Heat-resistant resin composition

• US 4,994,515 A
• Filed: 06/27/1989
• Issued: 02/19/1991
• Est. Priority Date: 06/27/1988
• Status: Expired due to Fees

• Current Assignee: Showa Denko KK
• Original Assignee: Showa Denko KK
• Inventors: Yasuda, Tetsuo, Washiyama, Junichiro, Aoyama, Chikara
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Smith, J.
• Application Number:
  US07/371,863
• Time in Patent Office: 602 Days
• Field of Search: 524/269, 524/504, 525/65, 525/73
• US Class Current: 524/269
• CPC Class Codes: C08G 59/1444 Monoalcohols
• CPC Class Codes: C08G 59/30 containing atoms other than carbon, hydrogen, oxygen and nitrogen
• CPC Class Codes: C08K 3/2279 of antimony
• CPC Class Codes: C08K 5/54 Silicon-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: C08L 25/08 Copolymers of styrene C08L29/08, C08L35/06, C08L55/02 take precedence
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/04 grafted on to rubbers
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Abstract

A resin composition comprising (A) at least one heat-resistant resin, (B) at least one thermoplastic resin, (C) an antimony oxide, (D) at least one bromine-containing reaction product selected from the group consisting of (1) a compound having a molecular weight of from 1,200 to 6,000 and a bromine content of from 5.0 to 60% by weight which is obtained by reacting a bromine-containing epoxy compound and 1,3,5-tribromophenol, and (2) a compound obtained by reacting a bromine-containing epoxy compound having an epoxy equivalent of from 450 to 7,000 and a bromine content of from 5.0 to 52% by weight and an acrylonitrile-butadiene copolymer having a carboxyl group at the both terminals thereof and a molecular weight of from 1,000 to 10,000, and (E) at least one silicon-containing compound selected from the group consisting of (1) silicone oil, (2) a ladder silicone resin, and (3) an alkoxysilane having a mercapto group, a vinyl group or a methacryloyl group, is disclosed. The resin composition is excellent in heat resistance, impact resistance, flame retardancy, and molding properties.

Claims

1. A resin composition comprising:

(A) at least one heat-resistant resin selected from group consisting of (1) a copolymer comprising a styrene compound and an α

,β

-unsaturated dicarboxylic acid imide compound and (2) a rubber-reinforced copolymer comprising a styrene compound and an α

,β

-unsaturated dicarboxylic acid imide compound,

(B) at least one thermoplastic resin selected from the group consisting of (1) a high-impact resin obtained by graft-copolymerizing (i) styrene and acrylonitrile or (ii) styrene and methyl methacrylate to (iii) a butadiene rubber, an ethylene-propylene rubber or an acrylic ester rubber, and (2) a copolymer resin comprising (i) styrene and acrylonitrile or (ii) styrene and methyl methacrylate,

(C) an antimony oxide,

(D) at least one bromine-containing reaction product selected from the group consisting of (1) compound having a molecular weight of from 1,200 to 6,000 and a bromine content of from 5.0 to 60% by weight which is obtained by reacting a bromine-containing epoxy compound and 1,3,5-tribromophenol, and (2) a compound obtained by reacting a bromine-containing epoxy compound having an epoxy equivalent of from 450 to 7,000 and a bromine content of from 5.0 to 52% by weight and an acrylonitrile-butadiene copolymer having a carboxyl group at the both terminals thereof and a molecular weight of from 1,000 to 10,000, and

(E) at least one silicon-containing compound selected from the group consisting of (1) silicone oil, (2) a ladder silicone resin, and (3) an alkoxysilane having a mercapto group, a vinyl group or a methacryloyl group,

wherein the amounts of the styrene compound and α

,β

-unsaturated dicarboxylic acid imide compound in said heat-resistant resin (A) are from 10 to 50% by weight based on the total amount of said heat-resistant resin (A) and thermoplastic resin (B), respectively;

the ratio of the α

,β

-unsaturated dicarboxylic acid imide compound to the total amount of said styrene compound and α

,β

-unsaturated dicarboxylic acid imide compound is from 5 to 50% by weight;

the total amount of a rubber reinforcement used in the rubber-reinforced copolymer of said heat-resistant resin (A) and the butadiene rubber, ethylene-propylene rubber and acrylic ester rubber used in said high-impact resin is from 5 to 35% by weight based on the total amount of said heat-resistant resin (A) and thermoplastic resin (B);

the amount of said antimony oxide is from 0.5 to 10 parts by weight per 100 parts by weight of the total amount of said heat-resistant resin (A) and thermoplastic resin (B);

the amount of said bromine-containing reaction product (D) is from 5.0 to 40 parts by weight per 100 parts by weight of the total amount of said heat-resistant resin (A) and thermoplastic resin (B); and

the amount of said silicon-containing compound (E) is from 0.01 to 15 parts by weight per 100 parts by weight of the total amount of said heat-resistant resin (A) and thermoplastic resin (B).

2. A resin composition as claimed in claim 1, wherein the copolymerization ratio of the α

,β

-unsaturated dicarboxylic acid imide compound to the total amount of the styrene compound and the α

,β

-unsaturated dicarboxylic acid imide compound in said heat-resistant resin ranges from 5 to 30% by weight.

3. A resin composition as claimed in claim 1, wherein said bromine-containing reaction product consists mainly of a compound represented by formula (III) ##STR8## wherein R₅ represents a hydrogen atom or a methyl group;

m represents 0 or an integer of from 1 to 7; and

i₁ to i₄ each represents 0 or an integer of from 1 to 4, provided that i₁ to i₄ are not 0 at the same time, which is obtained by reacting a bromine-containing epoxy compound represented by formula (II);

##STR9## wherein R₅, m, and i₁ to i₄ are as defined above; and

R₄, which may be the same as or different from R₅, represents a hydrogen atom or a methyl group, with 1,3,5-tribromophenol.

4. A resin composition as claimed in claim 3, wherein i₁ to i₄ in formula (III) each represents an integer of from 1 to 4.

5. A resin composition as claimed in claim 1, wherein said bromine-containing epoxy compound having an epoxy equivalent of from 450 to 7,000 and a bromine content of from 5.0 to 52% by weight is represented by formula (IV):

##STR10## wherein R₄ and R₅, which may be the same or different, each represents a hydrogen atom or a methyl group;

m'"'"' represents 0 or an integer of from 1 to 30; and

i₁ '"'"' to i₄ '"'"' each represents an integer of from 1 to 4.

6. A resin composition as claimed in claim 1, wherein said acrylonitrile-butadiene copolymer having a carboxyl group at both terminals thereof has an acrylonitrile content of 40% by weight or less.

7. A resin composition as claimed in claim 1, wherein said acrylonitrile-butadiene copolymer having a carboxyl group at both terminals thereof is reacted in an amount of from 5.0 to 100 parts by weight per 100 parts by weight of the bromine-containing epoxy compound.

8. A resin composition as claimed in claim 1, wherein said silicone oil has a viscosity of from 10 to 100,000 cps as measured at 25°

C.

9. A resin composition as claimed in claim 1, wherein said ladder silicone resin is represented by formula (V):

##STR11## wherein R₆ and R₇, which may be the same or different, each represents a straight chain alkyl group having from 1 to 4 carbon atoms, a phenyl group, a hydroxyl group, a carboxyl group, or an aminoalkyl group having from 1 to 4 carbon atoms, the total number of the hydroxyl, carboxyl and aminoalkyl groups being not more than 10 mol% based on the number of the groups for R₆ and R₇ ; and

n represents an integer of from 10 to 100.

10. A resin composition as claimed in claim 1, wherein said ladder silicone resin is heated at a temperature of from 80°

to 300°

C. for a period of from 5 to 1 hour.

11. A resin composition as claimed in claim 1, wherein said alkoxysilane is represented by formula (VI):

##STR12## wherein R and R'"'"', which may be the same or different, each represents a straight-chain or branched alkyl group having from 1 to 6 carbon atoms;

Y represents a vinyl group (CH₂ ═

CH--), a mercaptoalkyl group represented by formula HS--R₈ --, wherein R₈ represents a straight chain or branched alkylene group having from 1 to 6 carbon atoms, or a methacryloylalkyl group represented by formula ##STR13## wherein R₉ represents a straight-chain branched alkylene group having from 1 to 6 carbon atoms; and

x represents 2 or 3.

12. A resin composition as claimed in claim 1, wherein said bromine-containing reaction product is present in an amount of from 1 to 5 parts by weight per part by weight of the antimony oxide.

13. A resin composition as claimed in claim 1, wherein said silicone oil is present in an amount of from 0.1 to 3.0 parts by weight per 100 parts by weight of the total amount of said heat-resistant resin and thermoplastic resin.

14. A resin composition as claimed in claim 1, wherein said ladder silicone resin is present in an amount of from 0.01 to 15 parts by weight per 100 parts by weight of the total amount of said heat-resistant resin and thermoplastic resin.

15. A resin composition as claimed in claim 1, wherein said alkoxysilane is present in an amount of from 0.1 to 5.0 parts by weight per 100 parts by weight of the total amount of said heat-resistant resin and thermoplastic resin.

16. A resin composition as claimed in claim 1, wherein said silicone oil is present in an amount from 0.1 to 0.4 by weight per 100 parts by weight of the total of the heat-resistant resin (A) and the thermoplastic resin (B).

17. A resin composition as claimed in claim 1, wherein said silicone oil is polydimethylsiloxane.

18. A resin composition as claimed in claim 17, wherein said polydimethylsiloxane has a viscosity of 10 to 100,000 cp at 25°

C.