JPH0488046A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent heat resistance, impact resistance, fire retardance and processability comprising a heat-resistant resin, a thermoplastic resin, antimony oxide, a reaction product of a bromine- containing epoxy compound and a specific copolymer and silicone oil. CONSTITUTION:The aimed resin composition is composed of (A) a heat-resistant resin composed of a copolymer of a styrene-based compound arbitrarily reinforced with rubber and an alpha,betaunsaturated dicarboxylic acidimide-based compound, (B) a thermoplastic resin composed of a copolymer derived from polymerization of styrene and acrylonitrile, or styrene and methyl methacrylate arbitrarily in the presence of rubber such as butadiene-based rubber, (C) antimony oxide, (D) a reaction product of a bromine-containing epoxy-based compound derived from reaction of 2,4,6-tribromophenol and an acrylonitrile-butadiene copolymer having COOH on both of the chain ends and (E) silicone oil.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a heat-resistant hazy resin composition. 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 useful as an abrasive for parts of electronic and electrical equipment.

[Conventional technology]

Currently, flame-retardant 7'-nitrile-butane-styrene binary copolymer resin (ABS) is used for the housing 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.

In addition, synthetic resins with a heat resistance temperature of 100°C or higher and 157
511), brominated (meth)acrylate compounds (JP-A No. 52-82990) and other halogen-containing compounds.
Attempts have also been made to copolymerize with diamers.

[Problem to be solved by the invention]

However, the heat resistance temperature of styrene-based resins such as the above-mentioned flame-retardant ABS resins (as measured by ASTM D648, 18.5 kg/cJ) is usually 70-90'C.
However, depending on the use and size of the product, there are often problems with heat resistance.

Furthermore, compositions in which PPO or PC is blended with a heat-resistant resin such as a styrene-maleimide polymer have good heat resistance and moldability, but have problems in terms of flame retardancy. Furthermore, compositions made of vinyl chloride resin and styrene-maleimide polymers have excellent flame retardancy, but there are problems with heat resistance. Compositions to which a flame agent is added tend to cause dripping and have problems with flame retardancy. In addition, styrene compounds and maleimide are used to produce polyphenylene oxide resin (PPO) and polycarbonate resin (PPO).
C) etc., but there are problems in terms of moldability,
There is a need for synthetic resins or compositions thereof that are flexible, heat resistant, and flame retardant. moreover,
In order to improve the moldability of PPO and PC, it has been proposed to blend heat-resistant resins such as styrene maleimide polymers into these synthetic resins (US Pat. Nos. 4,278,775 and 4,160,792).

These compositions have good heat resistance and moldability, but
There is a problem with flame retardancy. Furthermore, it has been proposed to blend a styrene-maleimide polymer into a vinyl chloride resin (US Pat. No. 4,458,048).

Furthermore, it has been proposed to add a halokene flame retardant such as decadibromodiphenyl ether to a styrene-maleimide polymer (Japanese Patent Laid-Open No. 112950/1983).

In addition, in addition to monomers such as styrene compounds and maleimide compounds, brominated phenylmaleimide compounds (11XfTh forms of JP-A-1988 compounds, brominated phenylmaleimide compounds, brominated (meth)acrylate compounds, etc.) Multi-component copolymers obtained by copolymerizing with halogen-containing monomers require the use of a large amount of expensive halogen-containing monomers in order to impart sufficient flame retardancy, which is difficult to achieve in practice. There is a notification.

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 not only has excellent heat resistance and impact resistance, but also has good flame retardancy and moldability, and is relatively inexpensive. The purpose is to obtain a resin composition.

[Means and effects for solving the problems] According to the present invention, these problems are solved by (A) (+) a copolymer of at least a styrene compound and an imide compound of an α,β unsaturated dicarboxylic acid; and (2) at least one heat-resistant resin selected from 111-, which is a copolymer of a styrene compound and an α1β-unsaturated/carboxylic acid imide compound reinforced with a rubber reinforcing material; (B)
Impact resistant resin obtained by graft copolymerization of styrene and acrylonitrile or styrene and methyl methacrylate to butadiene rubber, ethylene-propylene rubber or acrylic ester rubber, and copolymerization of styrene and acrylonitrile or styrene and methyl methacrylate. At least one thermoplastic resin selected from the group consisting of resins, (C) antimony oxide, and (D) an epochine group at both ends reacted with 2,4.6-tribromophenol, the molecular weight of which is 1.200 to 1.200. 2
0.000, and the bromine content is 0 to 56% by weight.
A reaction product of a bromine gold white-epoxy compound and an acrylonitrile-butanene copolymer having white carboxyl groups at both ends and having a molecular weight of 1.000 to 10.000, and (A) a heat-resistant resin book. The heat-resistant resin used in the 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 “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 “
Even in the case of the above heat-resistant resin (1), the heat-resistant resin (2)
In this case, the styrene compound which is a copolymerization component is styrene or its derivatives, and the derivatives include α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, and chlorostyrene. It will be done.

Examples of imide compounds of α,β-unsaturated dicarboxylic acids include those whose -shipman is represented by formula (I).

(1) Consisting of silicone oil, 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 is 10 to 50 weight as a total amount, respectively. %, and the proportion of imide compounds in the total amount of styrene compounds and imide compounds is 5.
~50% by weight, and the proportions of rubber reinforcement +a used in the production of heat-resistant resins and butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber used in the production of impact-resistant resins are 51% by weight. The amount is 5 to 35% by weight, and antimony oxide is 0% per 100 parts by weight of the heat-resistant resin and thermoplastic resin.
．． 5 to IO parts by weight, the reaction product is 5.0 to 40 parts by weight, and the silicone oil is 0.1 to 3.0 parts by weight. The present invention will be specifically explained above.

In formula (I), R, R 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.

Furthermore, in producing the heat-resistant resin (2), the rubber reinforcing material used as a reinforcing material is styrene-butadiene copolymer rubber (of styrene) (polymerization ratio is usually 40
(% by weight or more), butadiene homopolymer rubber, hydrogenated styrene-butanene copolymer rubber obtained by hydrogenating the above-mentioned styrene-butane copolymer rubber, and polymer rubber of ethylene and propylene.

]0 The heat-resistant resin (2) is obtained by graft polymerizing a styrene compound and the above-mentioned imide compound to a rubber reinforcing material. The proportion used is usually 3 to 20 parts by weight (preferably 5 to 15 parts by weight).

In both cases of heat-resistant resin (1) and 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 as a copolymerization component and the imide compound of α,β-unsaturated dicarboxylic acid is 5. ~50% by weight, 10-50% by market weight
It is desirable that the weight is 110 to 45% by weight.

If the copolymerization ratio of the imide compound in the total amount of the styrene compound and the imide compound is less than 5% by weight,
If heat resistance is insufficient, impact resistance can be obtained by graft copolymerizing styrene and acrylonitrile or styrene and methyl methacrylate to a rubber selected from the group consisting of butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber. It is selected from the group consisting of resins and "copolymer 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 composed of butadiene homopolymer rubber and 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 small amounts of ethylene and propylene (generally,
a straight or branched diolefin (for example, 1.4 pentanene) containing only one double bond at the end; on the other hand,
When the content exceeds 50%, 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 be copolymerized with unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile or methyl methacrylate. It may be copolymerized as a polymerization component (copolymerization ratio, usually at most 30% by weight).

Furthermore, a relatively large amount of rubber reinforcing material is used as the heat-resistant resin (2), and graft copolymerization is performed to obtain a graft.
(The polymer may be used as a masterbatch and mixed with a heat-resistant resin (+).

Even in the case of heat-resistant resin (+) above, 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.

(13) Thermoplastic resin The thermoplastic resin used in the present invention can also be used with linear or branched diolefins (for example, 1.4 hexadiene) and bicyclo[2,2,1]-heptene-2 or its derivatives. Ethylene-propylene rubber selected from multi-component copolymer 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 substances, those having a Mooney viscosity of 20 to 140 are preferable, although it varies depending on the type of the rubber-like substance, and those having a Mooney viscosity of 30 to 120 are particularly preferable. It is. Moreover, these rubber-like materials are widely manufactured industrially and are used in many directions. Their manufacturing methods, properties and uses are widely known.
For example, Shu Kambara, "Synthetic Rubber Handbook" (1962, published by Chokai 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 graph I polymerization methods (for example, There is a method in which bulk polymerization is followed by aqueous suspension 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,
The amount is preferably 5 to 35 parts by weight, and particularly preferably 5 to 30 parts by weight. In addition, the homopolymer resin of styrene, acrylonitrile, methyl methacrylate or Monomers attached as graft chains (styrene, acrylonitrile,
methyl methacrylate) is usually 1,000~
300.000, especially between 2,000 and 200.000.
000 is desirable. In general, it is rare for a monomer to be completely bonded to a rubber-like material, and examples include graft copolymer resins (AES resins) in which monomers that do not currently exist are obtained by combining a graft material with a rubber-like material to obtain an Ill monopolymer.

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. An impact-resistant resin with a high rubber concentration (for example, an acrylonitrile-butanene-styrene ternary copolymer resin with a high rubber concentration) obtained by 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. Moreover, the manufacturing method is well known.

(2) Styrenic copolymer resins Furthermore, the styrene copolymer resins used as thermal 1-IJ plastic resins include copolymer resins of styrene and acrylonitrile (AS resin) and copolymer resins of styrene and methyl methacrylate (MS resin). ) There is a copolymer (1
do. These i and li 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 butane copolymer rubber (NBR).
Acrylonitrile-butadiene-styrene ternary copolymer resin (ABS resin) obtained by graft copolymerizing styrene and acrylonitrile, and acrylonitrile-butadiene-styrene ternary copolymer resin (ABS resin) obtained by graft copolymerizing styrene and methyl methacrylate to butadiene homopolymer rubber or SBH. Methyl methacrylate-butadiene styrene terpolymer resin (MBS resin) obtained by graft copolymerization of acrylonitrile and styrene onto acrylic ester rubber, acrylonitrile-acrylic ester-styrene terpolymer resin (AAS resin) Graph of acrylonitrile and styrene for resin) and ethylene-propylene rubber!・By copolymerization. The copolymerization ratio of styrene in these styrene-based copolymer resins is generally 40 to 85% by weight (preferably 50 to 80% by weight).
It is.

This styrene-based copolymer 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 Furthermore, the antimony oxide used in the present invention is a typical flame retardant aid for bromine-containing compounds, and timon is a typical example. The average particle size of the antimony oxide is 1-
It is 150 μm.

(D) Reaction product The reaction product used in the present invention has a molecular weight of 1.200 to 20.000 and a bromine content of 10 to 560 to 56 parts by weight of the bromine-containing epoxy compound. The carboxyl group is added to the end, and the molecular weight is 1.000~
10,000 acrylonitrile-butanene copolymer.

The bromine content a of the bromine-containing epoxy compound is 10 to 56
It is preferably 15 to 56% by weight, particularly preferably 20 to 56% by weight.

If a bromine-containing epoxy compound with a bromine H content of less than 10% by weight is used, the flame retardance of the resulting composition will be poor. Moreover, the molecular weight of the bromine-containing epoxy compound is 1.2
00-20.000 and 1.500-15.000
A value of 2.000 to 10.000 is particularly preferred. If a bromine-containing epoxy compound with a molecular weight of less than 1.200 is used, the heat resistance will be poor. On the other hand, if it exceeds 20,000, the compatibility will be poor and the surface gloss of the molded article will be low, which is undesirable.

The general formula of the bromine-containing epoxy compound is the one-do formula [(■)
The following formula can be mentioned.

When one combination is used, there is a problem with the impact resistance of the resulting composition. On the other hand, acrylonitrile exceeding 10,000
When a butane copolymer is used, there is a problem in terms of compatibility with the above-mentioned bromine-containing epoxy compound. Further, the copolymerization ratio of acrylonitrile in the acrylonitrile-butadiene copolymer portion of this compound is at most 40%.

If the copolymerization ratio of acrylonitrile exceeds 40% by weight, the viscosity increases significantly, making handling difficult.

The reaction product of the present invention can be obtained by reacting a bromine-containing epoxy compound with an acrylonitrile-butadiene copolymer having carboxyl groups at both ends. As a method for obtaining a reaction product, there is a method in which an acid catalyst is used and heated in the presence or absence of a solvent. Any method can be applied to obtain the reaction product of the present invention.

Acrylonitrile with H carboxyl groups at both ends based on 100 parts by weight of the bromine-containing epoxy compound] Furthermore, the molecular weight of the acrylonitrile butadiene copolymer used in the present invention is 1,000 to +0.000,
I is preferably 500 to 8,000, particularly preferably 2.000 to 7.000. The reaction ratio of acrylonitrile-butadiene copolymer with a molecular weight of less than 1.000 is generally 5.0 to 5.0.
100 parts by weight, particularly preferably 5.0 to 90 parts by weight. If the reaction ratio of the acrylonitrile-butadiene copolymer having carboxyl groups at both ends to 100 parts by weight of the bromine-containing epoxy compound is less than 50 parts by weight, the effect of improving impact resistance will not be sufficient. On the other hand, if it exceeds 100 parts by weight, there is a problem in terms of heat resistance.

(E) Silicone oil Furthermore, the viscosity of the silicone oil used in the present invention is 25°C? In M a, generally 10 to lo
o, ooocP (centipoise), 50-50.
000 ePO is desirable, especially 50 to 20.0
00eP is preferred. If a silicone oil with a viscosity of less than 1 ocP at a temperature of 25° C. is used, there is a risk of volatilization during kneading. On the other hand, lO,000c
If more than P is used, the compatibility will be poor.

In addition, if silicone oil is heated to a higher temperature, it will react with the carbon in the heat-resistant resin and hot-opening plastic resin,
It generates 5i-C bonds and becomes mineralized, resulting in 9 dripping and 11 protection.

In this way, silicone oil has flame retardant properties, especially drip resistance! /J+I. In particular, the effect of combined use with the above reaction products is remarkable.

(1) Composition ratio: The proportions of the styrene compound and imide compound, which are copolymer components of the heat resistant resin, are each 10 C31nt. ~50 vehicles (λ0, 10~
450 to 45 parts by weight, particularly preferably 12 to 45% by weight. The proportion of styrene compounds and imide compounds in the polymer substance is 10 as the total amount of each.
When the weight R is less than 90, the resulting composition has poor heat resistance. On the other hand, if it exceeds 500 parts by weight, the processability of the resulting composition is poor.

In addition, the butanene rubber, ethylene-propylene rubber, and ethylene-propylene rubber used in the production of rubber reinforcing materials and impact-resistant resins used in the production of heat-resistant resin (heat-resistant resin (2)) The composition ratio of the acrylic reaction product is 5.0 to 40 parts by weight, particularly preferably 5.0 to 35 parts by weight. If the composition ratio of the reaction product to 100 parts by weight of the polymeric material is less than 5.0 parts by weight, the composition will not exhibit sufficient flame retardancy. On the other hand, if it exceeds 40 parts by weight, not only will the cost increase, but the impact resistance of the resulting composition will be poor.

Further, the ratio of the reaction product that is λ·1 to 1 part by weight of antimony oxide is preferably 1 to 5 parts by weight.

Furthermore, the illumination ratio of silicone oil to 100 parts by weight of the polymeric material is 0.1 to 3.0 parts by weight,
Particularly desirable is 0.1 to 2.5 parts by weight. The composition ratio of silicone oil to 100 parts by weight of the polymeric material is 0. If the amount is less than the lfflQ portion, the composition cannot sufficiently exhibit the anti-dripping effect.

On the other hand, if it exceeds 3.0 parts by weight, slippage will occur during production of the composition, and the heat resistance of the resulting composition will be poor.

(G) Composition production, molding method, etc. In producing the composition of the present invention, fractional sulfuric acid ester rubber"
(hereinafter referred to as "rubber component") is the sum of these + 1
Illjl is 5 to 35% by weight, preferably 5 to 30% by weight, particularly preferably 5 to 25% by weight.

5 as the percentage or total amount of rubber components in the polymer material
If it 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 composition properties of the composition will be poor, but also the heat resistance will be poor.

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

If the composition ratio of antimony oxide to 00 parts by weight of the polymer substance exceeds 10 parts by weight, the mechanical strength of the resulting composition will decrease.

Combining antimony oxide and reaction products synergistically improves flame retardancy. In order to develop a synergistic effect, antimony oxide must be used in an amount of at least 0.5 parts by weight per 100 parts by weight of the molecular substance, especially 1 part by weight.
．． 0 to 8.0 parts by weight is desirable.

Furthermore, the objective can be achieved by uniformly blending the heat-resistant resin, thermoplastic resin, antimony oxide, reaction product, and silicone oil, which are the same as the above-mentioned 100% polymer material. However, depending on the intended use of the composition, additives such as heat, oxygen and light stabilizers, fillers, blue agents, lubricants, IIJ plasticizers and antistatic agents, which are widely used in the field of polymeric materials, may be added. They may be added to the extent that the properties of the composition of the present invention are not essentially impaired.

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 mixture to be removed may be mixed with the remaining composition components.

Mixing methods include a tri-blending method using a mixer such as a Henschel mixer, which is commonly used in the field of synthetic resins, and a method of tri-blending using a mixer such as an open roll, extrusion mixer, kneader, and Banbury mixer while melting. One method is to mix them. Among these mixing methods, two or more of these mixing methods may be used in combination to obtain a uniform composition (for example, tri-blending is performed in advance, and then the mixture is melt-mixed). In particular, when using tri-blend together or when using one or more melt-kneading methods, when producing a molded product using the molding method described below, it is important to use a pelletizer to produce pellets. Or preferable.

Of the above mixing methods, both melt kneading and molding using the molding method described below must be carried out at a temperature at which the polymeric substance used is melted. but,
If carried out at a high temperature, the polymer substance may undergo thermal decomposition or deterioration, or the reaction product may decompose, so it is necessary to carry out the process 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. In addition, after molding into a sheet using an extrusion molding machine, this [(A) heat-resistant resin] As the heat-resistant resin, heat-resistant resin (A) and heat-resistant resin (B) manufactured as follows. It was used.

6,000g water in 10g autoclave, 2.40
Loaded with 0 g of styrene (ST), 800 g of acrylonitrile (AN) and 800 g of N-phenylmaleimide (N-PMI), plus 8 g of lauryl peroxide and 96 g of primary monobutyl peroxylaurate as initiators. , 8 g of primary butane (chain transfer agent) and 20.0 g as suspension stabilizer. of tricalcium phosphate and 0.3 g of sodium dodenlebenzene sulfonate were added, and polymerization was carried out at a temperature of 80° C. for 2 hours with stirring. Then, the polymerization system was
The temperature was raised to .degree. C., and polymerization was carried out at this temperature for 3 hours, after which the polymerization system was allowed to cool to room temperature. As a result, approximately 3.5
00 g of pale yellow powder was obtained. When the obtained powder was determined by infrared absorption spectroscopy (solution method), it was determined that the terpolymer (the following two sheets were formed by vacuum forming method, It may be formed into a desired shape by a secondary processing method such as a molding method.

[Examples and comparative examples]

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

In the Examples and Comparative Examples, the melt flow index (hereinafter referred to as rMIJ) was measured at a temperature of 250° C. and a load of 5 kg according to 5K7210. In addition, the tensile yield strength is A according to ASTM D638.
Measurements were made using STM No. 1 dumbbells at a strain rate of 5 mm/min. Furthermore, the Izot impact strength is 8STM D2
5B, measurements were made with a notch at a temperature of 23°C. In addition, in the heat resistance test, changes in the state of the sample were observed after it was left in a 2509C press machine for 60 minutes.

The manufacturing method, type, physical properties, etc. of the heat-resistant resin, thermoplastic resin, impact-resistant resin, styrene copolymer resin, antimony oxide, bromine-containing material, and silicone oil used in the examples and comparative examples are shown below. .

It was called "Heat-resistant resin (A)J".The intrinsic viscosity of this heat-resistant resin (in chloroform at a temperature of 0.05g/
50m1, 30℃) [η] is 0.950, and the heat resistance temperature (A!liTM D64g, 18.5k) is 0.950.
The temperature was 118°C (measured under a load of 100g, hereinafter the same).

2.400g styrene (ST), gQOg acrylonitrile (AN) and N-phenylmaleimide (
Mooney viscosity (ML,
280 g of butadiene homopolymer rubber having a temperature (+4.100° C.) of 35 was charged, and this rubber was completely dissolved in the monomer mixture. The temperature of the polymerization system was raised to 110°C, and bulk polymerization was carried out for 2.5 hours. The monomer mixture containing the obtained prepolymer was added to 6.0 OOs- of water containing the same amounts of initiator, chain transfer agent and suspension stabilizer as above, and
Aqueous suspension polymerization was carried out for 2 hours at a temperature of °C. The temperature of the polymerization system was immediately raised to 120° C., and aqueous suspension polymerization was carried out at this temperature for 3 hours, after which the polymerization system was allowed to cool to room temperature. As a result, about 3.300 g of yellow powder was obtained. When the obtained powder was weighed in the same manner as heat-resistant resin (A), it was found that a graft polymer (hereinafter referred to as "heat-resistant resin ( B)"). The intrinsic viscosity [η] of this heat-resistant resin (B) is 0.850
The heat resistant temperature was 108°C.

[(B) Thermoplastic resin] Among the thermoplastic resins, as an impact-resistant resin, acrylonitrile-butanene-styrene binary copolymer resin (r
ABsJ), methyl methacrylate-butadiene-styrene ternary copolymer resin (rMBSJ),
Acrylonitrile acrylic acid ester rubber-styrene five-component copolymer resin (rAAsJ) and acrylonitrile-olefin rubber-styrene multi-component copolymer resin (rAEsJ) are disclosed in JP-A-58-13, respectively.
ABS resin, MBS resin, AAS resin and AE used in the Examples and Comparative Examples of Publication No. 4144
It was manufactured and used in the same manner as S resin.

In addition, as a styrene-based copolymer resin, a copolymerization ratio of acrylonitrile was 23% by weight, and drying was performed. As a result, 1,150 g of light brown powder (hereinafter referred to as "bromine (A)") was obtained. Further, for comparison, decabromo biphenyl ether (hereinafter referred to as "bromine (B)") was used.

[(E) Silicone oil]

Further, as silicone oils, polydimethyl silicone oil (hereinafter referred to as rsi(i)J) having a viscosity (measured at 25°C, the same shall apply hereinafter) of 5.000 cP, and polymethylhydrodiene having a viscosity of I, 000eP are used. Silicone oil (hereinafter referred to as rsi(2)J) and aminosilicone oil (hereinafter referred to as rSi(3)J) having a viscosity of 100 cP were used.

Examples 1 to 11, Comparative Examples 1 to 5 Table 1 shows the types and amounts of heat-resistant resin, thermoplastic resin, bromine-containing material, and silicone oil. 5b203 (antimony oxide) as shown in the table and 0.2
Parts by weight of 2,6-di-tert-butyl-p-cresol (as a stabilizer) were each added to a 5'3'3 lylonitrile-styrene copolymer (average degree of polymerization of about 750) using a Hennel mixer.
, hereinafter referred to as rAsJ) and methyl methacrylate in a copolymerization ratio of 25% by weight.
Styrene copolymer (![Degree of homopolymerization approximately 800, hereinafter rM
sJ) was used.

[(C) Antimony oxide]

Furthermore, antimony trioxide (hereinafter referred to as "5b203") was used as antimony oxide.

[(D) Reaction product]

Further, the bromine-containing fTm of the reaction product is 56% by weight, and [the above (II) with a homogeneous molecular weight of 5.000]
The epoxy compound represented by the formula is 1,000 g, the amount is 3,500, the copolymerization ratio of acrylonitrile is 17 times ff196, and carboxyl groups are attached to a at both ends.
200 g of acrylonitrile-butadiene copolymer was dissolved in 2,000 g of cellosolve acetate and stirred until uniform. Then, 0.5 g of p-
Toluenesulfonic acid was added, the temperature of the reaction system was raised to 150°C, and the reaction was continued for 4 hours without stirring. The solvent was removed from the resulting solution by evaporation, and tri-blending was performed in vacuo. Each mixture obtained was heated to 200°C in cylinder 1;
220℃ in cylinder 2, 240℃ in cylinder 3
, a vent-type twin-screw extruder (diameter 80+n+a) set at 240°C for the adapter and 230°C for the die.
) to produce pellets (composition).

Measurement of Ml, tensile yield strength, isot impact strength (notched), and heat resistance temperature of each composition obtained, and flame retardance [1. fimm (+/16 inch)] and heat resistance test. These results are shown in Table 2.

/ 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 poor flame retardancy and impact resistance, but also has good heat resistance.

〔Effect of the invention〕

That is, by combining the reaction product and silicone oil, 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 is a composition that exhibits the above-mentioned effects (characteristics), including flame retardancy, impact resistance, and heat resistance.

(1) Good moldability (LM, dynamics).

(2) Light d (bright) of the molded product.

(3) Less weather resistance, less fading, and less discoloration.

The resin composition obtained by the present invention has the above-mentioned excellent characteristics, and as a result, the resin composition obtained by the present invention has the following characteristics.
Can be used on surfaces.

(1) Three television receivers (2) Housings for facsimile machines, word processing sensors, microcomputers, printers, etc. (3) Parts for various fire alarms (4) Nozzlings 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) epoxy groups at both ends reacted with 2,4,6-tribromophenol and the molecular weight is 1,200 to 20,0.
00 and a bromine content of 10 to 56% by weight, and an acrylonitrile-butadiene copolymer having carboxyl groups at both ends and a molecular weight of 1,000 to 10,000. Consisting of the reaction product and (E) silicone oil, the proportions of the styrene compound and imide compound, which are copolymerization components of the heat resistant resin, in the total amount of the heat resistant resin and thermoplastic resin are each 10 as a total amount. ~50% by weight, and the proportion of imide compounds in the total amount of styrene compounds and imide compounds is 5% by weight.
~50% by weight, and the proportion of the rubber reinforcing material used in the production of heat-resistant resins and the butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber used in the production of impact-resistant resins is the total amount of these. As 5～
The amount of antimony oxide is 35% by weight, and the amount of antimony oxide is 0.5 to 1% per 100 parts by weight of the total amount of heat-resistant resin and thermoplastic resin.
0 parts by weight, the reaction product is 5.0 to 40 parts by weight, and the silicone oil is 0.1 to 3.0 parts by weight.