Water/oil repellent composition, method for its production, and article
View Patent ↗To provide a water/oil repellent composition whereby it is possible to obtain an article which is excellent in each of water repellency, oil repellency and heavy rain durability, a method for its production, and an article which is excellent in each of water repellency, oil repellency, heavy rain durability and texture. The water/oil repellent composition comprises a copolymer containing structural units based on a monomer (a), structural units based on a monomer (b) and structural units based on a monomer (c). Here, the monomer (a) is a compound represented by (Z—Y) n X (wherein Z is a C 1-6 perfluoroalkyl group, etc.; Y is a bivalent organic group, etc.; n is 1 or 2; and X is a polymerizable unsaturated group). The monomer (b) is a (meth)acrylate having no polyfluoroalkyl group and having an alkyl group with at least 12 carbon atoms. The monomer (c) is a monomer having a poly(oxypolyfluoroalkylene) chain.
1. A water/oil repellent composition comprising a copolymer containing structural units based on the following monomer (a), structural units based on the following monomer (b) and structural units based on the following monomer (c), and a liquid medium:
Monomer (a): a compound represented by the following formula (1).
(Z—Y) n X (1)
wherein Z is a C 1-6 perfluoroalkyl group or a group represented by the following formula (2), Y is a divalent organic group having no fluorine atom, or a single bond, n is 1 or 2, and X is, when n is 1, any one of groups represented by the following formulae (3-1) to (3-5), or, when n is 2, any one of groups represented by the following formulae (4-1) to (4-4):
C s F 2s+1 CH 2 CF 2 —(CH 2 CF 2 ) t (CF 2 CF 2 ) u — (2)
wherein s is an integer of from 1 to 6, t is an integer of from 0 to 3, and u is an integer of from 1 to 3,
—CR═CH 2 (3-1) ,
—C(O)OCR═CH 2 (3-2),
—OC(O)CR═CH 2 (3-3),
—OCH 2 -φ-CR═CH 2 (3-4),
—OCH═CH 2 (3-5),
wherein R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group,
—CH[—(CH 2 ) m CR═CH 2 ]— (4-1),
—CH[—(CH 2 ) m C(O)OCR═CH 2 ]— (4-2),
—CH[—(CH 2 ) m OC(O)CR═CH 2 ]— (4-3),
—OC(O)CH═CHC(O)O— (4-4),
wherein R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer of from 0 to 4,
Monomer (b): a(meth)acrylate haying no polyfluoroalkyl group and having an alkyl group with at least 12 carbon atoms,
Monomer (c): a monomer having a poly(oxypolyfluoroalkylene) chain wherein the proportion of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is at least 70%,
wherein the proportion of structural units based on the monomer (a) in the copolymer is from 5 to 40 mass % among the structural units (100 mass %) based on all monomers constituting the copolymer,
the proportion of structural units based on the monomer (b) in the copolymer is from 40 to 94.9 mass % among the structural units (100 mass %) based on all monomers constituting the copolymer, and
the proportion of structural units based on the monomer (c) in the copolymer is from 0.1 to 20 mass % among the structural units (100 mass %) based on all monomers constituting the copolymer.
2. The water/oil repellent composition according to claim 1 , wherein the copolymer further contains structural units based on following monomer (d):
Monomer (d): a halogenated olefin.
3. The water/oil repellent composition according to claim 2 , wherein the proportion of structural units based on the monomer (d) in the copolymer is at most 30 mass % among the structural units (100 mass %) based on all monomers constituting the copolymer.
4. The water/oil repellent composition according to claim 1 , wherein the copolymer further contains structural units based on following monomer (e):
Monomer (e): a monomer having a crosslinkable functional group.
5. The water/oil repellent composition according to claim 4 , wherein the proportion of structural units based on the monomer (e) in the copolymer is at most 20 mass % among the structural units (100 mass %) based on all monomers constituting the copolymer.
6. The water/oil repellent composition according to claim 1 , wherein the copolymer further contains structural units based on following monomer (f):
Monomer (f): a monomer containing no fluorine atom, other than the above monomer (b), halogenated olefin and monomer having a crosslinkable functional group.
7. The water/oil repellent composition according to claim 6 , wherein the proportion of structural units based on the monomer (f) in the copolymer is at most 35 mass % among the structural units (100 mass %) based on all monomers constituting the copolymer.
8. The water/oil repellent composition according to claim 1 , wherein the water/oil repellent composition further contains a surfactant, the liquid medium is an aqueous liquid medium, and the copolymer is emulsified in the aqueous liquid medium.
9. An article treated by using the water/oil repellent composition as defined in claim 1 .
10. The article according to claim 9 , wherein the article is a fiber product.
11. A method for producing a water/oil repellent composition, which comprises polymerizing monomer components comprising the following monomer (a), the following monomer (b) and the following monomer (c) in a liquid medium in the presence of a surfactant and a polymerization initiator, to form a copolymer:
Monomer (a): a compound represented by the following formula (1):
(Z—Y) n X (1)
wherein Z is a C 1-6 perfluoroalkyl group or a group represented by the following formula (2), Y is a divalent organic group having no fluorine atom, or a single bond, n is 1 or 2, and X is, when n is 1, any one of groups represented by the following formulae (3-1) to (3-5), or, when n is 2, any one of groups represented by the following formulae (4-1) to (4-4):
C s F 2s+1 CH 2 CF 2 —(CH 2 CF 2 ) t (CF 2 CF 2 ) u — (2)
wherein s is an integer of from 1 to 6, t is an integer of from 0 to 3, and u is an integer of from 1 to 3,
—CR═CH 2 (3-1)
—C(O)OCR═CH 2 (3-2),
—OC(O)CR═CH 2 (3-3),
—OCH 2 -φ-CR═CH 2 (3-4),
—OCH═CH 2 (3-5),
wherein R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group,
—CH[—(CH 2 ) m CR═CH 2 ]— (4-1),
—CH[—(CH 2 ) m C(O)OCR═CH 2 ]— (4-2),
—CH[—(CH 2 ) m OC(O)CR═CH 2 ]— (4-3),
—OC(O)CH═CHC(O)O— (4-4),
wherein R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer of from 0 to 4,
Monomer (b): a (meth)acrylate having no polyfluoroalkyl group and having an alkyl group with at least 12 carbon atoms,
Monomer (c): a monomer having a poly(oxypolyfluoroalkylene) chain wherein the proportion of the number of fluorine atoms to the total number of fluorine atoms and hydrogen atoms is at least 70%,
wherein the proportion of the monomer (a) in the monomer components is from 5 to 40 mass % among the monomer components (100 mass %),
the proportion of the monomer (b) in the monomer components is from 40 to 94.9 mass % among the monomer components (100 mass %), and
the proportion of the monomer (c) in the monomer components is from 0.1 to 20 mass % among the monomer components (100 mass %).
12. The method for producing a water/oil repellent composition according to claim 11 , wherein the monomer components further contain the following monomer (d):
Monomer (d): a halogenated olefin.
13. The method for producing a water/oil repellent composition according to claim 11 , wherein the monomer components further contain the following monomer (e):
Monomer(e): a monomer having a crosslinkable functional group.