JP2000290450A - Flame retardant rubber-reinforcd styrene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having a low volatility and equipped with a high flame resistance, a good processabilty and mechanical characteristics simultaneously in a good balance by incorporating specific 3 kinds of resins and an aromatic phosphoric acid ester. SOLUTION: This objective composition is obtained by incorporating (A) 100 pts.wt. non-halogen-based rubber-reinforced styrene-based resin obtained by blending (i) a copolymer obtained by graft copolymerizing an aromatic vinyl compound and a vinyl monomer copolymerizable with it on a rubber-based polymer with (ii) a vinyl copolymer obtained from an aromatic vinyl compound and a vinyl monomer copolymerizable with it, (B) 5-20 pt.wt. non-halogen-based polyphenylene ether-based resin, (C) 3-35 pt.wt. aromatic phosphoric acid ester of the formula [R1 to R8 are each H or a lower alkyl and >=1 of R1 to R4 are each the lower alkyl; X is a bond, S, CO or the like; (n) is 0, 1; (m) is 0-5] and (D) 5-15 pt.wt. novolak type phenol resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel flame-retardant rubber-reinforced styrenic resin composition. For more information,
The present invention has good processability, can obtain a molded article having high flame retardancy and good mechanical properties, and has a corrosive property due to thermal decomposition of the resin composition during molding and combustion. The present invention relates to a non-halogen flame-retardant rubber-reinforced styrenic resin composition which does not generate toxic gas.

[0002]

2. Description of the Related Art Thermoplastic resins have excellent properties such as being relatively inexpensive to manufacture and easy to mold, and are used in various fields. In particular, ABS resins have excellent mechanical properties, heat resistance, workability, and the like, and are widely used in electric / electronic parts, automobile parts, and the like. However, thermoplastic resins are generally flammable, and use thereof requires a flame retarding treatment in which a flame retardant and a flame retardant aid are added to the thermoplastic resin. In recent years, with the diversification of uses of thermoplastic resins and the enlargement of molded products, higher performance (flame retardancy,
Mechanical properties, heat resistance, electrical insulation, etc.).

[0003] In order to impart flame retardancy to a thermoplastic resin, a method of adding a halogen-based flame retardant during preparation of a resin composition has been widely used. However, while this halogen-based flame retardant can impart flame retardancy to the resin, it thermally decomposes at the time of molding to generate hydrogen halide, and causes the metal parts of molding dies, molding machines, peripheral equipment, and electric and electronic parts to be formed. May corrode. Although a method of recovering such corrosive gas is conceivable, a special device is required. In addition, a large amount of smoke is generated at the time of combustion, and furthermore, hydrogen halide has toxicity, so that not only the working environment is deteriorated, but also the human body is adversely affected by the combustion. Therefore, in recent years, non-halogen flame retardants have been widely used as flame retardants.

[0004] Non-halogen flame retardants include magnesium hydroxide, aluminum hydroxide, calcium hydroxide,
Inorganic metal compounds such as basic magnesium carbonate have been used. In particular, magnesium hydroxide has been widely used in practice because of its high dehydration decomposition temperature and excellent smoke suppression effect during combustion. However, in order to obtain a sufficient flame-retardant effect, it is necessary to add a large amount thereof, thereby significantly lowering the intrinsic physical properties of the resin, particularly the mechanical properties.

[0005] Organic phosphorus compounds are widely used as non-halogen flame retardants other than inorganic metal compounds. Representative organic phosphorus compounds include trimethyl phosphate,
There are low molecular phosphate esters such as triphenyl phosphate. However, these low molecular phosphate esters have high volatility and volatilize during molding processing, and there is a problem that desired flame retardancy cannot be obtained.

JP-A-8-34926 discloses a flame-retardant resin composition containing a thermoplastic resin containing a combination of a polystyrene resin and a polyphenylene ether, a phosphorus compound, a silicon-containing compound and a phenolic polymer as essential components. The article describes that it has excellent flame retardancy. However, although the resin composition described in this publication is excellent in flame retardancy, mechanical properties, particularly impact resistance, are not always satisfactory.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and balances low volatility, high flame retardancy, good workability and mechanical properties (particularly impact resistance). An object of the present invention is to provide a flame-retardant rubber-reinforced styrenic resin composition which has both good properties and does not generate corrosive or toxic gas during molding and combustion.

[0008]

Means for Solving the Problems The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, a non-halogen rubber-reinforced styrene resin composed of a specific combination is added to a non-halogen polyphenylene ether resin and an aromatic resin. The combination of an aromatic phosphate ester and a novolak type phenol resin to obtain a resin composition having a high balance of high flame retardancy, good processability and mechanical properties, and the above resin composition It has been found that the impact resistance can be improved by further adding a thermoplastic elastomer to the product, and the present invention has been completed.

That is, according to the present invention, (A) (A
1) A copolymer obtained by graft copolymerizing an aromatic vinyl compound and a vinyl monomer copolymerizable therewith with a rubbery polymer, and (A2) an aromatic vinyl compound and a vinyl monomer copolymerizable therewith Non-halogen rubber-reinforced styrene resin blended with a vinyl copolymer consisting of
(B) a non-halogen polyphenylene ether resin,
(C) General formula (I):

[0010]

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Wherein R ^{1 to} R ⁸ are the same or different and are each a hydrogen atom or a lower alkyl group (provided that R ^{1 to} R ⁴
At least one is a lower alkyl group), X
Is a _{bond, -CH 2 -, - C (} CH 3) 2 -, - S -, -
SO ₂ —, —O—, —CO— or —NＮN—, where n is 0
Or 1, m is an integer of 0 to 5], and a flame-retardant rubber-reinforced styrene-based resin composition characterized by containing an aromatic phosphate represented by the formula (I) and (D) a novolak-type phenol resin. .

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The "non-halogen rubber-reinforced styrenic resin" of the component (A) used in the present invention is a resin containing no halogen atom and (A1)
A copolymer obtained by graft copolymerizing an aromatic vinyl compound (eg, styrene) and a vinyl monomer copolymerizable therewith (eg, acrylonitrile) with a rubbery polymer (eg, polybutadiene or styrene-butadiene copolymer rubber). It is a polymer blend obtained by blending a coalesced product with a vinyl copolymer (A2) comprising an aromatic vinyl compound and a vinyl monomer copolymerizable therewith.

As the "aromatic vinyl compound" in the component (A1) and the component (A2), for example, styrene, α
-Methylstyrene, paramethylstyrene and the like, among which styrene is particularly preferred.

The "vinyl monomer copolymerizable with the aromatic vinyl compound" in the component (A1) and the component (A2) includes, for example, alkyl (meth) acrylates such as methyl acrylate, ethyl acrylate and methyl methacrylate. (Meth) acrylic acid such as acrylic acid and methacrylic acid; vinyl cyanide monomer such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acid such as maleic anhydride; N-phenylmaleimide; Maleimide monomers such as (methylphenyl) maleimide, N-cyclohexylmaleimide and N-methylmaleimide; and glycidyl monomers such as glycidyl (meth) acrylate. Of these vinyl monomers, alkyl (meth) acrylates, vinyl cyanide monomers (especially acrylonitrile), and maleimide monomers (especially N-phenylmaleimide) are preferred.

The "rubber polymer" in the component (A1) means a polymer having rubber elasticity, and is not particularly limited as long as it has a glass transition temperature of 0 ° C. or lower. Specifically, diene rubbers such as polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber; acrylic rubbers such as polybutyl acrylate; polyisoprene, ethylene-propylene rubber, ethylene-propylene-diene Examples include block copolymers such as terpolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, and hydrogenated products thereof. Among these rubbery polymers, diene rubbers such as polybutadiene, styrene-butadiene copolymer rubber, and acrylonitrile-butadiene copolymer rubber are particularly preferred.

The proportion of the rubbery polymer in the graft copolymer of the component (A1) is preferably 30 to 95% by weight, and 50 to 90% by weight in terms of balance between impact resistance and processing fluidity. More preferred. Further, the proportion of the aromatic vinyl compound in the graft copolymer and the proportion of the graft component comprising a vinyl monomer copolymerizable therewith is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. When the proportion of the graft component is less than 5% by weight, the compatibility between the rubbery polymer and the matrix resin decreases, and the rubbery polymer aggregates to lower the surface gloss of the resin.
It is not preferable that the ratio exceeds the range, since it adversely affects the moldability of the resin composition.

Specific examples of the graft copolymer of the component (A1) include impact-resistant polystyrene, polystyrene, AB
S resin (acrylonitrile-butadiene-styrene terpolymer), AAS resin (acrylonitrile-acryl-styrene terpolymer) and AES resin (acrylonitrile-ethylenepropylene-styrene terpolymer), and the like, Above all, ABS resin is particularly preferred.

Specific examples of the vinyl copolymer of the component (A2) include polystyrene and an AS resin (acrylonitrile-styrene copolymer).
Resins are particularly preferred.

The ratio of the component (A1) to the component (A2) in the polymer blend of the component (A), that is, the non-halogen rubber-reinforced styrene resin is 25 to 25 by weight.
45: 75-55, preferably 30-40: 60-40
It is. When the blending ratio of the polymer blend is within the above range, a resin composition having excellent flame retardancy can be obtained.

The "non-halogen polyphenylene ether resin" of the component (B) used in the present invention may be any thermoplastic polyphenylene ether resin containing no halogen atom, and is not particularly limited. (Converted viscosity) η _sp / c (0.5 g / dl, chloroform solution, measured at 30 ° C) 0.2 to 0.7 dl / g is preferable.

Specific examples of the non-halogen polyphenylene ether-based resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), and poly (2,6-diethyl-1,4-phenylene ether). (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether) And 2,6-dimethylphenol and 2,3,
Copolymers containing 6-trimethylphenol as a component, and the like, among which 2,6-dimethylphenol and 2,3,6-
A copolymer containing trimethylphenol as a constituent component is preferred. Further, a copolymer obtained by grafting a styrene compound to the above-mentioned polyphenylene ether may be used.
Examples of the styrene compound used for the grafting include styrene, α-methylstyrene, vinyltoluene, and the like.

The "aromatic phosphate ester" of the component (C) used in the present invention is represented by the general formula (I):
It has a specific binding structure and a terminal structure. Here, the specific bonding structure means a bifunctional phenol residue, and the specific terminal structure means having at least one 2,6-dialkylphenol residue. As the bifunctional phenol, resorcin, hydroquinone, bisphenol A, bisphenol S and biphenol are preferred.
As the 6-dialkylphenol, 2,6-dimethylphenol is preferred.

The lower alkyl group of the substituents R ^{1 to} R ⁸ in the general formula (I) means an alkyl group having 1 to 6 carbon atoms, among which an alkyl group having 1 to 4 carbon atoms is preferable. , Methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl. The melting point of the aromatic phosphate is preferably 80 ° C. or higher from the viewpoint of heat resistance of the obtained resin composition.
C. or higher is particularly preferred.

The aromatic phosphate can be obtained by a known method. For example, at least one phenol compound in which the 2,6-position is substituted with an alkyl group (for example,
2,6-dimethylphenol) and phosphorus oxychloride (see Synthesis Example 6 of JP-A-9-291093), and 2,6-dimethylphenol is reacted with phosphorus oxychloride to form di (2,2-dimethylphenol). (6,6-dimethylphenyl) phosphorochloridate, followed by reaction with resorcin or hydroquinone (see JP-A-5-1079).

Specific examples of the aromatic phosphate ester include:
Tris phosphate (2,6-dimethylphenyl), tris phosphate (2,6-diethylphenyl), tris phosphate (2,6-di-n-
Propylphenyl), tris (2,6-diisopropylphenyl) phosphate, tris (2,6-di-n-butylphenyl) phosphate, tris (2,6-di-sec-butylphenyl) phosphate,
Tris (2,6-di-tert-butylphenyl) phosphate, tris [(2,3,6-, 2,4,6-) trimethylphenyl], tris [(2,3,6- , 2,4,6-) triethylphenyl]
And aromatic phosphate ester monomers such as tris phosphate ((2,3,6-, 2,4,6-) tri-n-propylphenyl),

Resorcinol bis [bis (2,6-dimethylphenyl) phosphate], resorcinol bis (2,6-dimethylphenyl) cresyl phosphate, resorcinol Bis [phosphoric acid (2,
6-dimethylphenyl) phenyl], hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], hydroquinonebis [(2,6-dimethylphenyl) cresyl phosphate],
Hydroquinone bis [bis (2,6-dimethylphenyl) phenyl phosphate], bisphenol A bis [bis (2,6-dimethylphenyl) phosphate], bisphenol A bis [(2,6-dimethylphenyl) cresyl phosphate] , Bisphenol A bis [(2,6-dimethylphenyl) phenyl phosphate], bisphenol S bis [bis (2,6-dimethylphenyl) phosphate], bisphenol S bis [phosphoric acid (2,
6-dimethylphenyl) cresyl], bisphenol S bis [(2,6-dimethylphenyl) phenyl phosphate], biphenol bis [bis (2,6-dimethylphenyl) phosphate], biphenol bis [phosphoric acid (2,6 -Dimethylphenyl) cresyl] and biphenol bis [phosphoric acid (2,
6-dimethylphenyl) phenyl] and the like.

[0027] Among the above aromatic phosphate esters, general formula (II):

[0028]

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Wherein R ^{9 to} R ¹² are the same or different and are a hydrogen atom or a lower alkyl group, and X, n and m have the same meanings as defined in formula (I).
It is particularly preferable because flame retardancy can be imparted without lowering the mechanical properties of the resin composition. In the formula, the lower alkyl group for the substituents R ^{9 to} R ¹² includes the substituent R ¹ in the general formula (I).
The same thing can be mentioned as to R ^8. Among the aromatic phosphates represented by the general formula (II), tris (2,6-dimethylphenyl) phosphate and the formula (III):

[0030]

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A compound represented by the formula (III) is preferred, and a compound represented by the formula (III) is particularly preferred.

The above-mentioned aromatic phosphate may be one kind or a mixture of two or more kinds. Further, the above aromatic phosphates have different physical properties such as acid value, hue, purity, heat resistance and hydrolysis resistance, and the performance required for a product obtained by molding the resin composition of the present invention. It is appropriately selected and used according to the characteristics and properties.

The novolak type phenol resin of the component (D) used in the present invention may be any one which forms a char when burned, and can be generally synthesized by a condensation reaction of a phenol compound and an aldehyde compound. Phenol compounds include phenol, o-cresol, m-cresol, p-cresol, 2,5-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl Phenol, p-tert-butylphenol, pn-octylphenol, p-phenoxyphenol, resorcinol, hydroquinone and the like. Examples of the aldehyde compound include formaldehyde and acetaldehyde.

Specific examples of the novolak type phenol resin include phenol formaldehyde novolak resin, cresol phenol formaldehyde novolak resin,
Xylenol phenol formaldehyde novolak resin, tert-butylphenol formaldehyde novolak resin, p-octylphenol formaldehyde novolak resin, nonylphenol formaldehyde novolak resin, resorcinol phenol formaldehyde novolak resin, bisphenol A formaldehyde novolak resin, and p-cyanophenol formaldehyde novolak resin, and their co-polymers And phenol formaldehyde novolak resin. The novolak type phenol resin has a weight average molecular weight of 300 to 10,000.
By using 0, it is possible to obtain a resin composition having excellent ability to form char during combustion.

The mixing ratio of each component of the resin composition of the present invention is as follows.
The amount is preferably 20 parts by weight, 5 to 35 parts by weight of the component (C) and 5 to 15 parts by weight of the component (D).

When the compounding amount of the non-halogen polyphenylene ether resin of the component (B) is within the above range, a resin composition having excellent flame retardancy can be obtained, but more preferably 7.5 to 7.5. 10 parts by weight.

The amount of the aromatic phosphate ester of the component (C) is determined by the type and amount of each component, particularly the component (D), according to the required flame retardancy of the resin composition.
In general, if the amount is less than 5 parts by weight, it is not preferable because sufficient flame retardancy cannot be obtained, and if it exceeds 35 parts by weight, the mechanical properties of a molded article of the resin composition deteriorate. However, it is not preferable because of poor practicality. Therefore, a more preferable blending amount is 10 to 25 parts by weight.

The amount of the novolak phenolic resin of the component (D) is determined by the type and amount of each component, particularly the component (C), according to the required flame retardancy and mechanical properties of the resin composition. Is done. In general, if the amount is less than 5 parts by weight, it is not preferable because sufficient flame retardancy cannot be obtained. If the amount exceeds 15 parts by weight, the mechanical properties of the resin composition molded article deteriorate. However, it is not preferable because of poor practicality. Therefore, a more preferable blending amount is 7.5 to 10.
Parts by weight.

In the present invention, it is possible to improve the mechanical properties, particularly impact resistance, of the obtained resin composition by further blending an impact strength modifier as a component (E) with the above resin composition. it can.

The "impact strength modifier" of the component (E) used in the present invention is also called a compatibilizer or an impact modifier, and enhances the compatibility of the matrix comprising the components (A) to (D). Improve impact strength. As the impact strength modifier, specifically, a vinyl group-containing silicone compound, a styrene-based thermoplastic elastomer which is a block copolymer composed of polystyrene, polybutadiene, and polyisoprene, a maleic acid-modified resin, a phenoxy resin, and a silicone And the like. Above all, a styrene-based thermoplastic elastomer is particularly preferable in terms of a compatibilizing effect of the matrix composed of the components (A) to (D) and a point that the mechanical properties of the resin composition can be favorably maintained.

As the styrene-based thermoplastic elastomer, polystyrene-polybutadiene-polystyrene (S
(BS type) thermoplastic elastomer, polystyrene-polyisoprene-polystyrene (SIS type) thermoplastic elastomer, polystyrene-poly (ethylene-butylene)
-Polystyrene (SEBS type) thermoplastic elastomer and polystyrene-poly (ethylene-propylene)-
Examples include a polystyrene (SEPS type) thermoplastic type elastomer, and among others, an SBS type styrene type thermoplastic type elastomer is particularly preferable.

The compounding amount of the impact strength modifier of the component (E) is as follows:
The type and amount of each component are determined according to the required mechanical properties of the resin composition.
3 to 30 parts by weight is appropriate for 00 parts by weight. If the amount of component (E) is less than 3 parts by weight, it is not preferable because sufficient impact strength cannot be obtained, and if it exceeds 30 parts by weight, sufficient flame retardancy cannot be obtained. Therefore, the compounding amount of the component (E) is 3 to 2
0 parts by weight is preferable, and 5 to 15 parts by weight is more preferable.

The resin composition of the present invention may contain an appropriate amount of at least one of various additives usually blended in a resin, as long as the physical properties are not impaired. Such additives include, for example, flame retardants and flame retardant auxiliaries other than the aromatic phosphate ester of component (C); antioxidants and stabilizers such as phenolic, amine and sulfur-based; mica, talc And inorganic fillers such as alumina;
Antistatic agents such as cationic and nonionic activators; reinforcing materials such as glass fibers, metal fibers and whiskers; benzophenone compounds, salicylate compounds,
UV absorbers and light stabilizers such as benzotriazole compounds and acrylonitrile compounds; lubricants such as fatty acid derivatives and high melting point waxes; softeners; pigments such as titanium oxide and phthalocyanine compounds.

Component (C) which may be added as an additive
Other flame retardants include trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, tri-sec-butyl phosphate, and tri-tert-phosphate phosphate. Butyl, tri-n-octyl phosphate, tri (2-ethylhexyl) phosphate, tridecyl phosphate, tristearyl phosphate;

Triphenyl phosphate, triphosphate [(o-,
m-, p-) methylphenyl], triphosphate [(o-, m-, p
-) Ethylphenyl], triphosphate [(o-, m-, p-) n-
Propylphenyl], tri [(o-, m-, p-) isopropylphenyl], tri [(o-, m-, p-) n-butylphenyl], tri [(o-, m-, p-) sec-butylphenyl], tri [(o-, m-, p-) tert-butylphenyl], tri [(o-, m-, p-) pentylphenyl], Tri [(o-, m-, p-) hexylphenyl], tri [(o-, m-, p-) heptylphenyl], tri [(o-, m-, p-) phosphate Octylphenyl], tri [(o-, m-, p-) nonylphenyl phosphate]
Tri [(o-, m-, p-) decylphenyl] phosphate;

Tris phosphate [(2,3-, 2,4-, 2,5-, 3,4
-, 3,5-) dimethylphenyl], trisphosphate [(2,3
-, 2,4-, 2,5-, 3,4-, 3,5-) diethylphenyl], trisphosphate ((2,3-, 2,4-, 2,5-, 3,4- , 3,5-) di-n-
Propylphenyl], trisphosphate [(2,3-, 2,4-, 2,
5-, 3,4-, 3,5-) diisopropylphenyl], tris [(2,3-, 2,4-, 2,5-, 3,4-, 3,5-) di-n -Butylphenyl], trisphosphate ((2,3-, 2,4-, 2,5-, 3,4
-, 3,5-) di-sec-butylphenyl], tris [(2,3-, 2,4-, 2,5-, 3,4-, 3,5-) di-tert-butyl Phenyl]; tris [(2,3,4-, 3,4,5-) trimethylphenyl], tris [(2,3,4-, 3,4,5-) triethylphenyl], phosphorus Tris acid [(2,3,4-, 3,4,5-)
Phosphate monomers such as tripropylphenyl] and cresyldiphenyl phosphate;

Further, alkylenebis [di (o-, m-, p-) phosphate, which is a condensate of these phosphate ester monomers,
Methylphenyl], resorcin bis [di-phosphate (o-, m
-, P-) methylphenyl], resorcin bis [di (o-, m-, p-) ethylphenyl], resorcin bis [bis (2,3-, 2,4-, 2,5-phosphate) , 3,4-, 3,5-) dimethylphenyl], hydroquinone bis [di (o-, m-, p-) phosphate
Methylphenyl], hydroquinone bis [phosphate di (o-,
m-, p-) ethylphenyl], hydroquinone bis [bis (2,3-, 2,4-, 2,5-, 3,4-, 3,5-) dimethylphenyl phosphate], bisphenol A bis [ Diphosphate (o-, m-, p-)
Methylphenyl], bisphenol A bis [di [(o-, m-, p-) ethylphenyl]], bisphenol A bis [bis [(2,3-, 2,4-, 2,5- , 3,4-, 3,5
-) Dimethylphenyl]], bisphenol S bis [di (o-, m-, p-) methylphenyl phosphate]] and bisphenol S bis [bis [(2,3-, 2,4-, 2, 5-, 3,
4-, 3,5-) dimethylphenyl]]

And phosphorus-based flame retardants such as red phosphorus and ammonium polyphosphate; inorganic flame retardants such as magnesium hydroxide, aluminum hydroxide, antimony oxide and titanium oxide; melam, melamine cyanurate, melamine phosphate and melamine resin, etc. And a flame retardant auxiliary such as a triazine skeleton-containing resin.

In the examples of the flame retardant other than the component (C), "(o-, m-, p-)" and "(2,3-, 2,4-, 2,5
-, 3,4-, 3,5-) "and the like each independently represent a substitution position on the benzene ring. For example, the notation containing "(o-, m-, p-)" means three compounds having a substituent at the ortho, meta or para position on the benzene ring.

The resin composition of the present invention comprises the components (A) to
It can be obtained by mixing (D), if necessary, component (E) and the above-mentioned various additives by a known method, and melt-kneading. For mixing and melt kneading, general-purpose devices such as a single-screw extruder, a twin-screw extruder such as a twin-screw extruder with a vent, a Henshall type mixer, a Banbury mixer, a kneader mixer and a roll may be used alone or in combination. it can. The obtained resin composition is further processed by a known method (for example, injection molding) to obtain a desired shape, for example, a plate-like, sheet-like or film-like molded product.

[0051]

The present invention will be described more specifically with reference to the following examples, which do not limit the scope of the present invention.

The components used in the examples and comparative examples are shown below with their abbreviations. Component (A) [Polymer blend of component (A1) and component (A2)] (a) [ABS of component (a1) and A of component (a2)
Polymer blend in which S resin is blended at a weight ratio of 35:65] Component (B) (b) Polyphenylene ether resin Nippon GE Plastics Co., Ltd. Product name: Noryl PPO-640 Component (C) (c) The following formula ( III) Aromatic phosphate compound, melting point 95 ° C, manufactured by Daihachi Chemical Industry Co., Ltd. Product name: PX-200

[0053]

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Component (D) (d) Phenol formaldehyde novolak resin Arakawa Chemical Industry Co., Ltd. Product name: Tamanol-759 Component (E) (e) SBS type styrene-based thermoplastic elastomer Shell Japan Co., Ltd. Product name: Clayton D -KX408CP

Examples 1-2 The resin compositions were blended in the components and blending ratios (parts by weight) shown in Table 1, and mixed with a Henschel mixer (trade name: Super Mixer SMV-20, manufactured by Kawata Corporation). , Vented twin screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM
-37BS) to obtain a pelletized resin composition. Each of the obtained resin compositions was molded by an injection molding machine (SAV-60-52, manufactured by Yamashiro Seiki Co., Ltd.) to obtain samples for a flame retardancy (combustibility) test and a mechanical property measurement, respectively.

[0056]

[Table 1]

The physical properties of these samples were evaluated by the following methods. (Flame Retardancy) (1) Flame Retardancy (UL) Vertical Flammability Complies with UL94 / V test method V-0, V-1, and V
-2 standards, and those outside the standards are referred to as HB. (Mechanical properties) (2) Izod (Izod impact strength, kgf · cm /
cm ² ) According to JIS K-7110 test method

(Overall Evaluation) Based on the results of the above (1) and (2), the resin compositions were classified into the following ranks. "◎": UL is V-1 standard and Izod is 10k
gf · cm / cm ² or more “O”: UL is V-1 standard and Izod is 10k
Less than gf · cm / cm ² “x”: UL is less than V-1 standard and Izod is 1
Those of less than 0 kgf · cm / cm ² Table 1 shows the evaluation results of the obtained resin compositions.

Comparative Example 1 A sample was obtained in the same manner as in Examples 1 and 2, except that the resin composition was blended in the components and blending ratios shown in Table 1. Each physical property of the obtained resin composition was evaluated in the same manner as in the examples. Table 1 shows the evaluation results of the obtained resin compositions.

[0060]

The resin composition of the present invention maintains excellent mechanical properties inherent in rubber-reinforced styrenic resins while maintaining excellent mechanical properties.
A resin composition exhibiting a high flame retardant effect of V-1 in UL standard can be provided. Further, since the resin composition of the present invention does not contain a halogen element, even under combustion or high temperature conditions, there is no generation of corrosive or toxic halogen-containing gas, and there is also a problem of corrosion of equipment and adverse effects on human bodies. And can be used as various industrial materials such as OA equipment and home electric parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/12 C08L 71/12

Claims (6)

[Claims] (A1) (A1) an aromatic vinyl compound and a copolymer obtained by graft copolymerizing a vinyl monomer copolymerizable therewith with a rubbery polymer; (A2) an aromatic vinyl compound; A non-halogen rubber-reinforced styrene resin blended with a vinyl copolymer comprising a copolymerizable vinyl monomer and a vinyl copolymer; (B) a non-halogen polyphenylene ether resin; (C) a general formula (I) ): Wherein R ^{1 to} R ⁸ are the same or different and are a hydrogen atom or a lower alkyl group (provided that at least one of R ^{1 to} R ⁴ is a lower alkyl group), X is a bond,-
_{CH 2 -, - C (CH} 3) 2 -, - S -, - SO 2 -, -
O-, -CO- or -N = N-, n is 0 or 1, m
Is an integer of 0 to 5], and (D) a novolak-type phenol resin. 2. The resin composition according to claim 1, wherein the component (B) is blended in an amount of 5 to 20 parts by weight based on 100 parts by weight of the component (A). 3. Component (A1) and component (A) of component (A)
The resin composition according to claim 1, wherein 2) is blended in a weight ratio of 25 to 45:75 to 55. 4. 4. The resin composition according to claim 1, wherein the resin composition further comprises an impact strength modifier as component (E). 5. The resin composition according to claim 4, wherein the component (E) is a styrene-based thermoplastic elastomer. 6. The resin composition according to claim 4, wherein component (E) is blended in an amount of 3 to 20 parts by weight based on 100 parts by weight of component (A).