JPH01188544A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, excellent in physical properties, improved in flame retardance, especially dripping, god in resistance to impact and heat and useful as a material for electronic devices, by using a bromine compound and silicon oil in combination. CONSTITUTION:The aimed composition, consisting of (A) at least one heat- resistant resin consisting of a copolymer of (i) at least one styrene based compound and an imide based compound of an alpha,beta-unsaturated dicarboxylic acid and (ii) a copolymer of a styrene based compound and the above-mentioned imide based compound reinforced with a rubber reinforcing material, (B) an impact-resistant resin prepared by graft copolymerizing (iii) a butadiene based rubber or ethylene-propylene based rubber with (iv) styrene and (v) acylonitrile or the component (iv) and (vi) methyl methacrylate, (C) at least one styrene based resin of the group consisting of the components (iv) and (v) or components (iv) and (vi) and (D) antimony oxide, deca(octa)bromodiphenyl ether and a silicone oil.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition having excellent heat resistance. More specifically, it not only has excellent heat resistance, but also
The present invention relates to a resin composition that has good impact resistance and excellent flame retardancy and is promising as a material for parts of electronic devices, electrical devices, etc.

[Conventional technology]

Currently, flame-retardant acrylonitrile-butadiene-styrene terpolymer resin (ABS) is used in the housings of electronic and electrical equipment such as television sets, CRTs, various computers, facsimile machines, and word processors.
Styrenic resins such as resin) are commonly used. Heat-resistant temperature of these flame-retardant resins (ASTM D648
(measured at 18.5 kg/crn') is usually 70 to 90°C, and depending on the use and size of the product, problems often arise regarding heat resistance.

On the other hand, polyphenylene oxide resin (PPO), polycarbonate resin (PC), etc. are synthetic resins that have a heat resistance temperature of 90°C or higher, but there are problems in terms of price and moldability. There is a need for synthetic resins or compositions thereof that have excellent properties and flame retardancy. In addition, in order to improve the moldability of PPO and PC, it has been proposed to make heat-resistant resins such as styrene-maleimide polymers resin-friendly to these synthetic resins (U.S. Pat. Nos. 4,278,775 and 416).
No. 0792). Although these compositions have good heat resistance and moldability, they have problems in terms of flame retardancy. Furthermore, it has been proposed that a styrene-maleimide polymer be used as a resin friend for vinyl chloride resin (U.S. Patent No. 4
No. 458046). The resulting composition has good flame retardancy, but has problems with heat resistance. It has also been proposed to add a halogen flame retardant such as decabromodiphenyl ether to a styrene-maleimide polymer (Japanese Patent Laid-Open No. 82950/1983). The resulting composition is prone to dripping. In order to prevent dripping, a large amount must be added, and therefore,
It has the disadvantage that physical properties such as impact resistance are significantly reduced. In addition to monomers such as styrene compounds and maleimide compounds, brominated phenylmaleimide compounds (Japanese Unexamined Patent Publication No. 157511/1982) and brominated (meth)acrylate compounds (Japanese Unexamined Patent Publication No. 82990/1989) are also used. Attempts have also been made to copolymerize with halogen-containing monomers, but in order to provide sufficient flame retardance, large amounts of expensive halogen-containing monomers must be used, which poses a practical problem.

[Problem to be solved by the invention]

For these reasons, it not only has excellent flame retardancy, but also
There is a demand for synthetic resins or compositions thereof that have good heat resistance and impact resistance as well as excellent moldability.

From the above, the present invention does not have these drawbacks (problems), that is, it has not only excellent heat resistance and impact resistance, but also flame retardancy and moldability, and is relatively inexpensive. This is how the composition is obtained.

[Means and effects for solving the problems] According to the present invention, these problems are solved by (A) (1) At least the combination of a styrene compound and an imide compound of an α,β-unsaturated dicarboxylic acid. (B) at least one heat-resistant resin selected from the group consisting of a polymer and (2) a copolymer of a styrene compound and an imide compound of an α,β-unsaturated dicarboxylic acid reinforced with a rubber reinforcing material; ) impact-resistant resin obtained by graft copolymerizing styrene and acrylonitrile or styrene and methyl methacrylate to butadiene rubber, ethylene-propylene rubber, or acrylic ester rubber;
(C) at least one styrenic resin selected from the group consisting of copolymer resins of styrene and acrylonitrile or styrene and methyl methacrylate, (D) antimony oxide, (E) decabromodiphenyl ether, (F) octaflorodiphenyl ether and (G) a styrene compound and an imide compound that are copolymerized components of the heat resistant resin, which are made of silicone oil and account for the total amount of the heat resistant resin, impact resistant resin, and styrene resin that are polymeric substances. The proportion is 10 to 50% by weight as a total amount, and the proportion of the imide compound in the total amount of the styrene compound and the imide compound is 5 to 50% by weight. The proportion of the rubber, ethylene-propylene rubber, and acrylic ester rubber is 5 to 45% by weight in total, and the composition proportion of the styrene resin in the total amount of the heat-resistant resin and the styrene resin. is 20 to 80% by weight, and the total amount of heat-resistant resin, impact-resistant resin, and styrene resin is 1
00 parts by weight, the total amount of decabromodiphenyl ether and octaflorodiphenyl ether is 15 to 40 parts by weight, but the composition ratio of decabromodiphenyl ether in this total amount is 20 to 40 parts by weight.
80 parts by weight, antimony oxide is 0.5 to 15 parts by weight, and silicone oil is 0.1 to 3.0 parts by weight. The present invention will be explained in detail below.

(A) Heat-resistant resin The heat-resistant resin used in the present invention is selected from the following.

(1) Copolymer of at least a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid [hereinafter referred to as “heat-resistant resin (1)”] (2) At least styrene reinforced with a rubber reinforcing material Copolymer of α, β-unsaturated dicarboxylic acid imide compound [hereinafter referred to as “heat-resistant resin (2)”] In the case of the above heat-resistant resin (1), the heat-resistant resin ( 2)
In this case, the styrene compound which is the copolymerization component is styrene or its derivatives, and the derivatives include α-methylstyrene, 〇-methylstyrene, m-methylstyrene, p-methylstyrene, and chlorostyrene. can give.

Examples of the imide compound of α,β-unsaturated dicarboxylic acid include those represented by the formula (I).

ON.

In formula (I), R□, R2 and R:l may be the same or different and are a hydrogen atom or a hydrocarbon group having at most 12 carbon atoms.

Representative examples of the imide compounds include maleimide, N-
Phenylmaleimide, N-methylphenylmaleimide,
N-ethylphenylmaleimide, N-laurylmaleimide, etc. can be used.

Further, in producing the heat-resistant resin (2), rubber reinforcing materials used as reinforcing materials include styrene-butadiene copolymer rubber (styrene copolymerization ratio is usually 40% by weight or less), butadiene homopolymer rubber, Styrene
Examples include hydrogenated styrene-butadiene copolymer rubber obtained by hydrogenating butadiene copolymer rubber and copolymer rubber of ethylene and propylene.

The heat-resistant resin (2) is obtained by graft polymerizing a styrene compound and the imide compound to a rubber reinforcing material, and the ratio of rubber reinforcing material used per 100 parts by weight of the heat-resistant resin (2) is is usually 3 to 20 parts by weight (preferably 5 to 15 parts by weight).

Both in the case of heat-resistant resin (1) and in the case of heat-resistant resin (2), the commonly used aqueous suspension polymerization method,
It can be produced by any one of emulsion polymerization, solution polymerization, and bulk polymerization, and the methods for producing these heat-resistant resins are well known.

In addition, in the case of any heat-resistant resin, the copolymerization ratio of the imide compound in the total amount of the styrene compound and the imide compound of α,β-unsaturated dicarboxylic acid, which are copolymerization components, is 5 to 30. It is preferably 10 to 30% by weight, particularly preferably 10 to 25% by weight. If the copolymerization ratio of the imide compound to the total amount of the styrene compound and the imide compound is less than 5% by weight, heat resistance will be insufficient. On the other hand, when it exceeds 50% by weight, moldability is significantly reduced.

In addition, in the case of any heat-resistant resin, it may be composed of a styrene compound and an imide compound as copolymerization components, but it may also contain unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, or methyl methacrylate. may be copolymerized as a co-electrical gold component (copolymerization ratio, usually at most 30% by weight).

Furthermore, it is also possible to perform graft copolymerization using a relatively large amount of rubber reinforcing material as the heat-resistant resin (2), and use the resulting graft copolymer as a masterbatch by blending the heat-resistant resin (1) etc. good.

Even in the case of the above heat-resistant resin (1), heat-resistant resin (2)
In this case, the rubber reinforcing material used in producing the styrene compound, imide compound, and heat-resistant resin (2) may be one type, or two or more types may be used in combination.

(B) Thermoplastic resin The thermoplastic resin used in the present invention is a rubber selected from the group consisting of butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber, and styrene and acrylonitrile or styrene and methyl methacrylate. It is selected from the group consisting of impact-resistant resins obtained by graft copolymerization and "coelectropolymer resins of styrene and acrylonitrile or styrene and methyl methacrylate" (hereinafter referred to as "styrenic copolymer resins").

(1) Impact-resistant resin The rubber used in the production of the impact-resistant resin in the present invention is a butadiene homopolymer rubber and a random or block copolymer rubber of butadiene and a small amount (usually 40% by weight or less) of styrene or acrylonitrile. Selected butadiene rubbers, copolymer rubbers of ethylene and propylene, and linear or branched diolefins containing ethylene and propylene and a small amount (generally 10% by weight or less) of two double bonds at the ends ( For example, 1.4-
pentagene), linear or branched diolefins containing just one double bond at the end (e.g. 1,4-hexadiene) and bicyclo(2,2,1)-hebutene-2
ethylene-propylene rubber selected from a multicomponent copolymer rubber with acrylic acid ester (e.g., phtyl acrylate) or a small amount (generally 10% by weight or less) of this ester and other monomers (e.g., , acrylonitrile).

In producing the impact-resistant resin of the present invention, among these rubber-like substances, those having a Mooney viscosity of 20 to 140 are preferable, and those having a Mooney viscosity of 30 to 120 are particularly preferable, although it varies depending on the type of the rubber-like substance. It is. Further, these rubber-like materials are widely produced industrially and are used in a wide variety of fields. Their manufacturing methods, properties and uses are widely known [
For example, Shu Kambara, "Synthetic Rubber Hunt Rack" (1962, published by Asakura Shoten).

In producing the impact-resistant resin of the present invention, graft polymerization methods include bulk polymerization, solution polymerization, emulsion polymerization, aqueous suspension polymerization, and methods that combine these graft polymerization methods (for example, bulk polymerization After that, there is a method of carrying out aqueous suspension polymerization). Generally, the amount of rubber material used to produce 100 parts by weight of impact resistant resin is 5 to 45 parts by weight, preferably 5 to 40 parts by weight,
In particular, 10 to 40 parts by weight is preferable (a relatively large amount of the rubbery material is used to produce a graft polymer containing a large amount of the rubbery material, and the above-mentioned styrene, acrylonitrile, methyl methacrylate is added to the grafted polymer). may be mixed with a homopolymer resin or a copolymer resin; in this case, the amount of rubber-like material used is calculated based on the mixture). Furthermore, the molecular weight of the polymer (styrene, acrylonitrile, methyl methacrylate) bonded to the rubber-like material as a graft chain is usually 1000 to 300.000, preferably 2000 to 200.000. In general, complete bonding of monomers to the rubbery material is rare, and there are grafted products and homopolymers or copolymers of monomers that do not bond to the rubbery material. These homopolymers and copolymers are used as they are without separation.

Typical examples of impact-resistant resins produced as described above include butadiene homopolymer rubber, block or random copolymer rubber of styrene and butadiene (SBR), or acrylonitrile and butadiene copolymer rubber (NBR),
Acrylonitrile-butadiene-obtained by graft copolymerization of styrene and acrylonitrile
Styrene ternary copolymer resin (ABS resin), methyl methacrylate-butadiene-styrene ternary copolymer resin (MBS resin) obtained by graft copolymerizing styrene and methyl methacrylate to butadiene homopolymer rubber or SBH, acrylic acid Acrylonitrile - acrylic acid ester - obtained by graft copolymerizing acrylonitrile and styrene to ester rubber
Examples include styrene terpolymer resin (AAS resin) and graft copolymer resin (AES resin) obtained by graft copolymerizing acrylonitrile and styrene to ethylene-propylene rubber.

Furthermore, in the production of the above impact resistant resin, a relatively large amount (generally 40 to 70% by weight) of rubber is graft copolymerized with styrene and acrylonitrile or styrene and methyl methacrylate in the same manner as in the production of the impact resistant resin. Using a high rubber concentration impact resistant resin (for example, a high rubber concentration acrylonitrile-butadiene-styrene ternary copolymer resin) obtained by the method, the heat-resistant resin described above, and the styrenic copolymer resin described later, The composition ratio may be adjusted within a range.

These impact-resistant resins are manufactured industrially and are used in a wide variety of fields, and the manufacturing method is well known.

(2) Styrenic resin Furthermore, the styrene resins used as thermoplastic resins are a copolymer resin of styrene and acrylonitrile (AS resin) and a copolymer resin of styrene and methyl methacrylate (MS resin). The copolymerization ratio of styrene in these styrenic resins is generally 40 to 85% by weight (preferably 50 to 80% by weight).

This styrenic resin is industrially produced by a polymerization method similar to the above-mentioned graft polymerization, and is used in a wide variety of fields.

(C) Antimony oxide Antimony oxide used in the present invention is widely used as a synergistic flame retardant auxiliary agent for bromine-containing compounds described below. Typical examples include antimony trioxide, antimony pentoxide, and these antimony oxides. The average particle size of the antimony oxide is 1 to 150 grs.
It is.

(D) Silicone oil Furthermore, the viscosity of the silicone oil used in the present invention is generally 10 to 10 at a temperature of 25°C.
0,000 cP (centipoise) and 50 to 5
0.000 cP is preferable, especially 50 to 20
,000 cP is suitable. Viscosity at a temperature of 25°C?1. If silicone oil with less than OcP is used, there is a risk of volatilization during kneading. On the other hand, 1
If more than 00,000 cP is used, the compatibility will be poor.

As typical examples of the silicone oil, polydimethylsiloxane, polymethylphenylsiloxane, and polymethylhydrogensiloxane are mainly used. Furthermore, polydialkyl (the number of carbon atoms in the alkyl group is usually 1 to 1)
(8) Modified silicone oil obtained by modifying the alkyl group of siloxane with epoxy, alkyl, amino, carboxyl, or alcohol can also be used.

(E) Composition ratio The styrenic compound and imide compound that are copolymerized components of the heat-resistant resin account for the total amount of the polymeric substance consisting of the heat-resistant resin and thermoplastic resin (impact-resistant resin and styrene-based resin). The ratio is 10 as the total amount of these
-50% by weight, preferably 15-50% by weight, particularly preferably 15-40% by weight. If the total proportion of the styrene compound and imide compound in the polymeric substance is less than 10% by weight, the resulting composition will have poor heat resistance. On the other hand, if it exceeds 50% by weight, the processability of the resulting composition is poor.

In addition, [butadiene-based rubber used as a rubber reinforcing material used as a starting material (raw material) for heat-resistant resin (2) and as a starting material for impact-resistant resin],
The proportion of "ethylene-propylene rubber and acrylic ester rubber" (hereinafter referred to as "rubber component") is 5 to 45% by weight as a total amount of these, preferably 5 to 40% by weight, especially 10 to 40% by weight. % is preferred. If the total proportion of the rubber component in the polymeric material is less than 5% by weight, the resulting composition will have poor impact resistance. On the other hand, if it exceeds 45% by weight, not only the moldability of the composition will be poor, but also the heat resistance will be poor.

Furthermore, the composition ratio of the styrene resin in the total amount of the heat resistant resin and the styrene resin is 20 to 80% by weight, preferably 20 to 70% by weight. If the composition ratio of the styrene resin to the total amount of the heat resistant resin and the styrene resin is less than 20% by weight, sufficient impact resistance cannot be obtained. On the other hand, if it exceeds 80% by weight, the resulting composition will have poor heat resistance.

Further, the composition ratio of antimony oxide to 100 parts by weight of the polymeric substance is 0.5 to 15 parts by weight.

If the composition ratio of antimony oxide to 100 parts by weight of the polymer substance exceeds 15 parts by weight, the mechanical strength of the resulting composition decreases.

Further, the composition ratio of "decabromodiphenyl ether and octadiphenyl ether" (hereinafter referred to as "bromine compound") to 100 parts by weight of the polymeric substance is 15 to 40 parts by weight, preferably 15 to 35 parts by weight, particularly 20 parts by weight. ~35 parts by weight is suitable. If the composition ratio of the bromine compound to 100 parts by weight of the polymeric material is less than 15 parts by weight, sufficient flame retardancy cannot be exhibited. On the other hand, if it exceeds 40 parts by weight, the resulting composition will have poor impact resistance. Further, the composition ratio of decabromodiphenyl ether in the bromine compound is 20 to 80% by weight. If the composition ratio of decabromodiphenyl ether in the bromine compound is less than 20% by weight, tripping is likely to occur and the flame retardancy is reduced. On the other hand, if it exceeds 80% by weight, impact resistance is poor.

Further, the ratio of the bromine compound to 1 part by weight of antimony oxide is preferably 1 to 5 parts by weight.

Further, the composition ratio of silicone oil to 100 parts by weight of the polymeric material is 0.1 to 3.0 parts by weight, and preferably 0.1 to 2.5 parts by weight. The composition ratio of silicone oil to 100 parts by weight of polymeric material is 0.
If the amount is less than 1 part by weight, the composition will not be able to sufficiently exhibit the tripping prevention effect. On the other hand, if it exceeds 3.0 parts by weight, when kneading to produce the composition,
Not only does this cause slippage, but the resulting composition has poor heat resistance.

(F) Production of composition, molding method, etc. In producing the composition of the present invention, the heat-resistant resin and thermoplastic resin, which are polymeric substances, and antimony oxide, bromine compound, and silicone oil are uniformly blended. Additives such as heat, oxygen and light stabilizers, fillers, colorants, lubricants, plasticizers and antistatic agents, which are widely used in the field of polymeric materials, can achieve the purpose by Depending on the intended use of the composition, they may be added to the extent that they do not essentially impair the properties of the composition of the present invention.

In producing the composition, all the composition components may be mixed at the same time, or some of the composition components may be roughly mixed,
The resulting mixture and the remaining composition components may be mixed.

Mixing methods include trifriending using a mixer such as a Henschel mixer, which is commonly used in the field of synthetic resins, and mixing while melting using mixers such as an open roll, extrusion mixer, kneader, and Banbury mixer. I can tell you how to do it. Among these mixing methods, two or more of these mixing methods may be used in combination to obtain a uniform composition (for example,
After dry mixing, the mixture is melt mixed). In particular, even when Tri-Friend is used in combination, or when one or more melt-kneading methods are used together, when producing a molded article by the forming method described later, it is necessary to use a beletizer to produce a pellet. It is preferable to use

Of the above mixing methods, both melt kneading and molding using the molding method described later must be carried out at a temperature that melts the polymeric substance used. but,
If the process is carried out at a high temperature, it is necessary to carry out the process at a temperature below 280°C since there is a risk that the polymer substance may undergo thermal decomposition or deterioration, or the bromine compound may decompose.

The composition of the present invention may be molded into a desired shape by applying molding methods commonly practiced in the field of synthetic resins, such as injection molding, extrusion molding, compression molding, and blow molding. Alternatively, after forming the sheet into a sheet using an extrusion molding machine, this sheet may be formed into a desired shape by a secondary processing method such as a vacuum forming method or a pressure forming method.

[Examples and comparative examples]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the melt 0-index (hereinafter referred to as rM, 1.J) is JISK 72
Measurements were made at a temperature of 250° C. and a load of 5 kg. In addition, the tensile yield strength and elongation rate are as per ASTM
Measurement was carried out using an ASTM No. 1 Tangier according to D638 at a strain rate of 5III1Z minutes. moreover,
Izotsu impact strength conforms to ASTM, D255,
Measurements were made with a notch at a temperature of 23°C. Also,
In the heat resistance test, the sample was allowed to stand in a press at 230°C for 60 minutes, and changes in the state of the sample were observed.

The manufacturing method, type, physical properties, etc. of the heat-resistant resin, thermoplastic resin (impact-resistant resin, styrene resin), antimony oxide, bromine compound, and silicone oil used in the Examples and Comparative Examples are shown below.

((A) Heat-resistant resin) Heat-resistant resin (1) and heat-resistant resin (2) manufactured as follows were used as the heat-resistant resin.

6000g of water in a 10 sentence autoclave, 2400g
g of styrene (ST), 800 g of acrylonitrile (AN) and 800 g of N-phenylmaleimide (N
-PMI) and further charged 8 g lauryl peroxide and 9.6 g tertiary-phthyl peroxylaurate as initiators, 8 g tertiary-todecyl mercaptan (chain transfer agent) and as suspension stabilizer. 20g
of tricalcium phosphate and 0.3 g of dodecylbenzene sulfone were added and polymerization was carried out at a temperature of 80°C for 2 hours with stirring. Then, the polymerization system was heated to 120°.
After the temperature was raised to C and polymerization was carried out at this temperature for 3 hours, the polymerization system was allowed to cool to room temperature. As a result, approximately 350
0 g of pale yellow powder was obtained. When the obtained powder was determined by infrared absorption spectroscopy (solution method), the weight ratio was ST・AN:N-PMI=60:20
: 20 [hereinafter referred to as "resin (a)"]. The intrinsic viscosity of this heat-resistant resin (in chloroform, temperature 0.05 g/50 m, 30°C
) [η] is 0.950, and the heat-resistant temperature (ASTM
It was measured with a load of 18.5 kg when using D648 (the same applies hereafter), and the temperature was 118°C.

2400 g styrene (ST), 800 g acrylonitrile (AN) and N-phenylmaleimide (N
-PMI) monomer mixture with Mooney viscosity (ML+
A butadiene homopolymer rubber having a temperature of 35 (+4, 100°C) was charged, and this rubber was completely dissolved in the 1,000 ml mixed solution. The temperature of the polymerization system was increased to 110°C.

Bulk polymerization was carried out for 2.5 hours. The resulting mixture containing the prepolymer was added to 6000 g of water containing the same amounts of initiator, chain transfer agent and suspension stabilizer as above, and aqueous suspension polymerization was carried out at a temperature of 80° C. for 2 hours. I did it. The temperature of the polymerization system was immediately raised to 120°C, and after aqueous suspension polymerization was carried out at this temperature for 3 hours, the polymerization system was allowed to cool to room temperature. As a result, approximately 3300 g of yellow powder was obtained. When the obtained powder was analyzed in the same manner as resin (a), it was found that it was a butadiene homopolymer rubber with 1,000 units of structural units or a graft polymer that was the same as resin (a) [hereinafter referred to as "resin (b)"]. It turned out to be. This resin (
The intrinsic viscosity (η) of b) was 0.850, and the heat resistance temperature was OBoC.

[(B) Thermoplastic resin]

Among thermoplastic resins, acrylonitrile-butadiene-styrene terpolymer resin (
(hereinafter referred to as rABSJ), methyl methacrylate-butadiene-styrene ternary copolymer resin (hereinafter referred to as BSJ), acrylonitrile-acrylic acid ester rubber.
Styrene ternary copolymer resin (hereinafter referred to as rAASJ) and acrylonitrile-olefin rubber-styrene type multi-component copolymer resin (hereinafter referred to as rAEsJ) are respectively
It was produced and used in the same manner as the ABS resin, MBS resin, AAS resin, and AES resin used in the Examples and Comparative Examples of Publication No. 8-134144.

In addition, as the styrene resin, an acrylonitrile-styrene copolymer (average degree of polymerization of about 750, hereinafter referred to as rASJ) with a copolymerization ratio of acrylonitrile of 23% by weight and methyl methacrylate with a copolymerization ratio of 25% by weight are used. A methacrylate styrene copolymer (average degree of polymerization approximately 800, hereinafter referred to as rMsJ) was used.

[(C) Antimony oxide] Furthermore, antimony trioxide (hereinafter referred to as r 5b203 J) was used as antimony oxide.

((D) Bromine Compound) In addition, as a bromine compound, decatromo diphenyl ether (hereinafter referred to as "bromine (1)") and octafuromodiphenyl ether (hereinafter referred to as "bromine (2)") are used. , and for comparison, tetrafluorobisphenol A
(hereinafter referred to as "bromine (3)") and 1, 2, 3, 4
,7,8,9,10,13,13,14.14-dodecachloro-1,4,4a,5,6.6a,7,10.10
a, 11, 12.12(a)-dodecahytone 1.4,
7.10-dimethanodibenzo(a,e)cyclooctene [hereinafter referred to as "chlorine compound (1)"] was used.

[(E) Silicone oil]

Furthermore, as a silicone oil, polydimethyl silicone oil [hereinafter referred to as rSi(A)J] whose viscosity (measured at 25°C, the same shall apply hereinafter) or 5,000 cP is used.
, polymethylphenyl silicone oil (referred to as Si(B) J) with a viscosity of 1,0 OOcP, clay 1,
Polymethylhydrodiene silicone oil (hereinafter referred to as rsi(C)J) with a viscosity of 1,000 cP,
000cP epoxy silicone oil (r.s.
i (D) J) and an amino silicone oil (hereinafter referred to as r 5i (E) J) having a viscosity of 60OcP.

Examples 1 to 18, Comparative Examples 1 to 8 Table 1 shows heat resistant resins, impact resistant resins, styrene resins,
The types and amounts of antimony oxide, bromine compound, and silicone oil are shown, as well as 0.2 parts by weight of 2,6-C.

Each of the tertiary-phthyl-P-cresols was triblended for 5 minutes using a Henschel mixer.

The resulting mixtures were heated to 2006°C in cylinder 1, 210°C in cylinder 2, and 220°C in cylinder 3.
, 220°C for the adapter and 240°C for the die.
Bent type twin screw extruder (diameter 30
A pellet (composition) was manufactured while kneading using a millimeter (mm).

Each of the obtained compositions was tested as M, 1. Measurement of tensile yield strength, IJIT impact strength (notched), and heat resistance temperature, as well as flame retardancy [test piece thickness 1.5 + ui (1/16 inch)] and heat resistance test (250°C for 16 minutes) were evaluated. . These results are shown in Table 2.

(Left below) From the results of the above Examples and Comparative Examples, it is clear that the resin composition obtained by the present invention has unprecedented flame retardancy and impact resistance, and also has good heat resistance. .

(Effects of the Invention) That is, by combining a bromine compound and silicone oil, it is possible to obtain a resin composition with well-balanced physical properties.Furthermore, flame retardance, especially trippin' resistance, is improved.

The resin composition obtained by the present invention not only has excellent flame retardancy, impact resistance, and heat resistance, but also exhibits the following effects (characteristics).

1) Good moldability (fluidity).

2) The gloss of the molded product is good.

3) Excellent weather resistance, little discoloration.

Since the resin composition obtained by the present invention has the above-mentioned outstanding characteristics, it can be used in a wide variety of fields as described below.

1) Television receiver 2) Housing for fax machines, printers, etc. 3) Various fire alarm parts 4) Housing for home appliances

Claims (1)

[Scope of Claims] (A) (1) A copolymer of at least a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid, and (2) a styrene compound reinforced with a rubber reinforcing material and α , at least one heat-resistant resin selected from the group consisting of a copolymer of β-unsaturated dicarboxylic acid with an imide compound, (B) butadiene rubber, ethylene-propylene rubber, or acrylic ester rubber with styrene added. and (C) at least one styrenic resin selected from the group consisting of a copolymer resin of styrene and acrylonitrile or styrene and methyl methacrylate. , (D) antimony oxide, (E) decabromodiphenyl ether, (F) octabromodiphenyl ether, and (G) silicone oil, and the total amount of the heat-resistant resin, impact-resistant resin, and styrene resin that are polymeric substances. The proportion of the styrene compound and the imide compound, which are copolymerized components of the heat-resistant resin, is 10 to 50% by weight in total, and the imide compound accounts for the total amount of the styrene compound and the imide compound. The proportion of the starting materials, which are the rubber reinforcing material, butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber, is 5 to 45 weight% in total. And the composition ratio of the styrene resin in the total amount of the heat resistant resin and the styrene resin is 20 to 80% by weight, and the total amount of the heat resistant resin, impact resistant resin, and styrene resin is 1
00 parts by weight, the total amount of decabromodiphenyl ether and octabromodiphenyl ether is 15 to 40 parts by weight, but the composition ratio of decabromodiphenyl ether to this total amount is 20 to 40 parts by weight.
80 parts by weight, antimony oxide is 0.5 to 15 parts by weight, and silicone oil is 0.1 to 3.0 parts by weight.