Fluorine-containing copolymer and curable composition containing the same

• US 5,216,081 A
• Filed: 09/30/1992
• Issued: 06/01/1993
• Est. Priority Date: 06/29/1990
• Status: Expired due to Term

• Current Assignee: Daikin Industries Ltd
• Original Assignee: Daikin Industries Ltd
• Inventors: Shimizu, Yoshiki, Mohri, Haruhiko, Saito, Hideya, Chida, Akira
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): SAROFIM, NABIL F
• Application Number:
  US07/953,792
• Time in Patent Office: 244 Days
• Field of Search: 525/199, 524/517, 524/520
• US Class Current: 525/199
• CPC Class Codes: C08F 210/00 Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 214/18 Monomers containing fluorine
• CPC Class Codes: C08F 214/186 with non-fluorinated comonomers
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 27/12 containing fluorine atoms
• CPC Class Codes: C08L 33/06 of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Abstract

A fluorine-containing copolymer comprising 20 to 60% by mole of the fluoroolefin unit (1), 5 to 45% by mole of the β-methyl substituted α-olefin unit (2), 1 to 45% by mole of the unit (3) derived from a monomer having a chemically curable functional group, 1 to 45% by mole of the unit (4) derived from a monomer having ester moieties in the side chains and 0 to 45% by mole of the unit (5) derived from a copolymerizable monomer other than the above monomers, if necessary, 0.1 to 15% by mole of the unit (6) derived from a monomer having carboxyl groups. The copolymer can provide a curable composition alone or with an acrylic polymer. The fluorine-containing copolymer is excellent in solvent-solubility, compatibility with curing agents, additives and other polymers, pigment dispersibility, curing reactivity, dispersibility to water, pot life, film forming ability, coating properties, and the like. The coating film prepared from the copolymer has a high weatherability and is excellent in film properties such as stain resistance, heat-yellowing resistance, dechlorination resistance, optical properties, adhesion to a substrate, mechanical properties, heat resistance, chemical resistance, solvent (gasoline) resistance, water resistance and good appearance of finished products.

Claims

1. A curable composition comprising an acrylic polymer and a fluorine-containing copolymer having a number average molecular weight of 1000 to 500000, which consists essentially of

(a) a fluoroolefin structural unit (1) represented by the formula (I):

space="preserve" listing-type="equation">--CF.sub.2 --CFX-- (I)

wherein X is fluorine atom, chlorine atom, hydrogen atom or trifluoromethyl;

(b) a β

-methyl substituted α

-olefin structural unit (2) represented by the formula (II);

##STR10## wherein R is an alkyl group having 1 to 8 carbon atoms;

(c) a structural unit (3) derived from a monomer having a chemically curable functional group; and

(d) a structural unit (4) derived from a monomer having ester moieties in the side chains;

wherein said copolymer contains the structural unit (1) in an amount of 20 to 60% by mole, the structural unit (2) in an amount of 5 to 45% by mole, the structural unit (3) in an amount of 1 to 45% by mole and the structural unit (4) in an amount of 1 to 45% by mole, provided that the sum of the units (1) and (2) is 40 to 90% by mole.

2. A curable composition as in claim 1, which is in the form of aqueous dispersion.

3. A curable composition as in claim 1, which is in a form of powder.

4. A curable composition comprising an acrylic polymer and a fluorine-containing copolymer having a number average molecular weight of 1000 to 500000, which consists essentially of

(a) a fluoroolefin structural unit (1) represented by the formula (I):

space="preserve" listing-type="equation">--CF.sub.2 --CFX-- (I)

wherein X is fluorine atom, chlorine atom, hydrogen atom or trifluoromethyl;

(b) a β

-methyl substitute α

-olefin structural unit (2) represented by the formula (II);

##STR11## wherein R is an alkyl group having 1 to 8 carbon atoms;

(c) a structural unit (3) derived from a monomer having a chemically curable functional group;

(d) a structural unit (4) derived from a monomer having ester moieties in the side chains; and

(e) a structural unit (5) derived from a copolymerizable monomer selected from the group consisting of an alkyl vinyl ether, an aromatic vinyl ether, a fluoroalkyl vinyl ether, a fluoroalkyl ethylene, a C_1-18 alkyl ether of acrylic acid, a C_1-18 alkyl ester of methacrylic acid, a C_2-18 alkoxyalkyl ester of acrylic acid, a C_2-18 alkoxyalkyl ester of methacrylic acid and a vinyl aromatic compound;

wherein said copolymer contains the structural unit (1) in an amount of 20 to 60% by mole, the structural unit (2) in an amount of 5 to 45% by mole, the structural unit (3) in an amount of 1 to 45% by mole, the structural unit (4) in an amount of 1 to 45% by mole and the structural unit (5) in an amount of not more than 45% by mole, provided that the sum of the units (1) and (2) is 40 to 90% by mole.

5. A curable composition as in claim 4, which is in the form of aqueous dispersion.

6. A curable composition as in claim 4, which is in a form of powder.

7. A curable composition comprising an acrylic polymer and a fluorine-containing copolymer having a number average molecular weight of 1000 to 500000, which consists essentially of

(a) a fluoroolefin structural unit (1a) derived from tetrafluoroethylene,

(b) a β

-methyl substituted α

-olefin structural unit (2) represented by the formula (II);

##STR12## wherein R is an alkyl group having 1 to 8 carbon atoms;

(c) a structural unit (3) derived from a monomer having a chemically curable functional group;

(d) a structural unit (4) derived from a monomer having ester moieties in the side chains; and

(e) a structural unit (5) derived from a copolymerizable monomer selected from the group consisting of an alkyl vinyl ether, an aromatic vinyl ether, a fluoroalkyl vinyl ether, a fluoroalkylethylene, a C_1-18 alkyl ester of acrylic acid, a C_1-18 alkyl ester of methacrylic acid, a C_2-18 alkoxyalkyl ester of acrylic acid, a C_2-18 alkoxyalkyl ester of acrylic acid, a C_2-18 alkoxyalkyl ester of methacrylic acid and a vinyl aromatic compound; and

(f) a structural unit (6) derived from a monomer having carboxyl groups;

wherein said copolymer contains the structural unit (1a) in an amount of 20 to 60% by mole, the structural unit (2) in an amount of 5 to 45% by mole, the structural unit (3) in an amount of 1 to 45% by mole, the structural unit (4) in an amount of 1 to 45% by mole, the structural unit (5) in an amount of not more than 45% by mole and the structural unit (6) in an amount of 0.1 to 15% by mole, provided that the sum of the units (1) and (2) is 40 to 90% by mole.

8. A curable composition as in claim 7, which is in the form of aqueous dispersion.

9. A curable composition as in claim 7;

which is in a form of powder.