JPH03265661A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To improve impact strength, elongation, and flame retardance by compounding a compsn. comprising a polyphenylene sulfide modified with a styrenic resin and a polyphenylene ether resin with a specific (auxiliary) flame retardant. CONSTITUTION:60-98 pts.wt. polyphenylene sulfide is reacted with 2-40 pts.wt. epoxidized styrenic resin in a solution at 180 deg.C for at least 10min, and the reaction product is washed with a solvent to remove the unreacted styrenic resin, giving a styrenic resin-modified polyphenylene sulfide. 40-98 pts.wt. said sulfide is compounded with 60-2 pts.wt. polyphenylene ether resin to give 100 pts.wt. compsn., which is then compounded with 0.01-40 pts.wt. flame retardant selected from the group consisting of a halogen compd., a phosphorus compd., and, if necessary, a mixture thereof with an auxiliary flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermoplastic resin m-parabolite having excellent compatibility and flame retardancy. More specifically, it consists of polyphenylene sulfide added with styrene resin, polyphenylene ether resin, and a specific flame retardant, or a flame retardant and a flame retardant aid, which substantially impairs the original properties of polyphenylene sulfide such as mechanical strength and heat resistance. The present invention relates to a flame-retardant resin composition with improved elongation and impact strength, and a good balance of mechanical properties.

[Conventional technology]

Polyphenylene sulfide (hereinafter simply referred to as PPS) has excellent mechanical strength, heat resistance, chemical resistance, etc., and is flame retardant, so it is used for the rigidity and heat resistance of electrical, mechanical, electronic parts, automobile parts, etc. Applications are being actively developed in fields where this is required.

However, when developing these applications, PPS could not be used alone as a molding material because its elongation and impact strength were extremely low and it was extremely brittle, so a resin m-parabolite was proposed that compensated for these drawbacks. .

PP5O attack! In order to improve strength, many resin compositions have been proposed in which PPS is melt-blended with various engineering plastics such as polyphenylene ether (hereinafter simply referred to as PPE).

For example, in Japanese Patent Publication No. 56-34032, PPS and P
A resin composition having a mixed composition with PEs is disclosed in Japanese Patent Application Laid-Open No. 59-16
No. 4360 discloses a resin composition consisting of a resin selected from pps, polyarylate, polysulfone, PPE, etc., and an epoxy resin, while Publication No. 59-213758 discloses a resin composition consisting of PPS, PPE, a boria compound resin, and an epoxy resin. In JP-A No. 1-213361, PPS, PPE and glycidyl group-containing styrene resin are used, and in JP-A No. 59-68367, PPS is used.
and a flame-retardant resin m-acid consisting of a thermoplastic polyester and a flame retardant, and JP-A No. 63-77965 proposes a flame-retardant resin composition consisting of PPS, a thermoplastic polyester, and a brominated styrene resin.

[Problem to be solved by the invention]

However, in the proposals regarding the various PPS improvements mentioned above, Japanese Patent Publication No. 56-34032,
In the resin compositions made of PPS and various engineering plastics disclosed in Publication No. 4360 and Publication No. 59-213758, the compatibility of PPS and the resin added and mixed is low, so the average dispersion of the dispersed components in the dispersed state is low. Not only is the particle size large and the improvement in elongation and impact strength is insufficient, but the tensile strength and flexural modulus are significantly reduced compared to PPS alone, and the flame retardance is also reduced.

PP disclosed in Japanese Unexamined Patent Publication No. 1-213361
A resin composition consisting of S, PPE, a glycidyl group-containing styrene resin, and a thermoplastic elastomer has improved impact resistance, but has the disadvantage that tensile strength and flame retardance are lower than PPS. Problems arise when applied to building material parts, electrical and electronic parts, and there are cases in which there are significant restrictions on the intended use.

JP-A-59-68367 discloses a flame-retardant resin composition consisting of PPS, thermoplastic polyester, and a flame retardant;
Publication No. 3-77965 discloses a flame-retardant resin composition comprising PPS, thermoplastic polyester, and brominated styrene resin. Although these prior art techniques provide resin compositions with improved flame retardancy, The drawback was that the improvement in elongation and impact strength was insufficient.

The present invention improves impact strength and elongation without impairing the excellent properties of PPS, such as mechanical strength and heat resistance, which could not be achieved with conventional PPS resin compositions, and has flame retardancy. The purpose is to provide a resin composition.

[Means to solve the problem]

According to the present invention, (40 to 98 parts by weight of polyphenylene sulfide added with an al-styrene resin) and 60 to 2 parts by weight of a polyphenylene ether resin per 100 parts by weight of (a) + (b) (one or more flame retardants selected from Cl halogen-containing compounds and phosphorus compounds, or a mixture consisting of these flame retardants and flame retardant aids)
．． A flame retardant resin &+1 material containing 01 to 40 parts by weight is provided.

The present invention further provides a flame-retardant resin composition containing 1 to 60 parts by weight of (d) a thermoplastic elastomer based on 100 parts by weight of the above-mentioned flame-retardant resin composition. .

As mentioned above, (a) 75 minutes is PPS with addition of styrene resin, (b) *minute is PPE, and (c) component is a specific flame retardant or these flame retardants and flame retardant aids are blended. By doing so, or if necessary, by blending a thermoplastic elastomer as component (d), the average dispersed particle size of the dispersed component is fine, improving elongation and impact strength, and reducing tensile strength. Provided is a resin composition that has low flame retardancy and low flame retardancy.

The present invention will be explained in detail below.

Generally, it is difficult to add other resins to PPS, but PPS added with styrene resin, component (21) of the present invention, has functional groups such as epoxy groups and aryl groups that have an affinity for PPS. It can be obtained by reacting a styrenic resin having the following with PPS under predetermined reaction conditions.

For example, PPS and a styrene resin having an epoxy group are mixed directly or in a solution of α-chlornaphthalene, N-methyl-2-pyrrolidone, etc. while stirring uniformly in the presence or absence of a peroxide or acid catalyst. After reacting at a temperature of 180°C or higher, preferably 200 to 250°C for 10 minutes or more, the reaction mixture is washed with a solvent such as acetone or chloroform to remove the unreacted styrene resin having epoxy groups ( It is possible to obtain component a) styrenic resin-added PPS.

Component (a) can also be obtained by directly reacting PPS and a styrene resin having an epoxy group using a melt mixer such as a twin-screw kneader. In this case, it is necessary to make the kneading or reaction time longer than in the above method. If unreacted styrene resin exists (PPB for blrfc)
This is not preferable because it has poor crosstalk with other materials and does not improve elongation, etc. The mixing ratio of PPS and styrene resin having a functional group is 60 to 98 parts by weight of PPS, 2 to 40 parts by weight of styrene resin having a functional group, preferably 7 parts by weight of PPS.
0 to 95 parts by weight, 5 to 95 parts by weight of styrenic resin having a functional group
The amount is 30 parts by weight. If pps exceeds 98 parts by weight, the compatibility of the BL component of the present invention deteriorates and impact strength cannot be improved, and if it is less than 60 parts by weight, heat resistance and mechanical strength decrease, which is preferable. do not have.

The PPS used in the present invention preferably has a phenylene sulfide unit structure represented by the following structural formula (1) in an amount of 70 mol % or more in view of heat resistance, chemical resistance, and mechanical properties. If the phenylene sulfide unit content is less than 70 mol%, heat resistance will decrease.

The remaining 30 mol% is a meta bond in Structural Formula (2), an ether bond in Structural Formula (31), a sulfone bond in Structural Formula (4), and an alkyl group in Structural Formula (5) in which R has 12 or less carbon atoms. or substituted phenylene sulfide bond of any of alkoxy group, phenyl group, and nitro group, structural formula (6)
It consists of a biphenyl bond, a naphthyl bond of structural formula (7), a trifunctional phenyl sulfide bond, etc.

In addition, the melt flow rate of PPS is ASTMD I
315 with melt indexer specified by 23B-74T
Measured at a load of 5 kg at °C, 5 to 10,000 g/10 minutes, preferably 5 to 500 g/10 minutes, is used.

Commercially available PPSs can be used as these PPSs. For example, the product name “Rydon P” manufactured by Philips
P5J, the product name "Tofren" manufactured by Tobren Co., Ltd., the product name "Susteel" manufactured by Tosoh Sasteel Co., Ltd., and the product name "Fortron" manufactured by Kureha Chemical Industry ■. For example, when the functional group of the styrenic resin having an affinity for PPS used in the present invention is an epoxy group,
General formula CHZ CRCOOCHZ CHCHZ,\
○/ Copolymerization of an α,β-unsaturated acid glycidyl compound such as α,β-unsaturated acid glycidyl ester or α,β-unsaturated acid glycidyl ether in which R is a hydrogen atom or a lower alkyl group and a styrene monomer. It can be obtained by reaction.

Specific examples of styrene monomers include styrene, methylstyrene, vinylxylene, dichlorostyrene, bromustyrene, dibromostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, etc.
In addition, as glycidyl esters of α,β-unsaturated acids, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, etc.
- Examples of the unsaturated acid glycidyl ether include allyl glycidyl ether and vinyl glycidyl ether. Among these, styrene and glycidyl methacrylate are preferably used.

The copolymerization reaction of the styrene monomer and the α,β-unsaturated acid glycidyl compound can be carried out by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization using a known radical polymerization reaction. In addition, this reaction may be carried out by directly reacting the α,β-unsaturated acid glycidyl compound with the styrene monomer, or by reacting the styrene resin obtained by polymerizing the styrene monomer in advance with the α,β-unsaturated acid glycidyl compound. It may also be reacted with a compound.

When reacting the styrene resin and the α,β-unsaturated acid glycidyl compound in a molten state, a melt mixer such as an extruder, co-kneader, Banbury mixer, etc. can be used.

The reaction ratio of the styrene monomer and the α,β-unsaturated acid glycidyl compound is α,β-unsaturated acid glycidyl compound:styrene monomer=0.5 to 50:9 by weight.
The ratio is preferably 9.5 to 50, preferably 2 to 20:98 to 80. α,β-unsaturated acid glycidyl compound is 0.5
If it is less than 50 parts by weight, the reaction rate with PPS will be slow and impractical, and if it is more than 50 parts by weight, a gelation reaction will occur, making it difficult to add the styrene resin to pps, which is not preferable.

As the styrenic resin having a functional group having an affinity for PPS of the present invention, a copolymer with an α,β-unsaturated glycidyl compound as described above can be used, and the copolymer can be a random copolymer. It may be a polymer, a block copolymer, a graft copolymer, or a mixture thereof.Usually, it is preferable to use a random copolymer. In addition, the number average molecular weight of this styrene resin is usually 3000 to 1200.
00, preferably 10,000 to 50,000, but the number average molecular weight depends on the amount of radical initiator used in the copolymerization reaction,
It can be adjusted by adjusting the reaction temperature, etc.

In addition, in the present invention, 20 parts by weight or less, preferably 10 parts by weight or less of ethylene, propylene, butylene, butadiene, etc., per 100 parts by weight of the styrene resin having a functional group having an affinity for PPS as described above. , isoprene, acrylonitrile, methyl acrylate, methyl methacrylate, and the like can also be used by copolymerizing one or more monomers.

PPE, which is the component (b) of the present invention, is represented by the following structural formula (in the formula, R+, Rz, Rs, Ra, Rs, R
& is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen group, a hydrogen group, and R5 and R6 are not hydrogen at the same time. ) as a repeating unit, and the structure WjcjIi
Structural formula (8) or structural formula (8) and structural formula (9)
) can be used as a homopolymer or a copolymer.

Specific examples of PPE include poly(2,6-cymethyl-1,
4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2,6-
Danicyl-1,4-phenylene) ether, poly(2
-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2゜6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-5-n-butyl-
1,4-phenylene)ether, poly(2-ethyl-
6isoprobyl-1,4-phenylene) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4)
-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene)ether, poly(2
, 6-diphenyl 1,4-phenylene) ether, etc.
These copolymers can be mentioned.

The PPE copolymer mainly has a polyphenylene ether structure obtained by copolymerizing an alkyl-substituted phenol such as 2,3,6-)limethylphenol represented by the following structural formula with, for example, 0-talezol. Also included are polyphenylene ether copolymers.

Furthermore, the PPE used in the present invention can contain a styrene resin. The styrenic resin that can be used in the present invention has the following structural formula αD (wherein R is hydrogen, lower alkyl, or halogen, Z is selected from the group consisting of vinyl, hydrogen, chlorine, and lower alkyl, and p is 0・At least 2 polymer units derived from the compound represented by
5% by weight, homopolymers such as polystyrene and polychlorostyrene, modified polystyrenes such as rubber-modified polystyrene and styrene-containing copolymers such as styrene-acrylonitrile copolymer (SAN), styrene-butadiene copolymer, styrene-acrylonitrile-butylene. Gencopolymer (AB
S), polyα-methylstyrene, and copolymers of ethylvinylbenzene and divinylbenzene. The mixing ratio of PPE and styrene resin may be arbitrary, but preferably,
10 to 10 parts by weight of styrenic resin to 90 to 10 parts by weight of PPE
90 parts by weight is good, more preferably 70 to 30 parts by weight of PPE.
It is preferable to use 30 to 70 parts by weight of the styrene resin. If the amount of styrene resin is 90 parts by weight or more, the heat distortion temperature will decrease, and if it is less than 10 parts by weight, moldability will deteriorate, which is not preferable.

(c) * of the present invention includes halogen-containing compounds,
One or more flame retardants selected from phosphorus compounds, or these flame retardants and flame retardant aids. Specific examples of halogen-containing compounds include 2,2-bis-(3,
5-dichlorophenyl)propane, bis(2-chlorophenyl)methane, bis(2,6-dibromophenyl)methane, 1,1-bis-(4-iodophenyl)ethane,
1.2-bis(2゜6-dichlorophenyl)ethane, 1
, 1-bis(2-chloro-4-iodophenyl)ethane, 1゜1-bis(2-chloro-4-methylphenyl)ethane, l, 1-bis(3,5-dichlorophenyl)ethane, 2.2 -bis(3-phenyl-4-bromophenyl)ethane, 2,3-bis(4,6-dichloronaphthyl)
Propane, 2,2-bis(2゜6-dichlorophenyl)
Pentane, 2,2-bis(3,5-dichlorophenyl)
Hexane, bis(4-chlorophenyl)phenylmethane, bis(3,5-dichlorophenyl)cyclohexylmethane, bis(3-nitro-4-bromophenyl)methane, bis(4-hydroxy-2,6-dichloro-3-methoxy) phenyl)methane, 2.2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2.2-bis(3-bromo-4-hydroxyphenyl)propane, tetrabromobenzene, hexachlorobenzene, hexabromobenzene , 2.2'-dichlorobiphenyl, 2.4
'Dibromobiphenyl, 2,4-dichlorobiphenyl,
Hexabromo biphenyl, octabromo biphenyl, decabromo biphenyl, perchloropentane cyclodecane, dechlorane plus, tetrabromo ethane, tetrabromo butane, brominated benzene, chlorinated biphenyls, chlorine-containing aromatic polycarbonates, halogenated diphenyl ethers, etc. .

Among these, it is preferable to use hexabromobenzene, brominated benzene, and brominated biphenyl. These compounds may be used alone or in combination with phosphorus compounds and flame retardant aids.

Specific examples of phosphorus compounds include triphenylphosphine oxide, phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phosphoric acid-hydrogen phenylethylene, phenyl-bis-3°5.5'-trimethylhexyl phosphate, ethyldiphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, hydrogen diphenyl phosphate, bis(2-ethylhexyl)
p-tolyl phosphate, tritolyl phosphate,
Bis(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl)phosphate, phenylmethyl phosphate-hydrogen, di(dodecyl)p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, halogenated triphenyl phosphate,
Dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-)lylbis(2,5,5'trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, nitrogen phosphorus chloride, phosphorus ester adduct, phosphoric acid amide, phosphonic acid amide, phosphine There are acid amides, etc.

Among these phosphorus compounds, preference is given to using triphenyl phosphate, which may be used alone or in combination with hexabromobenzene, chlorinated biphenyls and flame retardant aids.

Specific examples of flame retardant aids include antimony trioxide, triphenylstibine, zinc oxalate, barium meta oxalate, zirconium oxide, and polyphenyl compounds.

Among these flame retardant aids, antimony trioxide is preferably used. In addition, the amount of flame retardant aid used is 100% flame retardant.
1 to 200 parts by weight, preferably 5 to 15 parts by weight
It is 0 parts by weight.

In the present invention, the halogen-containing compounds and phosphorus compound flame retardants mentioned above (c1) can be used alone or in combination of two or more.

The flame-retardant resin composition of the present invention has an alrti content of 40 to 98 parts by weight, preferably 50 to 95 parts by weight, and a component (b) of 2 to 60 parts by weight, preferably 5 to 50 parts by weight. It can be obtained by mixing 0.01 to 40 parts by weight, preferably 0.05 to 30 parts by weight, of component (c) to 100 parts by weight of the resin composition. (For all bones (
If component b) is less than 2 parts by weight, impact strength cannot be improved. Moreover, if it exceeds 60 parts by weight, chemical resistance decreases, which is not preferable. If the amount of component (c) is less than 0.01 part by weight based on 100 parts by weight of the mixture consisting of components (a) and (b), a resin composition with excellent flame retardance cannot be obtained. Also,
If it exceeds 40 parts by weight, impact strength and mechanical strength decrease, which is not preferable.

Furthermore, in order to obtain a flame retardant resin U acid having excellent impact strength, the above (a) component, (bl component and (c)
A thermoplastic elastomer may be added as component (d) to the mixture consisting of component (d).

The +dl 79 minute thermoplastic elastomer of the present invention is, for example, a styrene-based, ethylene-based, olefin-based, urethane-based, polyester-based, boria noble thermoplastic elastomer, chlorinated polyethylene, 1,2-polybutadiene,
Fluorine-based elastomers, ionomers, and the above-mentioned elastomers having acid anhydride groups or epoxy groups can be used.

Specific examples of styrene-based thermoplastic elastomers include styrene/butadiene/styrene block copolymers, styrene/isoprene/styrene block copolymers, styrene/ethylene/butylene/styrene block copolymers, modified maleic anhydride products, glycidyl modified products, etc. can be mentioned.

Commercially available products of these styrenic thermoplastic elastomers include, for example, the product name CARIFLEX TR (Shell Chemical Co., Ltd.
Product name: Tuffprene (manufactured by Asahi Kakai), Product name: Toughtic (manufactured by Asahi Kakai), Product name: JSR-TR (specially made by Japan Synthetic Rubber), Product name: Clayton G (manufactured by Shell Chemical), Product name: There are Sumitomo TPESB series (manufactured by Sumitomo Chemical ■), etc.

In addition, specific examples of olefinic thermoplastic elastomers include:
Ethylene-(meth)acrylic acid copolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer,
Furthermore, various known elastomers such as those having acid anhydride groups or epoxy groups can be used as the above-mentioned elastomers.

Commercially available products of these olefinic thermoplastic elastomers include, for example, Milastomer (manufactured by Mitsui Petrochemical Industries), Sumitomo TPE (manufactured by Sumitomo Chemical), Thermolan (manufactured by Japan Synthetic Rubber), and Thermolan (manufactured by Japan Synthetic Rubber). Name 5 ANTOP
RENE (manufactured by Monsanto), product name LEVAFLE
Examples include X-EP (manufactured by Bayer).

Commercially available urethane thermoplastic elastomers include, for example, the trade name Elastran (manufactured by Nihon Elastran Co., Ltd.);
There are product names such as ESTENE (B, F, manufactured by Gradrich). Commercially available polyamide-based thermoplastic elastomers include, for example, the trade name Glilux (manufactured by Dainippon Ink), the trade name Tsubamitsu (manufactured by Mitsubishika TC@), the trade name Diamid-PAE (manufactured by Daicel-Hüls), etc. There is.

Commercially available 1.2-polybutadiene thermoplastic elastomers include, for example, the trade name JSRRB (manufactured by Japan Synthetic Rubber).

Commercially available ionomer thermoplastic elastomers include:
For example, there is the trade name Surlyn (manufactured by DuPont).

In the present invention, among the above thermoplastic elastomers, styrene thermoplastic elastomers are most preferred.

In the present invention, the above (d) component is combined with (a) 75 minutes and ff1
)1F7. Composition 10 consisting of component (e) and
1 to 60 parts by weight, preferably 3 to 40 parts by weight
Parts by weight additive resin compositions can be constructed. If component (d) is less than 1 part by weight, the impact strength will hardly be improved, and if it exceeds 60 parts by weight, the rigidity of the resin composition will decrease, which is not preferable.

In the present invention, the above (all bone ω) components and (c
A fibrous resin composition is added to the flame retardant resin composition consisting of one precept, or (a) component, (b) tc component, (c) component, and (d) component to the extent that it does not impair its moldability and physical properties. ,7
7) Reinforcing materials and fillers in various shapes, such as shapes, can be added.

These reinforcing materials and fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica/aluminum fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, stainless steel, and aluminum straw. , metal fibers such as titanium, copper, brass, magnesium, etc., organic fibers such as polyamide, fluororesin, polyester, acrylic resin, etc., metals such as copper, iron, nickel, zinc, soot, lead, stainless steel, aluminum, gold, silver, etc. Examples include powder, fumed silica, aluminum silicate, glass beads, carbon black, quartz powder, talc, titanium oxide, iron oxide, calcium carbonate, and diatomaceous earth.

The average fiber diameter of the fibrous reinforcing material and filler is 0.5 to 30μ.
(2) A fiber having a fiber length of 50 μm or more can be used.

These reinforcing materials and fillers can be used alone or in combination of two or more, and those that have been surface-treated with a known camplining agent such as a silane cuff pulling agent or a titanate coupling agent may be used. I can do it.

The amount of reinforcing material and filler used is 1 to 300 parts by weight, preferably 1 to 100 parts by weight of the flame-retardant resin composition of the present invention.
It is 0 to 250 parts by weight.

These reinforcing materials and fillers can be used alone or in combination of two or more.

The flame retardant resin composition of the present invention includes hindered phenol, hydroquinone,
Antioxidants and heat stabilizers such as thioethers, phosphites and their substituted products and copper compounds, resorcinol,
UV absorbers such as salicylate, benzotriazole, and benzophenone, stearic acid and its salts, mold release agents such as stearyl alcohol, antistatic agents such as sodium dodecylbenzenesulfonate and polyalkylene glycol, crystallization accelerators, dyes, pigments, etc. It is also possible to add one or more types of additives.

In addition, thermoplastic resins such as polystyrene, polypropylene, ethylene/vinyl acetate copolymer, polyamide, polyester, polyacetal, polycarbonate, PPS, polysulfone, phenolic resin, melamine resin, silicone, etc. Thermosetting resins such as resins and epoxy resins can also be added.

The flame-retardant resin W paraboloid of the present invention can be produced by mixing and kneading each component using a conventional melt-mixing processing apparatus such as an extruder, Banbury mixer, or kneader, as described above.

Among these, a melt mixing method using a twin-screw extruder is preferred.

The kneading temperature at this time is not particularly limited, but can usually be arbitrarily selected from 280 to 350°C.

The flame-retardant resin composition of the present invention thus obtained is
By various conventionally known methods, it can be processed into molded products of various shapes such as BRIATO wiring boards, electronic component sealing materials, various connectors, thin-walled molded products, fibers, sheets, films, tubes, etc., and injection molding. Processing methods such as , compression molding, and extrusion molding are possible.Specific application fields include heat resistance, flame retardance, moldability, and impact resistance in the fields of industrial materials such as electricity, electronics, automobiles, and machinery. It can be widely used as an excellent molding material.

Examples of the present invention will be described in detail below. However, the present invention is not limited to this embodiment.

The tensile strength, elongation, impact strength, average dispersed particle diameter, and flame retardancy described in Examples and Comparative Examples were measured by the following methods.

(1> Tensile strength, elongation: Measured according to ASTM D638. (Unit: k
gf/cd) (2) Impact strength (notched eye shift impact strength): AS
Measured according to TM D256.

Note that the thickness of the test piece was 1/8 inch. (Unit: kgf - (2)/am) (3) Average dispersed particle diameter: After cutting out the center of the tensile test piece using a fruit clodome and creating an ultra-thin section sample, the dispersed components were determined from transmission electron micrographs. The particle size was measured. (Unit: μ-) (4) Flame retardancy: Measured according to the UL-94 vertical test method.

Note that the thickness of the test piece was 1/16 inch.

[Production method for polystyrene resin having epoxy groups] 216 g of styrene, 24 g of glycidyl methacrylate, 160 g of toluene and 2 g of azobisisobutyronitrile were placed in a separable flask equipped with a stirrer, and the mixture was heated at 25°C for 20
The mixture was uniformly mixed while bubbling nitrogen for a minute. After that, the separable flask was placed in an oil bath at 85°C, and after stirring at 85°C for 60 minutes in a nitrogen atmosphere, the temperature was further lowered to 1°C.
The temperature was raised to 05°C, and the reaction was stirred for 45 minutes.

After the reaction, the reaction polymerization solution was allowed to cool and was added dropwise to methanol under strong stirring and fractionated. After that, it is dried and the epoxy group is 6.86X.
A polystyrene resin ES-1 having an epoxy group of 10-'mol/g and a number average molecular weight of 11,600 was obtained.

The blending ratio of styrene monomer and glycidyl methacrylate was set to 95:5, and the epoxy group concentration was 3.45X.
A polystyrene resin ES-2 having an epoxy group of 10-' mol/g and a number average molecular weight of 52,900 was obtained.

[Manufacture of component (a)] As PPS, trade name Toprene T-4 manufactured by Toprene Co., Ltd.
(Melting point 295°C, melt viscosity 5600 poise) 90 parts by weight were melted at 300°C, 10 parts by weight of the polystyrene resin ES-1 having an epoxy group obtained above was added, and using a Prabender type mixer, The 0 reactant was reacted for 20 minutes while stirring and mixing uniformly in a nitrogen gas atmosphere. After cooling, the reactant was crushed, thoroughly washed with acetone, and dried to obtain the reaction product A.
-1 was obtained.

Product A-1 had a melting point of 281°C and a melt viscosity of 8800 poise.

A reaction product A-2 was obtained in the same manner using 95 parts by weight of Toublen T-4 (trade name) and 5 parts by weight of ES-1. Product A-2 had a melting point of 280°C and a melt viscosity of 10,000 voids.

80 parts by weight of product name Torblen T-4, 20 parts by weight of ES-2
Reaction product A-3 was obtained in the same manner as in parts by weight. Product A-3 had a melting point of 281°C and a melt viscosity of 3500 poise.

Note that the melting point is the peak temperature measured with a differential scanning calorimeter (DSC). Further, the melt viscosity was measured at a temperature of 300° C. and a shear rate of 120 sec-' using a Cabilograph 2B manufactured by Toyo Seiki Seisakusho ■.

[Production of component (b)] After replacing the inside of the reactor equipped with an oxygen blowing device, a cooling coil, and a stirrer with nitrogen gas, 3 cups of cupric bromide was added to the reactor.
2.2g of di-n-butylamine, 666g of di-n-butylamine, and 5.25kg of 2.6-xylenol dissolved in 241g of toluene were mixed and added, stirred and dissolved uniformly, and then stirred and stirred while rapidly blowing oxygen. Polymerization was carried out at ℃ for 90 minutes.

Then, toluene 1811 ethylenediaminetetraacetic acid 2
The polymerization reaction was stopped by adding 0% aqueous solution. A dissolved phase of polymerized raw bottom material was separated and obtained by centrifugation, and methanol was stirred and added to separate the polymerized product, which was dried to obtain PPE. The intrinsic viscosity [η] (measured as a chloroform solution at 30° C.) of the obtained PPH was 0.50.

Examples 1 to 5 A-1 obtained above, PPE, a flame retardant, and a flame retardant aid were blended in the proportions shown in Table 1, and a twin-screw kneader with a screw diameter of 30 m set at 300°C was used. Pellets were produced by melt-kneading. Using the obtained pellets, the molding temperature was 30
Injection molding was performed at 0°C and a mold temperature of 145°C to obtain test pieces for measuring physical properties. The measurement results of various properties are shown in Table 1.

Comparative Example 1 Using the above-mentioned product name Toprene T-4, pellets were produced by melt-kneading using a twin-screw kneader with a screw diameter of 30 mm set at 300°C in the same manner as in Example 1, and the physical properties were similarly measured. A test piece was prepared. The measurement results of various properties are shown in Table 1.

Comparative Example 2 The above-mentioned product name Torbren T-4 and the above-manufactured PPE
were mixed in the proportions shown in Table 1, and test pieces for measuring physical properties were prepared in the same manner as in Example 1. The measurement results of various properties are shown in Table 1.

Comparative Example 3 The above-mentioned trade name TOBLEN T-4, the above-produced styrene resin B5-1 having an epoxy group, and PPE were blended in the proportions shown in Table 1, and a test piece for measuring physical properties was prepared in the same manner as in Example 1. The creation was contested. The measurement results of various properties are shown in Table 1.

Comparative Example 4 A-1 produced above and PPE were blended in the proportions shown in Table 1, and a test piece for measuring physical properties was prepared in the same manner as in Example 1.

The measurement results of various properties are shown in Table 1.

Comparative Example 5 The above trade name Toprene T-4 and the PPE produced above
and Ebicuron 3050 (trade name, bisphenol A type epoxy resin manufactured by Dainippon Ink & Chemicals, Ltd.) in the proportions shown in Table 1, and test pieces for measuring physical properties were prepared in the same manner as in Example 1. The measurement results of various properties are shown in Table 1.

Examples 6 to 10 A-1, A-2, A-3 and PPE produced above,
Thermoplastic elastomers used as flame retardants and flame retardant aids include trade names of Toughtic M1913 and Tuffic H1041 (both styrene-ethylene-butylene-styrene block copolymers manufactured by Asahi Kaei) and glass fiber (C3-03- manufactured by Asahi Fiber Rail). MA-411> was blended in the proportions shown in Table 2, and test pieces for measuring physical properties were prepared in the same manner as in Example 1. Table 2 shows the measurement results of various properties.

Comparative Example 6.7 The above trade name TOBLEN T-4 and polyethylene terephthalate (hereinafter simply PET) as the thermoplastic polyester were used.
shall be. ) Trade name PET 5A-1205 (manufactured by Unitika ■), a flame retardant, and a flame retardant aid were blended in the proportions shown in Table 2, and test pieces for measuring physical properties were prepared in the same manner as in Example 1. The measurement results of various properties are shown in Table 2.

[Effects of the Invention] PPS and PPE to which costyrene resin has been added and one or more flame retardants selected from halogen-containing compounds, phosphorous elements or phosphorus compounds, or flame-retardant resins consisting of these flame retardants and flame retardant aids. The &l1rfc material has good flexibility such as elongation and impact strength without substantially impairing the strength and flame retardance of PPS resin, so it can be suitably used as a molding material, particularly for electrical and electronic parts.

Claims (2)

[Claims] (1) A resin composition consisting of (a) 40 to 98 parts by weight of polyphenylene sulfide added with a styrene resin, and (b) 60 to 2 parts by weight of a polyphenylene ether resin (a).
) + (b) 100 parts by weight of (c) one or more flame retardants selected from halogen-containing compounds and phosphorus compounds, or a mixture of these flame retardants and flame retardant aids from 0.01 to
A flame-retardant resin composition containing 40 parts by weight. (2) A flame-retardant resin composition comprising 1 to 60 parts by weight of (d) a thermoplastic elastomer to 100 parts by weight of the flame-retardant resin composition according to claim (1).