JPH0413749A - Flame-retarding resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition having excellent heat resistance, impact resistance, processability and light resistance as well as good thermal stability by compounding a rubber-reinforced styrenic resin, a saturated polyester, a halogen compound having a specific structure and an antimony compound. CONSTITUTION:The objective resin composition comprises (A) 80-100 wt.% of a rubber-reinforced styrenic resin, (B) 10-85wt.% of a saturated polyester resin, (C) 5-35wt.% of a high mol.wt. halogen compound of formula I [n is an integer of 4-30 as an average polymerization degree; R, R' are hydrogen, methyl, epoxypropyl, (halogeno) phenyl or a group of formula II (m is 0-3); the content of bromine is >=45% and the epoxy equivalent of >=10000g/mol] and (D) 0-10 pts.wt. of an antimony compound such as antimony pentaoxide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a flame-retardant resin composition with excellent thermal stability, comprising a rubber-reinforced thermoplastic resin, a saturated polyester resin, a resin, and a halogen compound with a specific structure. .

(Prior art) A resin composition consisting of ABS resin or a rubber-reinforced styrene resin represented by ABS resin and a saturated polyester resin is expected to be used as a rubber-reinforced styrenic resin with improved chemical resistance or a saturated polyester resin with improved impact resistance. has been done. However, since such resin compositions are flammable materials, they have flame retardant properties, such as self-extinguishing properties (v-0, v-1) based on U.S. Underwriters Laboratories (UL) Standard 94.
, V-2 class) are subject to restrictions when used in electrical and electronic equipment that requires

As flame retardant methods, tetrabromobinupheno/L/A (TBA) and decabromodiphenyl ether/v have already been used.
(D B D E ), halogen compounds such as brominated polycarbonate oligomers, or combinations thereof with antimony compounds are known, but although flame retardation can be achieved by blending these compounds, the resin There is a problem that the heat resistance, impact resistance, and processability, which are the characteristics of the composition, are significantly reduced.

Light resistance is also required for materials for devices used near windows, such as personal computers and facsimile machines.

(Means for Solving the Problems) The inventors of the present invention have conducted intensive studies in view of the above problems, and have found that by using a halogen compound with a specific structure, the resin composition has excellent heat resistance and properties. The present invention was achieved by discovering a flame retardant composition that has significantly improved thermal stability and light resistance without sacrificing impact resistance or processability.

(B) 10 to 85% by weight, a high molecular weight halogen compound represented by the following formula (1) (C) 5 to 35% by weight, and an antimony compound (D) 0 to 10% by weight. Flame retardant with excellent thermal stability. The present invention provides a synthetic resin composition.

(In the formula, n is the average degree of polymerization, an integer of 4 to 30, R and R'
are each independently hydrogen, a methyl group, an epoxyproyl group, a phenyl group, a halogenated phenyl group, or have a bromine content of 45% by weight or more and an epoxy equivalent of 10,000 grams or 1 mole or more. ) The flame-retardant resin composition of the present invention will be explained in detail below.

The rubber-reinforced styrenic resin (A) in the present invention refers to a graft copolymer obtained by polymerizing an aromatic vinyl compound and, if necessary, another copolymerizable vinyl compound in the presence of a rubbery polymer. a combination or said graft copolymer;
It is a mixture of an aromatic vinyl compound and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound and, if necessary, another copolymerizable vinyl(V) compound.

Examples of the rubbery polymer constituting the rubber-reinforced styrenic resin (A) include diene rubbery polymers such as polybutadiene, butane-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, and ethylene. -Prohylene-Non-diene rubbery polymers such as non-conjugated diene copolymers, acrylic rubbery polymers, and chlorinated polyethylenes are exemplified, and one or more of them can be used. These rubbery polymers are produced by emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, and the like.

There are no particular restrictions on the particle size and gel content of the rubbery polymer when produced by emulsion polymerization, but the average particle size is 0.1 to 1 μm and the gel content is 0 to 9.
Preferably it is 5%.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene,
Examples include p-methylstyrene, t-butylstyrene, α-methylviny/L/L'ene, dimethylnutylene, chlorstyrene, dichlorostyrene, promnutylene, sibromustyrene, etc., and one or more of them can be used in combination. . Particularly preferred are styrene and α-methylstyrene.

Aromatic vinyl) Other vinyl copolymerizable with v-based compounds /l/
Examples of such compounds include vinyl cyanide compounds such as acrylonitrile and methacrylate, unsaturated carboxylic acid alkyl p esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, propyl methacrylate, and 2-ethylhexyl methacrylate. , maleimide, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide and the like are exemplified, and one or more types of each can be used. Particularly preferred are acrylonitrile, methyl methacrylate and N-phenylmaleimide.

As the graft polymerization method, known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or a combination thereof are used.

The aromatic vinyl compounds constituting the aromatic vinyl polymer used in combination with the graft copolymer and other copolymerizable vinyl compounds are from the same group as those used in the graft copolymer. Any one type or two or more types can be selected and used from the following. Further, as a polymerization method for the polymer, known methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof are used.

Although there is no restriction on the composition ratio of the rubbery polymer and the compound in the rubber-reinforced nutylene resin (A), it is preferably 5 to 80% by weight of the rubbery polymer and 95 to 20% by weight of the compound. There is also no particular restriction on the composition ratio of the aromatic vinyl compound and other vinyl compounds in such a compound, but the aromatic vinyl compound lO to 100% by weight, especially 30 to 7% by weight.
0% by weight, and 90 to 0% by weight, particularly 70 to 30% by weight of other vinyl/' compounds.

Further, the saturated V resin (B) constituting the nonflammable resin composition of the present invention is a resin represented by the following general formula.

(However, n and m are integers, and Ar is an aromatic group) Generally, terephthalic acid, isophthalic acid, orthophthalic acid, 1.5 (
or 2.5 or 2.6) - Polycondensation reaction of aromatic dicarboxylic acids such as naphthalene dicarboxylic acid with diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, 1,4-cyclohexane 6'nol, Alternatively, it can be obtained by a polycondensation reaction performed by carrying out a transesterification reaction between the above-mentioned ester of aromatic dicarboxylic acid and a diol, followed by heating.

Specifically, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene isophthalate.
Examples include terephthalate, polybutylene terephthalate-isophthalate, and one type or two or more types can be used. Particularly preferred is polybutylene terephthalate. In addition, there is no particular restriction on the molecular weight, but the viscosity average molecular weight is 20
,000 to 40,000 is preferred.

The high molecular weight halogen compound (C) used in the present invention is a compound represented by the following formula.

The average degree of polymerization "n" should be 4 to 30; if it is less than 4, the impact resistance, heat resistance and thermal stability of the final composition will be poor;
If it exceeds 0, workability will be poor.

In terms of balance among impact resistance, heat resistance, thermal stability and processability, the average degree of polymerization is preferably 6 to 25, particularly 10 to 25.

R and R' are hydrogen, a methyl group, an epoxypropyl group, a phenyl group, a halogenated phenyl group, or both R and R' are halogenated phenyl groups, especially tribromophenyl. It is more preferable in terms of stability and flame retardancy.

If the bromine content is 45% by weight or more, the flame retardancy of the final composition is poor. Particularly preferably, it is 50% by weight or more.

Further, the epoxy equivalent weight is 10,000 grams/7p or more, and if it is less than that, the final composition will have poor thermal stability. Particularly preferred is 20,000 g/7 or more and less than 100,000.

The softening temperature of the high molecular weight halogen compound (C) is not particularly limited, but from the viewpoint of impact resistance and heat resistance of the final composition, a softening temperature of biso to 210° C. is particularly preferred.

The following methods can be used for producing the high molecular weight halogen compound (C).

! X-vinuphenol/l/A-type epoxy resin and brominated phenol/l/(particularly preferably tribromophenol)
and are subjected to a heating reaction in the presence of a basic catalyst such as lithium hydroxide. As a result of this reaction, most of the terminal epoxy groups of the epoxy resin become brominated phenols, and some of them become high molecular weight halogen compounds remaining as epoxy groups.

Antimony compounds that can be used in the present invention (
Examples of D) include antimony trioxide, antimony pentoxide, etc., and one or more types can be used.

The antimony compound (D) can be used in combination with the above-mentioned high molecular weight halogen compound (C), and has less plateout and light resistance compared to the antimony compound-known flame retardant (TBA, DBDE or brominated polycarbonate oligomer) combination system. The quality is also good.

The flame-retardant resin composition of the present invention contains 80 to 10% by weight of the above-mentioned rubber-reinforced styrene resin (A), 10 to 85% by weight of the saturated polyester resin (B), and a high molecular weight halogen compound (C
) 5 to 35% by weight and antimony compound (D) 0 to 1
It consists of 0% by weight. Outside this range, a composition having the desired performance cannot be obtained. impact resistance, heat resistance,
Surface characteristics such as processability, thermal stability, flame retardance, and light resistance (A) 7
5-12% by weight, (B) 20-80% by weight, (C) 8-80% by weight
25% by weight and (D) 0 to 5% by weight are preferred.

There are no restrictions on the mixing order or mixing method of each of the above-mentioned components, and it is possible to mix all at once or to mix the remaining components after premixing specific components. Also, Banbury mixer
Known methods such as low TV, n-pressure machine, etc. can be employed.

In addition, at the time of mixing, antistatic agents, lubricants, dyes and pigments, plasticizers, mold release agents, fillers, etc. can be added as necessary.

Next, the present invention will be specifically explained using Examples and Comparative Examples. Parts and percentages are given on a weight basis.

Reference Example-1 (ABS Resin-1) Graft polymer obtained by known emulsion graft polymerization of 50 parts of polybutadiene, 75 parts of styrene, and 15 parts of acrylonitrile, and 75 parts of styrene and 2 parts of acrylonitrile.
Rubber-reinforced styrenic resin (ABS resin-1) with a rubber content of 20%, consisting of 5 parts of a copolymer obtained by suspension polymerization of known
I got it.

Reference Example-2 (ABS Resin-2) Rubber content 15% consisting of the graft polymer used in ABS Resin-1 and a copolymer obtained by known emulsion polymerization of 75 parts of α-methylstyrene and 25 parts of acrylonitrile. A rubber-reinforced styrene resin (ABS resin-2) was obtained.

Reference example-3 (PBT) Below - viscosity average molecular weight expressed by the formula 80.000 polybutylene terephthalate.

Reference Examples 4 to 12 Brominated bisphenolv A-type epoxy resin and tribromophenol were reacted at 200°C in the presence of lithium hydroxide. By changing the synthesis conditions, eight types of high molecular weight halogen compounds (C-1 to 4, X-1 to 4) having different average polymerization degrees, bromine contents, or epoxy equivalents were obtained.

Reference Example-13 Antimony trioxide (5b) commercially available as an antimony compound
20a) was used.

Examples and Comparative Examples Rubber-reinforced styrenic resin (AB
S resin), a saturated polyester resin, a high molecular weight halogen compound (or a known flame retardant), and an antimony compound were kneaded at the blending ratios shown in Tables 1 to 3 to obtain various compositions.

The properties of the obtained compositions are shown in Tables 1 to 3.

(Effects of the Invention) The present invention provides a composition that is superior in thermal stability, heat resistance, impact resistance, processability, and light resistance as compared to conventionally known flame-retardant resin compositions.

Claims (1)

[Claims] Rubber-reinforced styrene resin (A) 80 to 10% by weight, saturated polyester resin (B) 10 to 85% by weight, the following formula (
High molecular weight halogen compound (C) 5 to 3 represented by I)
5% by weight and antimony compound (D) 0-10% by weight
A flame-retardant resin composition with excellent thermal stability. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) (wherein n is an integer of 4 to 30, R and R' are the average degree of polymerization
are independently hydrogen, methyl group, epoxypropyl group, phenyl group, halogenated phenyl group, or ▲a mathematical formula, chemical formula, table, etc.▼ (where m is an integer from 0 to 3), and the bromine content is 45% by weight or more, and the epoxy equivalent is 10,000 g/mol or more. )