JP2001139785A - Flame retardant resin composition - Google Patents

Abstract

(57) [Problem] To provide a flame-retardant resin composition having excellent oil resistance. SOLUTION: The total of (a) 75 to 20% by weight of an aromatic polyester and (b) 25 to 80% by weight of a styrene resin is 1 in total.
Flame retardant resin containing (c) 5 to 25 parts by weight of one or more brominated flame retardants represented by the following general formula (I) and (d) 2 to 10 parts by weight of antimony trioxide with respect to 00 parts by weight. Composition. Embedded image (In the formula, R represents oxygen or an alkylene group having 1 to 6 carbon atoms, and i and j each represent an integer of 0 to 5, provided that i + j ≧ 1 is satisfied.)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a flame-retardant resin composition used as a molding material for home electric appliances, OA equipment, building materials, automobile interior parts and the like.

[0002]

2. Description of the Related Art A styrene resin blended with a flame retardant is widely used as a molding material for home appliances and OA equipment.
JP-169997 discloses a flame-retardant styrene resin composition comprising a styrene resin, a bromine flame retardant, antimony trioxide, an organotin compound, pentaerythritol, and a fatty acid amide. The flame-retardant styrenic resin composition having such a composition is excellent in impact resistance, heat resistance, flame retardancy, etc., but the oil resistance required in some applications is not sufficient, When high resistance is required, it is necessary to improve oil resistance without impairing impact resistance, heat resistance, flame retardancy and the like.

[0003] An object of the present invention is to provide a flame-retardant resin composition capable of obtaining a molded article having excellent oil resistance as well as excellent impact resistance, heat resistance and flame retardancy.

[0004]

The present invention relates to (c) a compound represented by the following general formula: (a) 75 to 20% by weight of an aromatic polyester and (b) 25 to 80% by weight of a styrene resin in a total of 100 parts by weight. One or more brominated flame retardants 5-2 represented by (I)
Provided is a flame-retardant resin composition containing 5 parts by weight and (d) 2 to 10 parts by weight of antimony trioxide.

[0005]

Embedded image

(Wherein, R represents oxygen or an alkylene group having 1 to 6 carbon atoms, i and j each represent an integer of 0 to 5, provided that i + j ≧ 1 is satisfied)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic polyester as the component (a) used in the present invention is obtained by condensation of an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof) as main components. A polymer and / or copolymer obtained by the reaction.

Examples of the aromatic dicarboxylic acid include dicarboxylic acids having a benzene nucleus such as terephthalic acid and isophthalic acid, naphthalene-1,5-dicarboxylic acid, and naphthalene-
Examples thereof include dicarboxylic acids having a naphthalene nucleus such as 2,6-dicarboxylic acid, and ester-forming derivatives thereof. Further, as the acid component, a dicarboxylic acid (eg, adipic acid, sebacic acid) or an ester-forming derivative thereof other than the aromatic dicarboxylic acid of 20 mol% or less can be used in combination.

The diol component includes fatty acid glycols such as ethylene glycol, trimethylene glycol, 1,4-butanediol, hexamethylene glycol, diethylene glycol and cyclohexanediol;
Aromatic diols such as 1,4-bis (2-oxyethoxy) benzene and bisphenol A, or ester-forming derivatives thereof, and the like.

As the aromatic polyester as the component (a), polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate are preferable, and polybutylene terephthalate is particularly preferable.

The aromatic polyester as the component (a) preferably has an intrinsic viscosity (measured at 25 ° C. using o-chlorophenol as a solvent) in the range of 0.5 to 1.6.

The styrene resin as the component (b) used in the present invention may be a homopolymer of an aromatic vinyl monomer, an aromatic vinyl monomer and a maleimide monomer, a vinylcyan monomer or other And at least one selected from a copolymer with a copolymerizable vinyl monomer and a rubber-modified styrene resin.

As the aromatic vinyl monomer, styrene,
Alkyl-substituted styrene such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 2,4-dimethylstyrene, α-methylstyrene, α-methyl-4- Examples thereof include α-alkyl-substituted styrenes such as methylstyrene, halogenated styrenes such as 2-chlorostyrene and 4-chlorostyrene, and vinylnaphthalene, among which styrene is preferable.

The maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide,
-Phenylmaleimide, N-cyclohexylmaleimide, etc., of which N-phenylmaleimide and N-cyclohexylmaleimide are preferred.

Examples of the vinyl cyan monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred.

Other copolymerizable vinyl monomers include (C1-C10) alkyl (meth) acrylate,
(Meth) acrylate monomers such as hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; and (meth) acrylate monomers such as glycidyl (meth) acrylate; Examples include carboxyl group-containing monomers such as acrylic acid, maleic anhydride, maleic acid, itaconic anhydride, and citraconic anhydride.

The rubber-modified styrene resin includes (i) a graft copolymer of a rubber component obtained by polymerizing at least an aromatic vinyl monomer in the presence of a rubber component and an aromatic vinyl monomer ( (Ii) a block copolymer (ABA type block copolymer) of a rubber block and an aromatic vinyl polymer block. Such a block copolymer may be linear or star (star-shaped) and may form a thermoplastic elastomer; (iii) selected from a mixture of a rubber component and a non-rubber modified styrene resin. One or more types may be mentioned. The graft ratio of the monomer to be grafted to the rubber component is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50 to 150%.
% By weight.

The rubber component contained in the rubber-modified styrene resin includes butadiene rubber, butadiene-isoprene rubber, butadiene-acrylonitrile rubber, ethylene-
One or more selected from non-styrene rubbers such as propylene rubber, isoprene rubber, acrylic rubber, and ethylene-vinyl acetate rubber, and styrene rubbers such as styrene-butadiene rubber and styrene-isoprene rubber. In addition,
The butadiene rubber may be a high cis type having a high content of the cis-1,4 structure or a low cis type having a low content of the cis-1,4 structure. ５5 μm is preferred.

As the styrene resin of the component (b), polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), acrylonitrile-butadiene rubber-methacrylic Methyl acid-styrene copolymer (ABSM resin), acrylonitrile-styrene copolymer (AS resin), styrene-methacrylate copolymer (MS resin), high-impact polystyrene (HIPS), acrylonitrile-n-butyl acrylate rubber Examples include a styrene copolymer (AAS resin) and a styrene-butadiene copolymer (SBS resin).

The mixing ratio of the components (a) and (b)
75 to 20% by weight of component (a), preferably 75 to 30%
% By weight, more preferably 70 to 40% by weight,
Component (b) is 25 to 80% by weight, preferably 25 to 70% by weight.
%, More preferably 30 to 60% by weight.
20% by weight or more of component (a) (80% by weight of component (b)
Below), the mechanical properties, heat resistance and oil resistance are improved,
75% by weight or less of component (a) (25% by weight of component (b)
In the case of (above), warpage or the like is prevented from occurring, and dimensional stability is improved.

The component (c) used in the present invention is one or more brominated flame retardants represented by the above general formula (I). As the alkylene group having 1 to 6 carbon atoms represented by R in the formula, a methylene group or an ethylene group is preferable. Further, i and j in the formula have a bromine content of 30% by weight in order to enhance the flame retardancy.
It is preferable that the number is such as to be as described above.

The compounding ratio of component (c) is 5 to 25 parts by weight, preferably 10 to 20 parts by weight, more preferably 12 to 100 parts by weight of the total of components (a) and (b).
-20 parts by weight. When the amount is 5 parts by weight or more, the flame retardancy is enhanced, and when the amount is 25 parts by weight or less, a decrease in mechanical strength is prevented.

The antimony trioxide of the component (d) used in the present invention acts as a flame retardant aid, and preferably has an average particle size (by electron microscopy) of 1 to 150 μm.

The composition of the present invention may further contain a fibrous substance. Examples of the fibrous substance include glass fibers, glass fibers surface-treated with a coupling agent, etc., carbon fibers, metal fibers, ceramic fibers, various organic fibers, and the like. Of these, chopped strand type glass fibers are preferable. . The compounding amount of these fibrous substances is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight based on 100 parts by weight of the total of the components (a), (b), (c) and (d). Parts, more preferably 10 to 100 parts by weight.

The composition of the present invention may further comprise, if necessary,
Fillers, lubricants, reinforcing agents, stabilizers, light stabilizers, heat stabilizers,
An ultraviolet absorber, a plasticizer, an antistatic agent, a hue improver, and the like can be added.

Since the molded article obtained from the flame-retardant resin composition of the present invention is particularly excellent in oil resistance, it can be used in home electric appliances, OA
It is suitable for use as a sliding member used by applying grease or the like to equipment, building materials, and automobile interior members.

[0027]

〔Evaluation test〕

(1) Flexural Modulus Based on ASTM D790, it was measured using a 1/4 inch thick test piece. (2) Izod impact strength Measured based on ASTM D256 using a 1/4 inch thick test piece. (3) Heat resistance (deflection temperature under load) Based on ASTM D648, a test piece having a thickness of 1/4 inch was used and measured under a load of 1.82 MPa. (4) Flame Retardancy Based on the vertical flammability test (94V-2, V-0) specified in UL94 of the U.S.A. standard, evaluation was performed using a 1/16 inch thick test piece (bar sample). (5) Oil resistance A test piece (bar sample) having a thickness of 1/8 inch was given a strain amount equivalent to 30% of the maximum bending stress, and a brake (General 240) was applied to the convex portion of the test piece. After standing for 30 days, the appearance change and strength retention (% of the maximum bending strength after the test to the maximum bending strength before the test) of the test piece were evaluated. The criteria for the change in appearance are as follows: ○: good, Δ:
It was determined that the surface was slightly rough, and X: the change was large (dissolved) or cracks occurred. The maximum bending strength was measured using a test piece having a thickness of 1/8 inch based on ASTM D790. (6) Warp (Dimensional stability) A 120 mm x 120 mm x 1 mm flat plate was prepared, and the warp amount was measured at 23 ° C and 50% RH using a height gauge. Examples 1 to 6 and Comparative Examples 1 to 6 Each of the ratios shown in Table 1 [(a) and (b) are expressed in terms of% by weight, and others are expressed in parts by weight based on 100 parts by weight in total of (a) and (b)] After mixing the components with a tumbler, the mixture was melt-kneaded with an extruder to obtain a pellet-shaped flame-retardant resin composition. Each of the above evaluation tests was performed on these compositions. Table 1 shows the results
Shown in

[0028]

[Table 1]

[0029]

According to the flame-retardant resin composition of the present invention, a molded article having excellent impact resistance, heat resistance, flame retardancy, oil resistance and dimensional stability can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 25/04 C08L 25/04

Claims (2)

[Claims] 1. A total of (a) 75 to 20% by weight of an aromatic polyester and (b) 25 to 80% by weight of a styrene-based resin.
Flame retardant resin containing (c) 5 to 25 parts by weight of one or more brominated flame retardants represented by the following general formula (I) and (d) 2 to 10 parts by weight of antimony trioxide with respect to 00 parts by weight. Composition. Embedded image (In the formula, R represents oxygen or an alkylene group having 1 to 6 carbon atoms, and i and j each represent an integer of 0 to 5, provided that i + j ≧ 1 is satisfied.) 2. The method according to claim 1, further comprising the steps of:
1 to 20 based on a total of 100 parts by weight of (c) and (d)
A flame retardant resin composition containing 0 parts by weight.