Curable composition including fluorine-containing highly branched polymer and siloxane oligomer

Patent metadata

Field	Value
Publication number	US-9562170-B2
Application number	US-201314440385-A
Country	US
Kind code	B2
Filing date	Nov 1, 2013
Priority date	Nov 5, 2012
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

A curable composition including: (a) 100 parts by mass of a siloxane oligomer containing at least one radically polymerizable double bond, (b) 0.001 to 1 part by mass of a fluorine-containing highly branched polymer, (c) 0.01 to 40 parts by mass of a surface modifier containing a perfluoropolyether compound, and (d) 0.1 to 25 parts by mass of a polymerization initiator generating a radical upon active energy ray irradiation, wherein the fluorine-containing highly branched polymer (b) is a fluorine-containing highly branched polymer obtained by polymerization of a monomer A containing two or more radically polymerizable double bonds per molecule and a monomer B containing a fluoroalkyl group and at least one radically polymerizable double bond per molecule in the presence of a polymerization initiator C in an amount of 5 to 200 mol % with respect to the number of moles of the monomer A.

First claim

The invention claimed is:

1. A curable composition comprising:
(a) 100 parts by mass of a siloxane oligomer containing at least one radically polymerizable double bond,
(b) 0.001 to 1 part by mass of a fluorine-containing highly branched polymer,
(c) 0.01 to 40 parts by mass of a surface modifier containing a perfluoropolyether compound, and
(d) 0.1 to 25 parts by mass of a polymerization initiator generating a radical upon active energy ray irradiation, wherein
the fluorine-containing highly branched polymer (b) is a fluorine-containing highly branched polymer obtained by polymerization of a monomer A containing two or more radically polymerizable double bonds per molecule and a monomer B containing a fluoroalkyl group and at least one radically polymerizable double bond per molecule in the presence of a polymerization initiator C in an amount of 5 to 200 mol % with respect to the number of moles of the monomer A.

2. The curable composition according to claim 1 , wherein
the siloxane oligomer containing at least one radically polymerizable double bond (a) is a siloxane oligomer obtained through hydrolysis-condensation of an alkoxysilane D of Formula [3]:
R 3 a Si(OR 4 ) 4-a   [3]

(where R 3 is a monovalent organic group containing a radically polymerizable double bond, R 4 is a methyl group or an ethyl group, and a is 1 or 2).

3. The curable composition according to claim 2 , wherein
R 3 is a monovalent organic group containing a vinyl group or a (meth)acrylic group.

4. The curable composition according to claim 3 , wherein
the alkoxysilane D is a compound of Formula [4]:

(where R 4 is the same as defined above for Formula [3], R 5 is a hydrogen atom or a methyl group, and L 1 is a C 1-6 alkylene group).

5. The curable composition according to claim 2 , wherein
the siloxane oligomer containing at least one radically polymerizable double bond (a) is a siloxane oligomer obtained through hydrolysis-condensation of the alkoxysilane D and an alkoxysilane E of Formula [5]:
R 6 b Si(OR 7 ) 4-b   [5]

(where R 6 is a C 1-6 alkyl group that is optionally substituted with a fluorine atom or a phenyl group, R 7 is a methyl group or an ethyl group, and b is an integer of 0 to 2).

6. The curable composition according to claim 5 , wherein
the siloxane oligomer containing at least one radically polymerizable double bond (a) is a siloxane oligomer containing at least 10 mol % of the alkoxysilane D unit.

7. The curable composition according to claim 1 , wherein
the siloxane oligomer containing at least one radically polymerizable double bond (a) is a siloxane oligomer containing a structural unit of Formula [6] in an amount of at least 10 mol % of all the structural units:

(where L 1 is a C 1-6 alkylene group, R 4 is a methyl group or an ethyl group, and R 5 is a hydrogen atom or a methyl group).

8. The curable composition according to claim 1 , wherein
the monomer A is a compound containing one or both of a vinyl group and a (meth)acrylic group.

9. The curable composition according to claim 8 , wherein
the monomer A is a divinyl compound or a di(meth)acrylate compound.

10. The curable composition according to claim 1 , wherein
the monomer B is a compound containing at least either a vinyl group or a (meth)acrylic group.

11. The curable composition according to claim 10 , wherein
the monomer B is a compound of Formula [1]:

(where R 1 is a hydrogen atom or a methyl group and R 2 is a C 2-12 fluoroalkyl group that is optionally substituted with a hydroxy group).

12. The curable composition according to claim 11 , wherein
the monomer B is a compound of Formula [2]:

(where R 1 is the same as defined above for Formula [1], X is a hydrogen atom or a fluorine atom, m is 1 or 2, and n is an integer of 0 to 5).

13. The curable composition according to claim 1 , wherein
the polymerization initiator C is an azo polymerization initiator.

14. The curable composition according to claim 1 , wherein
the fluorine-containing highly branched polymer (b) is a highly branched polymer obtained by using the monomer B in an amount of 5 to 300 mol % with respect to the monomer A.

15. The curable composition according to claim 1 , wherein
the polymerization initiator generating a radical upon active energy ray irradiation (d) is an alkylphenone compound.

16. The curable composition according to claim 1 , further comprising:
as a hydrolysis catalyst, (e) an acid or an acid generator in an amount of 0.0001 to 10 mol % with respect to the alkoxysilyl group of the siloxane oligomer containing at least one radically polymerizable double bond (a).

17. A cured film obtained from the curable composition as claimed in claim 1 .

18. A laminate comprising:
a hard coating layer on at least part of a surface of a base material, wherein
the hard coating layer is obtained by applying the curable composition as claimed in claim 1 to the base material to form a coating and irradiating the coating with an active energy ray for curing.

19. The laminate according to claim 18 , wherein
the laminate is obtained by performing an additional baking process.

20. The laminate according to claim 18 , wherein
the base material is glass.

21. The laminate according to claim 18 , wherein
the hard coating layer has a thickness of 1 nm to 50 μm.

Assignees

• Nissan Chemical Ind Ltd

Inventors

• Haraguchi Masayuki
• Tamura Hiroyasu

Classifications

• C09D7/12

  Chemistry & Metallurgy · mapped topic

• C09D183/02

  Polysilicates · CPC title

• C09D183/10

  Block or graft copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00) · CPC title

• C08F259/08

  on to polymers containing fluorine · CPC title

• Y10T428/264

  Up to 3 mils · CPC title