Fluoropolyether-group-containing polymer, surface treatment agent, and article

Patent metadata

Field	Value
Publication number	US-11001670-B2
Application number	US-201716303439-A
Country	US
Kind code	B2
Filing date	May 10, 2017
Priority date	Jun 10, 2016
Publication date	May 11, 2021
Grant date	May 11, 2021

Abstract

A surface treatment agent which comprises a fluoropolyether-group-containing polymer represented by the following formula (1) or (2)

Rf 1 —[N(V) β (E) γ ] α   (1)

Rf 1 -[Q-(G) δ -(E′) ε -B] α   (2)

and/or a product of partial (hydrolytic) condensation of the polymer. The surface treatment agent forms a cured coating film excellent in terms of water and oil repellency and resistance to abrasion with erasers.

(In formulae (1) and (2), Rf 1 is a mono- or divalent polymer residue containing a fluorooxyalkylene group; N is C, Si, N, or a tri- to octavalent group optionally substituted by F; V is a monovalent group containing a hydroxy group or hydrolyzable group at the terminal; E is a monovalent group containing an oxyalkylene group; α is 1 or 2; β and γ are each 1-6, and β+γ is 2-7; Q is a single bond or a divalent group; G is a divalent group containing a hydroxy group or hydrolyzable group; E′ is a divalent group containing an oxyalkylene group; B is H, an alkyl group, or a halogeno; δ is 0-10; and ε is 1-10.)

First claim

The invention claimed is:

1. A fluoropolyether group-containing polymer having a hydrolyzable group and a polyether group, represented by the general formula (1) or (2):
Rf 1 —[N(V) β (E) γ ] α   (1)

wherein Rf 1 is a mono- or divalent fluorooxyalkylene group-containing polymer residue, N is independently a carbon atom, silicon atom, nitrogen atom or a tri- to octavalent organic group which may be substituted with fluorine, V is independently a monovalent group terminated with a hydroxyl or hydrolyzable group, E is independently a monovalent group containing oxyalkylene group, α is 1 or 2, 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 1 -[Q-(G) δ -(E′) ε -B] α   (2)

wherein Rf 1 and α are as defined above, 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 a divalent group containing oxyalkylene group, G and E′ are linearly linked, G and E′ may be randomly arranged, B is independently hydrogen, C 1 -C 4 alkyl or halogen group, δ is each independently an integer of 1 to 10, and ε is each independently an integer of 1 to 10.

2. The fluoropolyether group-containing polymer of claim 1 , represented by the general formula (3):

wherein Rf is a mono- or divalent fluorooxyalkylene group-containing polymer residue, Y is independently a di- to hexavalent hydrocarbon group which may contain a silicon atom and/or siloxane bond, W is independently a single bond, siloxane bond or silylene group, L is independently C 1 -C 4 alkylene group, 1 is an integer of 1 to 20, R is independently C 1 -C 4 alkyl or phenyl group, X is independently a hydroxyl or hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.

3. The fluoropolyether group-containing polymer of claim 2 wherein in formula (3), α is 1, and Rf is a group having the general formula (4):

wherein p, q, r and s each are an integer of 0 to 200, p+q+r+s is 3 to 200, each of the repeating units associated with p, q, r and s may be linear or branched, individual repeating units may be randomly bonded, d is an integer of 1 to 3, the unit associated with d may be linear or branched.

4. The fluoropolyether group-containing polymer of claim 2 wherein in formula (3), α is 2, and Rf is a group having the general formula (5):

wherein p, q, r and s each are an integer of 0 to 200, p+q+r+s is 3 to 200, each of the repeating units associated with p, q, r and s may be linear or branched, individual repeating units may be randomly bonded, d is an integer of 1 to 3, the unit associated with d may be linear or branched.

5. The fluoropolyether group-containing polymer of any one of claims 2 to 4 wherein in formula (3), Y is a group selected from the group consisting of a C 3 -C 10 alkylene group, an alkylene group containing C 6 -C 8 arylene group, a divalent group having alkylene moieties bonded via a silalkylene structure or silarylene structure, a di- to tetravalent group having a C 2 -C 10 alkylene moiety bonded to the valence bond of a di- to tetravalent linear organopolysiloxane residue of 2 to 10 silicon atoms, and a di- to tetravalent group having a C 2 -C 10 alkylene moiety bonded to the valence bond of a di- to tetravalent branched or cyclic organopolysiloxane residue of 3 to 10 silicon atoms.

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

7. The fluoropolyether group-containing polymer of claim 2 wherein in formula (3), X is each independently selected from the group consisting of hydroxyl group, C 1 -C 10 alkoxy group, C 2 -C 10 alkoxyalkoxy group, C 1 -C 10 acyloxy group, C 2 -C 10 alkenyloxy group, and halogen group.

8. The fluoropolyether group-containing polymer of claim 2 wherein the polymer having formula (3) is selected from those having the following formulae:

wherein p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1+q1 is an integer of 10 to 105.

9. A surface treating agent comprising a fluoropolyether group-containing polymer having a hydrolyzable group and a polyether group and/or a partial (hydrolytic) condensate thereof,
the fluoropolyether group-containing polymer having a hydrolyzable group and a polyether group, represented by the general formula (1) or (2):
Rf 1 —[N(V) β (E) γ ] α   (1)

wherein Rf 1 is a mono- or divalent fluorooxyalkylene group-containing polymer residue, N is independently a carbon atom, silicon atom, nitrogen atom or a tri- to octavalent organic group which may be substituted with fluorine, V is independently a monovalent group terminated with a hydroxyl or hydrolyzable group, E is independently a monovalent group containing oxyalkylene group, α is 1 or 2, 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 1 -[Q-(G) δ -(E′) ε -B] α   (2)

wherein Rf 1 and a are as defined above, 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 a divalent group containing oxyalkylene group, G and E′ are linearly linked, G and E′ may be randomly arranged, B is independently hydrogen, C 1 -C 4 alkyl or halogen group, δ is each independently an integer of 1 to 10, and ε is each independently an integer of 1 to 10.

10. The surface treating agent of claim 9 wherein in the fluoropolyether group-containing polymer having a hydrolyzable group and a polyether group, the polyether group is a group containing a monovalent oxyalkylene group at the end of the molecular chain.

11. The surface treating agent of claim 9 wherein the fluoropolyether group-containing polymer having a hydrolyzable group and a polyether group is a fluoropolyether group-containing polymer represented by the general formula (1) or (2):
Rf 1 —[N(V) β (E) γ ] α   (1)

wherein Rf 1 is a mono- or divalent fluorooxyalkylene group-containing polymer residue, N is independently a carbon atom, silicon atom, nitrogen atom or a tri- to octavalent organic group which may be substituted with fluorine, V is independently a monovalent group terminated with hydrolyzable group, E is independently a monovalent group containing oxyalkylene group, α is 1 or 2, 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 1 -[Q-(G) δ -(E′) ε -B] α   (2)

wherein Rf 1 and α are as defined above, 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 a divalent group containing oxyalkylene group, G and E′ are linearly linked, G and E′ may be randomly arranged, B is independently hydrogen, C 1 -C 4 alkyl or halogen group, δ is each independently an integer of 1 to 10, and ε is each in

Assignees

• Shinetsu Chemical Co

Inventors

• Sakoh Ryusuke
• Matsuda Takashi
• Yamane Yuji

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

• C09D5/1662

  Synthetic film-forming substance · 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

• C08G65/336

  containing silicon · CPC title

• C08G65/323 Primary

  containing halogens · CPC title