JPH0195143A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having excellent heat resistance, impact resistance and flame retardancy, by blending three specified kinds of resins, Sb2O3 and a bromine compd. CONSTITUTION:A heat-resistant resin (A) which is a copolymer of a styrene compd., if necessary, reinforced with a rubber reinforcing material and an imide compd. of an alpha, beta-unsatd. dicarboxylic acid, an impact-resistant resin (a) obtd. by graft-copolymerizing styrene (ii) and acrylonitrile or methyl methacrylate (iv) onto butadiene rubber, ethylene-propylene rubber or acrylate rubber (i) and a thermoplastic resin (b) selected from copolymer resins of the components (i) and (ii) are mixed together to obtain a mixture contg. 10-50wt.% of the sum of the styrene compd. and 5-50wt.% imide compd. and 5-35wt.% of the sum of the rubber reinforcing material and the component (i). 100pts.wt. this mixture, 0.5-10pts.wt. Sb2O3 (C), 5.0-40pts.wt. bromine compd. (D) of formula (wherein n is 1-100) and 0.01-15pts.wt. ladder-type silicone resin (E) are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) 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 is promising as a material for parts of electronic devices, electrical devices, etc., which has good impact resistance and excellent flame retardancy.

[Conventional technology]

Currently, styrenic resins such as flame-retardant acrylonitrile-butadiene-styrene ternary copolymer resin (ABS resin) are used as housings for electronic and electrical equipment such as television sets, CRTs, various computer facsimiles, and word processors. Commonly used.

The heat resistance temperature of these flame-retardant wood fingers (ASTM D648
(measured at 18.5 kg/cm') 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, there are synthetic resins with a heat resistance temperature of 100°C or higher, such as polyphenylene oxide resin (PPO) and polycarbonate resin (PC), which have problems in terms of price and moldability. There is a need for synthetic resins or compositions thereof that have excellent flame retardancy. Additionally, in order to improve the moldability of PPO and PC, it has been proposed to blend #thermal resins such as styrene-maleimide polymers into these synthetic resins (U.S. Pat. Nos. 4,278,775 and 416).
No. 0792). Although these composites have good heat resistance and moldability, they have problems in terms of flame retardancy. Furthermore, it has been proposed to blend a styrene-maleimide polymer into a vinyl chloride resin (US Pat. No. 4,715,8046). The resulting compositions either have good flame retardancy or have problems with heat resistance. Furthermore, it has been proposed to add a halogen flame retardant such as decadibromodiphenyl ether to a styrene-maleimide polymer (Japanese Patent Laid-Open No. 82950/1983). The resulting composition is prone to dripping and has problems with flame retardancy. Furthermore, in addition to monomers such as styrene compounds and maleimide compounds, brominated phenylmaleimide compounds Th (Japanese Unexamined Patent Publication No. 157511/1982), brominated (meth)acrylate compounds (Japanese Unexamined Patent Publication No. 52-829)
Attempts have been made to copolymerize with halogen-containing monomers such as No. There's a problem.

(Problems to be solved by the invention) For these reasons, it not only has excellent flame retardancy, but also
There is a need 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. The purpose is to obtain a composition.

[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. At least one heat-resistant resin selected from the group consisting of a copolymer and (2) a copolymer of a styrene compound reinforced with a rubber reinforcing material and an imide compound of an α,β-unsaturated dicarboxylic acid.

(B) 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, and styrene and acrylonitrile or styrene and methyl methacrylate. at least one thermoplastic resin selected from the group consisting of copolymer resins, (C) antimony oxide, CD) a bromine-containing compound represented by the following formula n (where n is an integer from 1 to 100), and ( E) Consisting of a ladder-type silicone resin, the proportion of the styrene compound and imide compound, which are copolymer components of the heat-resistant resin, in the total amount of the heat-resistant resin and thermoplastic resin, which are polymeric substances, is the total amount. The proportion of the imide compound in the total amount of the styrene compound and the imide compound is 5 to 50 percent by weight, and the proportion of the imide compound in the total amount of the styrene compound and the imide compound is 5 to 50 percent by weight. The proportion of propylene rubber and acrylic ester rubber is 5 to 35% by weight as a total amount thereof, and 1. Antimony oxide is 0.5 to 10 parts by weight, and bromine-containing compound is 5.0 parts by weight.
~40 parts by weight, and the ladder type silicone resin is 0
．． 011-15 parts by weight of the resin composition. 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) A copolymer of at least a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid [hereinafter referred to as “thermal resin (1)”] (2) At least styrene reinforced with a rubber reinforcing material A copolymer of a copolymer of an α,β-unsaturated dicarboxylic acid imide compound [hereinafter referred to as “heat-resistant resin (2)”]. 2)
In this case, the styrene compound which is a copolymerization component is styrene or a derivative thereof, and the derivatives include α-methylstyrene, 0-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 following formula or formula (I).

NO In formula (I), R1, R2 and R3 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,
Examples include N-ethylphenylmaleimide and N-laurylmaleimide.

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
By hydrogenating butadiene copolymer rubber ([
) hydrogenated styrene-butadiene copolymer rubber and ethylene and propylene copolymer rubber.

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 suspended S polymerization method,
It can be produced by any one of the emulsion polymerization method, solution polymerization method, and bulk polymerization method, 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, the heat resistance will be insufficient. On the other hand, if 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 3 and methacrylonitrile, or methyl methacrylate. It may be copolymerized as a copolymerization component (copolymerization ratio, usually at most 30% by weight).

Furthermore, it is also possible to carry out 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 master hatch 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 used alone or in combination of two or more.

(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 "copolymer resins of styrene and acrylonitrile or styrene and methyl methacrylate" (hereinafter referred to as "styrenic copolymer resins").

(1) #Impact Resin The rubber used in the production of the impact resistant resin in the present invention is a phtadiene 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 or terminals ( For example, 1.4-
pentagene), linear or branched diolefins containing just one double bond at the terminal end (e.g. l,4-hexadiene), and polyvalent complexes with bicyclo(2,2,1)-hebutene-2 or its derivatives. Ethylene-propylene rubber selected from polymer rubber and acrylic ester (
For example, it is an acrylic ester rubber obtained by polymerizing a small amount (generally 10% by weight or less) of butyl acrylate or this ester with another monomer (eg, acrylonitrile).

In producing the impact-resistant resin of the present invention, among these rubber-like materials, those having a Mooney viscosity of 20 to 140 are preferable, depending on the type of rubber-like material, and those having a Mooney viscosity of 30 to 120 are particularly preferable. 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, "Synthetic Rubber Hunt Bluff" by Shu Kanbara (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 IIA polymerization, and methods that combine these graft polymerization methods (for example, bulk polymerization). After polymerization, there is a method of aqueous Q fi polymerization. Generally, the amount of rubber material used to produce 100 parts by weight of impact-resistant resin is 3 to 40 parts by weight, preferably 5 to 35 parts by weight, and particularly preferably 5 to 30 parts by weight. (A relatively large amount of rubbery material is used to produce a graft polymer containing a large amount of rubbery material, and this graft polymer is added to the above-mentioned Sino-German polymer resin or copolymer of styrene, acrylonitrile, methyl methacrylate. (If a polymer resin may be mixed, use of a rubber-like material in this case is calculated as the mixture).

Further, the molecular weight of the monomer (styrene, acrylonitrile, methyl methacrylate) bonded to the rubber-like material as a graft chain is usually from 1000 to 300,000, preferably from 200,000 to 200,000. In general, complete monomer bonding to the rubber material is rare, and there are graft products and heptad homopolymers or copolymers that do not bond to the rubber material. These homopolymers and copolymers are used as they are without separation.

Typical examples of #impact resins manufactured as described above include butadiene homopolymer rubber, styrene and phthalene copolymer rubber (SBR), or acrylonitrile and butadiene copolymer rubber (NBR), styrene Acrylonitrile-butadiene-styrene ternary copolymer resin (ABS resin) obtained by graft copolymerization of and acrylonitrile, methyl methacrylate obtained by graft copolymerization of styrene and methyl methacrylate to butadiene homopolymer rubber or SBH - phthadiene-styrene ternary copolymer resin (ABS resin), an acrylonitrile-acrylic ester-styrene ternary copolymer resin (AAS resin) obtained by graft copolymerizing acrylonitrile and styrene to acrylic ester rubber; Examples include graft copolymer resins (ES resins) obtained by graft copolymerizing acrylonitrile and styrene onto 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 obtained by (for example, a high rubber concentration acrylonitrile-butadiene-styrene terpolymer resin), the above-mentioned heat-resistant resin, 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) Styrene copolymer resin Furthermore, the styrene copolymer resin used as a thermoplastic resin is a copolymer resin of styrene and acrylonitrile (A
S resin) and a copolymer resin of styrene and methyl methacrylate (MS resin).

The copolymerization ratio of styrene in these styrenic copolymer resins is generally 40 to 85% by weight (preferably 50 to 8% by weight).
0! l! amount%).

This styrene copolymer resin is industrially produced by a polymerization method similar to the graft polymerization described above.

It is used in many ways.

(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 ILr.
It is a.

CD) Bromine-containing compound Further, the bromine-containing compound used in the present invention is represented by the following formula (Formula (II)).

In formula (II), n is an integer of 1 to 100.

The bromine-containing compound has a high decomposition temperature, and by adding it to the heat-resistant resin and thermoplastic resin, it not only maintains a high degree of heat resistance and impact resistance of the resulting composition, but also improves flame retardancy. It has a high ability, and adding a small amount of this compound can significantly improve flame retardancy. Moreover,
Because the thermal decomposition temperature of this compound is high, discoloration due to burning is unlikely to occur.

(E) Ratter type silicone resin The later type silicone resin used in the present invention is represented by the following formula [(■) formula].

In formula (m), R4 and R1 may be the same or different, and may be an alkyl group having 1 to 4 carbon atoms, a phenyl group,
A hydroxyl group, a carboxyl group having 1 to 4 carbon atoms, and an aminoalkyl group having 1 to 4 carbon atoms;
Carboxyl groups and aminoalkyl groups are present in a total molar amount of at most 10%, where 1 is 10 to 1.
It is an integer of 00.

When using this ladder-type silicone resin to produce the composition of the present invention, it may be used as it is, or it may be preliminarily condensed by heating in a temperature range of 80 to 300°C for 5 minutes to >. You can also use it in progress.

If this compound is further heated to a high temperature, it will react with the carbon in the above-mentioned heat-resistant resin or thermoplastic resin to form a 5i-C bond and become inorganic, thereby preventing dripping.

As described above, this ladder-type silicone resin exhibits great flame retardancy, particularly in preventing dripping. In particular, the effect of combined use with the bromine-containing compound is remarkable.

(F) Composition ratio The proportion of the styrene compound and imide compound, which are copolymer components of the heat resistant resin, in the total amount of the polymeric substance consisting of the heat resistant resin and thermoplastic resin is 10 to 10% as the total amount thereof. 50% by weight, 15-50% by weight
is preferable, and 15 to 40% by nail amount is particularly preferable. If the total proportion of the styrene compound and imide compound in the polymeric substance is less than 100% 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 35% by weight as a total amount of these, preferably 5 to 30% by weight, particularly 5 to 25% by weight. % is preferred.

The total proportion of rubber components in the polymer material is 5
If the amount is less than % by weight, the resulting composition will have poor impact resistance. On the other hand, if it exceeds 35% by weight, not only the moldability of the composition is poor, but also the heat resistance is poor.

The composition ratio of antimony oxide to 100 parts by weight of the polymeric material is 0.5 to 10 parts by weight.

When the composition ratio of antimony oxide to 100 parts by weight of the polymer substance exceeds 10 parts by weight, the mechanical strength of the resulting composition decreases.

Combining antimony oxide and bromine-containing compounds improves synergistic flame retardancy. In order to exhibit a synergistic effect, antimony oxide is required to be used in an amount of at least 0.5 parts by weight, preferably from 1.0 to 8.0 parts by weight, per 100 parts by weight of the polymeric substance.

Further, the composition ratio of the bromine-containing compound to 100 parts by weight of the polymeric substance is 5.0 to 40 parts by weight, preferably 5.0 to 35 parts by weight. If the composition ratio of the bromine-containing compound to 100 parts by weight of the polymeric material is less than 5.0 parts by weight, a composite material exhibiting sufficient flame retardance cannot be obtained. On the other hand, if it exceeds 40 weights, not only will the cost increase, but the impact resistance of the resulting composition will be poor.

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

Further, the composition ratio of the ladder type silicone resin to 100 parts by weight of the polymeric material was 0. Old ~ 15 parts by weight, Y parts, especially 0.05 to 10 parts by weight is 9! Delicious.

The composition ratio of the later type silicone resin to 100 parts by weight of the polymer material is 0. If the amount of O is less than 11 parts, the anti-dripping effect cannot be sufficiently exhibited. On the other hand, if it exceeds 15 parts by weight, it is not preferable because the compatibility with the polymeric substance becomes poor.

(G) Production of composition, molding method, etc. In producing the composition of the present invention, heat-resistant resin and thermoplastic resin, which are polymeric substances, as well as antimony oxide, bromine-containing compound, and ladder-type silicone resin are uniformly blended. Stabilizers against heat, oxygen and light, dehydrochlorination inhibitors, fillers, colorants, lubricants, plasticizers and Additives such as antistatic agents may be added depending on the intended use of the composition 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 mixed in advance,
The resulting mixture and the remaining composition components may be mixed.

Mixing methods include (1) Tri-blending 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 open rolls, extrusion mixers, kneaders, and Banbury mixers. Here are some ways 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,
(pre-triblending and then melt-mixing the mixture). In particular, when producing a molded product using the molding method described below, whether tri-blend is used in combination or when one or more melt-kneading methods are used together, it is necessary to produce pellets using a pelletizer. It is preferable to use it.

Of the above mixing methods, both melt kneading and molding using the molding method described below must be carried out at a temperature that melts the polymeric substance used. but,
If carried out at a high temperature, the polymer substance may undergo thermal decomposition or deterioration, or the bromine-containing compound may decompose, so it must be carried out at a temperature below 280°C.

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 flow index (hereinafter referred to as rM, 1.J) is JISK 72.
I set it to 10, the temperature is 250°C and the load is 5Kg.
It was measured with In addition, the tensile yield strength and elongation rate are AST
Measurement was performed at a strain rate of 51/min using ASTM No. 1 dumbbells in accordance with MD638. Furthermore, Izod impact strength was measured with a notch at a temperature of 23°C according to ASTM D256.

In addition, the manufacturing method, type, physical properties, etc. of the heat-resistant resin, thermoplastic resin, (impact-resistant resin, styrene copolymer resin), antimony oxide, bromine-containing compound, and ladder-type silicone resin used in the examples and comparative examples. is shown below.

((A) II! IJ Thermal Resin) As the heat resistant resin, heat resistant resin (1) and heat resistant resin (2) manufactured as follows were used.

In a 10-liter autoclave, 6000 g of water, 24 g of styrene (ST), 800 g of acrylonitrile (8N) and 800 g of N-phenylmaleimide (N-P) were added.
8 g of lauryl peroxide and 9.6 g of tertiary-butyl peroxylaurate as initiators, 8 g of tertiary-todecyl mercaptan (chain transfer agent) and 20 g as suspension stabilizer. of tricalcium phosphate and 0.3 g of dodecylbenzenesulfone were added at a temperature of 80° C. with stirring.
Time polymerization was performed. Then, the temperature of the polymerization system was raised to 120°C, and after polymerization was carried out at this temperature for 3 hours, the polymerization system was allowed to cool to room temperature. As a result, about 3500 g of pale yellow powder was obtained. When the obtained powder was determined by infrared absorption spectroscopy (solution method), the weight ratio of ST
: AN: N-PMI = 60: 20: A terpolymer (hereinafter referred to as "thermal resin (a)") was found. The intrinsic viscosity of this heat-resistant resin (in chloroform,
Temperature 0.05g150! I1 sentence, 30℃) (η) is 0
．． 950, and the heat resistance temperature (according to ASTM D648, measured with a load of 18.5 kg, the same applies hereinafter) is 11
The temperature was 8°C.

Mooney viscosity (M
A butadiene homopolymer rubber having a temperature of 100° C. or 100° C. was charged, and this rubber was completely dissolved in the seven-mer mixture. The temperature of the polymerization system was raised to 110°C, and bulk polymerization was carried out for 2.5 hours. The obtained 7mer mixture containing the prepolymer was added to 6000 g of water containing the same amount of initiator, chain transfer agent and suspension stabilizer, and heated at 80°C.
Aqueous suspension polymerization was carried out for 2 hours at a temperature of . 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 1300 g of yellow powder was obtained. When the obtained powder was analyzed in the same manner as the heat-resistant resin (a), it was found that Graph 1 to polymer (
It was found that the resin was a heat-resistant resin (hereinafter referred to as "heat-resistant resin (b)"). The intrinsic viscosity [η] of this heat-resistant resin (b) is 0.85
0, and the heat-resistant temperature was 108°C.

[(B) Thermoplastic resin]

Among thermoplastic resins, acrylonitrile-butadiene-styrene terpolymer resin (
(hereinafter referred to as rABSJ), methyl methacrylate-phthadiene-styrene ternary copolymer resin (hereinafter referred to as rMBSJ), acrylonitrile-acrylic acid ester rubber.
Styrene ternary copolymer resin (hereinafter referred to as "AS J"),
Acrylonitrile-olefin rubber-styrene multi-component copolymer resin (hereinafter referred to as rAESJ) is the ABS resin, MBS resin, and AAS resin used in the examples and comparative examples of JP-A-58-I:14144, respectively.
The resin was prepared and used in the same manner as the AES resin.

In addition, as a styrene-based copolymer resin, an acrylonitrile-styrene copolymer (average degree of polymerization of about 750, hereinafter referred to as rAsJ
) and the copolymerization ratio of methyl methacrylate
A 5% by weight methyl methacrylate styrene copolymer (average degree of polymerization approximately 800, hereinafter referred to as rMSJ) was used.

[(C) Antimony oxide]

Further, as antimony oxide, antimony trifoam (hereinafter referred to as "5b203") was used.

[(D) Bromine-containing compound]

In addition, bromine-containing compounds having a molecular weight of about 6000 and represented by the above formula (II) include polyditulomophenyl ether (hereinafter referred to as [compound Th(1) J)], decabromodiphenyl ether (hereinafter referred to as [compound (2) ”), tribromophenyl phosphate (hereinafter referred to as “compound Th
(3) J) and tetrafluorobisphenol A (hereinafter referred to as "compound (4)") were used.

((E) Ladder type silicone resin) Furthermore, as a ladder type silicone resin, in the formula (m), both R4 and R1 are methyl groups (molecular weight about 4000, hereinafter r
A silicone resin (molecular weight of about 3500, hereinafter referred to as rSi resin (B)) in which R4 and R5 have methyl groups and phenyl groups at a ratio of 1:1 (as a molar ratio). ) and a silicone resin in which both R4 and R5 are phenyl di^ [molecular weight approximately 3
000, hereinafter referred to as "Si resin (C)"] was used. For use, each of the various ladder-type silicone resins was heated at +50°C for 30 minutes, then ground, and a fraction of a 20() mesh bath was used.

Examples 1 to 16, Comparative Examples 1 to 8 Table 1 shows the types and amounts of heat-resistant resins, thermoplastic/plastic resins, antimony oxide, bromine-containing compounds, and ladder-type silicone resins, and 0.
2 parts by weight of 2,6-di-tert-butyl-P-cresol were each triblended for 5 minutes using a Henschel mixer. Each of the resulting mixtures was subjected to a vent-type twin-screw extrusion machine set at 200°C in cylinder 1, 220°C in cylinder 2, 240°C in cylinder 3, 240°C in adapter and 230°C in cylinder. A pellet (composition) was prepared by kneading using a pelletizer (diameter: 30 mm).

Each of the obtained compositions was tested for M,]0, tensile yield strength, isot impact strength (notched), and heat resistance temperature, as well as flame retardancy (test piece thickness 1.6a+m (1/16 inch)) and press. Heat resistance test (250℃, 6 minutes)
was 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 not only has excellent flame retardancy and impact resistance, but also has good heat resistance. It is.

(Effects of the Invention) That is, by combining a bromine-containing compound and a ladder-type silicone resin, a resin composition with well-balanced physical properties can be obtained. It also improves flame retardancy, especially drip resistance.

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).

l) Good moldability (fluidity).

2) The molded product has good gloss.

3) Excellent IIV1 symptoms, little discoloration.

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

l) Television receiver 2) Housing for facsimiles, printers, etc. 3) Various fire alarm parts 4) House sinks 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. at least one thermoplastic resin selected from the group consisting of an impact-resistant resin obtained by graft copolymerizing and acrylonitrile or styrene and methyl methacrylate, and a copolymer resin of styrene and acrylonitrile or styrene and methyl methacrylate, (C ) antimony oxide, (D) a bromine-containing compound represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where n is an integer from 1 to 100) and (E) a ladder-type silicone resin, which is a polymer. The proportion of the styrene compound and imide compound, which are copolymerized components of the heat resistant resin, in the total amount of the heat resistant resin and thermoplastic resin as substances is 10 to 50% by weight as a total amount, and the styrene compound The proportion of the imide compound in the total amount of the compound and the imide compound is 5 to 50% by weight, and the proportion of the starting raw material rubber reinforcing material, butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber is 5 to 35% by weight in total, antimony oxide is 0.5 to 10 parts by weight, and bromine-containing compound is 5.0 to 100 parts by weight in total of the heat-resistant resin and thermoplastic resin. ~
40 parts by weight, and the ladder type silicone resin contains 0.
01 to 15 parts by weight of the resin composition.