, r and s each are an integer of 0 to 200, p+q+r+s is 3 to 200, wherein in each instance, a repeating unit in the general formula (7) selected from —(CF 2 O) p —, —(C 2 F 4 O) q —, —(C 3 F 6 O) r —, or —(C 4 F 8 O) s — may be linear or branched, individual repeating units may be randomly bonded, d is an integer of 0 to 3, and the units associated with d may be linear or branched.

11. The fluorochemical coating composition of claim 1 or 6 wherein in the formulae (1) to (6), α=2 and Rf is a divalent fluorooxyalkylene-containing polymer residue having the general formula (8):

wherein p, q, r and s each are an integer of 0 to 200, p+q+r+s is 3 to 200, wherein in each instance, a repeating unit in the general formula (8) selected from —(CF 2 O) p —, —(C 2 F 4 O) q —, —(C 3 F 6 O) r —, or —(C 4 F 8 O) s — may be linear or branched, individual repeating units may be randomly bonded, d is each independently an integer of 0 to 3, and the units associated with d may be linear or branched.

12. The fluorochemical coating composition of claim 1 or 6 wherein in the formulae (1) and (4) to (6), X is selected from the group consisting of hydroxyl, C 1 -C 10 alkoxy groups, C 2 -C 10 alkoxyalkoxy groups, C 1 -C 10 acyloxy groups, C 2 -C 10 alkenyloxy groups, and halogens.