JPH115879A - Fluororesin-containing dripping type flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a styrene-based resin composition containing a fluororesin and having dripping-type flame retardancy. SOLUTION: This resin composition comprises 100 pts.wt. of a resin component composed of (A) 1-99 pts.wt. of a styrene-based resin and (B) 99-1 pts.wt. of polyphenylene ether, (C) 1-100 pts.wt. of a flame retardant (in particular, an aromatic phosphoric ester) and (D) 0.001-0.09 pt.wt. of a fluororesin, and as necessary, (E) 0.1-50 pts.wt. of a novolak resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition containing a fluororesin. More specifically, the present invention relates to a styrene-based resin composition containing a fluorine-based resin and having dripping flame retardancy.

[0002]

2. Description of the Related Art Styrene-based resins are excellent in impact resistance in addition to excellent moldability.
Although it is used in various fields such as home electric appliance parts and OA equipment parts, its use is limited due to the flammability of styrene resins.

[0003] As a method of making a styrene resin flame-retardant,
It is known to add a halogen-based, phosphorus-based, or inorganic flame retardant to a thermoplastic resin, thereby achieving some degree of flame retardancy. However, in recent years, the demands for fire safety have been noticeably highlighted,
US UL (Underwriters Laboratories) vertical method combustion test regulations for OA equipment have become stricter over the years, and products and parts have become thinner to reduce weight and improve economics. Thus, the fire drops when burning, which may damage other products and parts, and there is a strong demand for the development of a technique for preventing the spread of fire due to the drop of the fire. As a technique for preventing the spread of fire from dropping fire, a method of increasing the amount of flame retardant is known.However, using a large amount of expensive flame retardant is not only economical but also causes environmental problems and lowers mechanical properties. Is not preferred to promote

[0004] As a conventional technique for preventing the spread of fire from dropping fire, there is disclosed a technique in which polytetrafluoroethylene (PTFE) is blended with a styrene resin and / or polyphenylene ether together with a flame retardant (US Patent No. 410723).
2, 4332714, 4355126). Since the above-mentioned publication is a flame-retardant composition having no dripping of fire, PTFE is used.
Is usually added in an amount of 0.1 part by weight or more based on 100 parts by weight of the resin component. For this reason, excessive fibrillation proceeds during the production of the resin composition, or melt extrusion becomes unstable,
There is a problem that appearance and fluidity are reduced. Japanese Unexamined Patent Publication No. Hei 8-225357 discloses PTFE, "It is difficult to mix and melt-mix a pure additive in a PPE resin composition using a commercially available processing apparatus. For example, an extruder The operability is poor, for example, the PTFE adheres to the flight of the screw. In addition, PTFE remains as an unmelted white point in the resin composition. "

The inventor of the present invention has overcome the above-described problems by suppressing the spread of fire due to a dropped fire by delaying the dropping of the fire with a specific amount of PTFE. This fact is not disclosed or even implied in the above four publications.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention does not have the above-mentioned problems, that is, it prevents the spread of fire due to the dripping of molten metal during combustion, and provides flame retardancy, appearance and impact resistance. It is an object of the present invention to provide a styrene resin composition having excellent heat resistance and fluidity.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on preventing the spread of fire by melting and dropping during the burning of a styrene-based resin composition. As a result, the polystyrene-based resin, the flame retardant, It has been surprisingly found that the addition of a fluorine-based resin dramatically improves the fluidity and appearance while preventing fire retardancy, especially fire spread due to molten dropping, and completed the present invention.

That is, the present invention relates to (A) a styrene resin 1
To 99 parts by weight, (B) polyphenylene ether 99 to 1
With respect to 100 parts by weight of the resin component consisting of parts by weight, (C)
1 to 100 parts by weight of flame retardant, (D) fluorinated resin 0.00
1 to 0.09 parts by weight of a fluororesin-containing drop-type flame-retardant resin composition, particularly (C) the flame-retardant is an aromatic phosphate ester, and if necessary, (E) novolak resin 0.1 to An object of the present invention is to provide a fluororesin-containing dripping type flame retardant resin composition containing 50 parts by weight.

Hereinafter, the present invention will be described in detail.

The present invention relates to (A) a styrenic resin, (B)
It is a drop-type flame-retardant resin composition comprising polyphenylene ether, (C) a flame retardant, and (D) a fluororesin.

The above (A) and (B) are the main components of the molding resin composition and play a role in maintaining the strength of the molded article, and (C) is a component for imparting flame retardancy to the resin component. , (D)
Is a component for suppressing the spread of fire due to the dropped fire by delaying the drop of the fire.

Here, (D) is 0.001 to 0.09 with respect to 100 parts by weight of the resin component composed of (A) and (B).
It is important to be in the range of parts by weight. (D) is 0.0
If the amount is less than 01 parts by weight, there is no effect of delaying the dropping of the fire, and the fire drops at the beginning of combustion and the fire spreads. On the other hand, (D) is 0.0
If it exceeds 9, it has been found that not only the melt viscosity of the resin is increased and the fluidity is reduced, but also the appearance is reduced due to excessive (D) fibrils, thereby completing the present invention.

In the present invention, the styrene resin (A) is a rubber-modified styrene resin and / or a non-rubber-modified styrene resin, particularly a rubber-modified styrene resin alone or a rubber-modified styrene resin and a rubber-unmodified styrene resin. It is preferable that the resin is made of a resin and is not particularly limited as long as it is compatible with or homogeneously dispersed with (B) to (D). The rubber-modified styrenic resin refers to a polymer in which a rubbery polymer is dispersed in a matrix in a matrix composed of a vinyl aromatic polymer, and an aromatic vinyl monomer is present in the presence of the rubbery polymer. The monomer and, if necessary, a vinyl monomer copolymerizable therewith, are added, and the monomer mixture is obtained by known polymerization methods such as bulk polymerization, emulsion polymerization, and suspension polymerization.

Examples of such resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acryl rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene copolymer). Propylene rubber-styrene copolymer).

The rubbery polymer must have a glass transition temperature (Tg) of -30 ° C. or less,
If the temperature exceeds -30 ° C, the impact resistance decreases.

Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene) and the like, saturated rubber obtained by hydrogenating the above diene rubber, isoprene rubber, chloroprene rubber. , An acrylic rubber such as polybutyl acrylate, and an ethylene-propylene-diene monomer terpolymer (EPDM). A diene rubber is particularly preferred.

The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or the like. Yes, styrene is most preferred, but other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as components of the rubber-modified styrenic resin in (A). When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

If it is necessary to lower the melt viscosity during blending, an acrylate comprising an alkyl group having 1 to 8 carbon atoms can be used. Further, when it is necessary to further increase the heat resistance of the resin composition, α-methylstyrene, acrylic acid, methacrylic acid,
Monomers such as maleic anhydride and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is from 0 to 40.
% By weight.

The rubbery polymer in the rubber-modified styrenic resin is preferably 5 to 80% by weight, particularly preferably 1 to 80% by weight.
0 to 50% by weight, a graft-polymerizable monomer mixture,
Preferably 95 to 20% by weight, more preferably 90 to 5% by weight.
It is in the range of 0% by weight. Within this range, the balance between impact resistance and rigidity of the target resin composition is improved. Further, the rubber particle diameter of the styrene-based polymer is 0.1 to 5.0.
μm is preferred, and 0.2 to 3.0 μm is particularly preferred. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / c of the resin portion, which is a measure of the molecular weight of the rubber-modified styrenic resin (0.5 g / dl,
30 ° C. measurement: toluene solution when the matrix resin is polystyrene, methyl ethyl ketone when the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer)
It is preferably in the range of 0.30 to 0.80 dl / g, and more preferably in the range of 0.40 to 0.60 dl / g. Reduced viscosity ηsp of rubber-modified styrenic resin
Means for satisfying the above requirement regarding / c include adjustment of the amount of polymerization initiator, polymerization temperature, and amount of chain transfer agent.

In the present invention, (B) the polyphenylene ether is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula (1).

[0023]

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(However, R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of hydrogen, hydrocarbon and substituted hydrocarbon groups, and may be the same or different. Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Preferred, especially poly (2,6-dimethyl-1,4-phenylene ether)
Is preferred. The method for producing the polyphenylene ether is not particularly limited. For example, a complex of a cuprous salt and an amine according to the method described in US Pat. No. 3,306,874 is used as a catalyst, and for example, 2,6-xylenol Can be easily produced by oxidative polymerization, and in addition, U.S. Patent No. 3,306,875, U.S. Patent No. 3,257,357, U.S. Patent No. 3,257,358, and 52-1
It can be easily produced by the methods described in JP-A-7880 and JP-A-50-51197. The reduced viscosity ηsp / c of the polyphenylene ether used in the present invention (0.5
g / dl, chloroform solution, measured at 30 ° C) is 0.2
It is preferably in the range of 0 to 0.70 dl / g,
More preferably, it is in the range of 0.30 to 0.60 dl / g. Reduced viscosity ηsp / c of polyphenylene ether
Means for satisfying the above requirements include adjustment of the amount of catalyst in the production of the polyphenylene ether.

In the present invention, the amount of (B) occupies 1 to 100 parts by weight of the resin component comprising (A) and (B).
99% by weight, preferably 1 to 50% by weight, more preferably 3 to 40% by weight, and most preferably 5 to 25% by weight.
% By weight.

The flame retardant used as (C) in the present invention is a halogen-based, phosphorus-based or inorganic flame retardant.

The halogen-based flame retardant (C) is as follows:
Halogenated bisphenols, aromatic halogen compounds, halogenated polycarbonates, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenylene ethers, and the like, preferably decabromodiphenyl oxide, tetrabromobisphenol A, tetrabromo Oligomer of bisphenol A, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, brominated polystyrene,
Brominated cross-linked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, halogen-containing phosphoric acid ester, fluorine resin and the like.

As the phosphorus-based flame retardant in the above (C),
Organic phosphorus compounds, red phosphorus, inorganic phosphates and the like can be mentioned.

Examples of the organic phosphorus compound include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate, phosphite and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrocatechol hypopositive phosphate.

Here, as the organic phosphorus compound, an aromatic phosphate ester monomer represented by the following formula (2) and an aromatic phosphate ester condensate represented by the following formula (3) are particularly preferred.

[0031]

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[0032]

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(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , A
r ₅ and Ar ₆ represent a phenyl group, a xyenyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group,
An aromatic group selected from 4,4'-dioxydiarylalkane groups. N represents an integer of 0 to 3;
Represents an integer of 1 or more. Among the above aromatic phosphate ester monomers, one or two or more phenols may be used, particularly, in a hydroxyl group-containing aromatic phosphate ester monomer, for example, tricresyl phosphate or triphenyl phosphate. Phosphoric acid ester monomer containing a hydroxyl group, or the following formula (4)
Are preferred.

[0034]

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(Where a, b, and c are from 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or an alkyl group having 1 to 30 carbon atoms, and the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 12 to 30 on average as the whole compound. Here, when it comprises a plurality of aromatic phosphates having different substituents, the total number of carbon atoms of the substituents R ¹ , R ² , R ³ of the flame retardant is represented by a number average, It is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituent of each component. In the present invention, among the aromatic phosphate ester monomers, the number average of the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 1
5-30 are preferable, and 20-30 are more preferable,
25 to 30 are most preferred.

Specific substituents include butyl such as nonyl, t-butyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, decyl, undecyl, dodecyl and tridecyl. Pentadecyl group, pentadecyl group, hexadecyl group, heptadecyl group, otadecyl group, nonadecyl group, octadodecyl group and the like.
It can be produced by a known method disclosed in, for example, JP-A-294284. For example, there is a method of reacting an alkylphenol, phosphorus oxychloride, and anhydrous aluminum chloride as a catalyst under heating, or a method of oxidizing a phosphite triester with oxygen to convert it to a corresponding aromatic phosphate.

Among the aromatic phosphate ester condensates, bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate) and the like are particularly preferable.

Another preferred aromatic phosphate condensate used as (C) in the present invention is represented by the following formula (5).

[0039]

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(Where a, b, c, d, and e are 0 to 3, R ¹ to R ⁵ are hydrocarbons having 1 to 10 carbon atoms, and n represents an integer of 1 to 3) The flame retardant is particularly preferably a condensate of an aromatic phosphate ester substituted at the 2,6-position, and can be produced by a known method disclosed in JP-A-5-1079. For example, a monofunctional phenol substituted at the 2,6-position is reacted with phosphorus oxyhalide in the presence of a Lewis acid catalyst to obtain a diaryl phosphorohalide, which is then reacted with a bifunctional phenol in the presence of a Lewis acid catalyst. There is a way to react.

In the above (C), red phosphorus, which is one of the phosphorus-based flame retardants, is obtained by preliminarily selecting the surface of aluminum hydroxide, magnesium hydroxide, zinc hydroxide or titanium hydroxide in addition to general red phosphorus. Coated with a metal hydroxide coating, coated with a coating composed of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, and a thermosetting resin , Aluminum hydroxide, magnesium hydroxide,
Examples thereof include those obtained by double-coating a thermosetting resin film on a metal hydroxide film selected from zinc hydroxide and titanium hydroxide.

In the above (C), one of the inorganic phosphates of the phosphorus-based flame retardant is typically ammonium polyphosphate.

The inorganic flame retardant (C) includes aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, and tin oxide. And hydrates of inorganic metal compounds such as hydrates of, for example, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, and barium carbonate. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite have particularly good flame retardant effects and are economically advantageous.

In the present invention, the amount of (C) added is
(A) With respect to 100 parts by weight of the resin component composed of (B),
1 to 100 parts by weight, preferably 1 to 50 parts by weight,
More preferably, 3 to 20 parts by weight, most preferably 5
１５15 parts by weight.

In the present invention, the fluororesin used as (D) is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene,
Polydifluoroethylene, polytrifluoroethylene,
Examples thereof include polytetrafluoroethylene and a tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.

The method for producing these fluororesins is described in US Pat. No. 2,393,697 and US Pat.
No. 534,058, for example, using tetrafluoroethylene in an aqueous medium with a radical initiator such as ammonium persulfate and potassium persulfate in an amount of 7 to 70 kg.
The polymerization is carried out at a temperature of from 0 to 200 ° C. under a pressure of / cm ² and then a polytetrafluoroethylene powder is obtained by coagulation from a suspension, dispersion or emulsion or by precipitation.

Here, it is preferable to perform the melting and kneading at a temperature higher than the melting point of the fluororesin. For example, in the case of polytetrafluoroethylene, it is preferable to melt in a temperature range of 300 to 350 ° C. Under the shearing force, by melting at a temperature higher than the melting point, the fibers are highly fibrillated and oriented and crystallized. And
A fluorine-based resin having a special higher-order structure in which the fluorine-based resin is branched from the trunk fiber can be obtained. As a result, it is three-dimensionally entangled with the thermoplastic resin and suppresses the melting of the molded article. Further, in order to impart a high shear force, it is preferable to melt in a hard resin having a high melt viscosity such as polyphenylene ether, rather than a rubber-modified resin (for example, rubber-modified polystyrene).

The method for producing the above-mentioned fluororesin having a special higher-order structure is to prepare a masterbatch by melting and kneading a fluororesin, a thermoplastic resin and, if necessary, a dispersant at a temperature higher than the melting point of the fluororesin. Then, using a two-stage process method of melt-kneading the thermoplastic resin and flame retardant, or using an extruder consisting of two zones capable of side feeding, the thermoplastic resin and the fluorine-based resin and the dispersant if necessary Is melt-kneaded at a temperature equal to or higher than the melting point of the fluororesin, and the melting temperature is lowered in the subsequent stage to feed the flame retardant and melt-knead, for example, a one-step process method.

In the present invention, in particular, when further improvement in flame retardancy and heat resistance is required, (E) a novolak resin can be blended. When (E) is used in combination with an aromatic phosphate, it is also an agent for improving fluidity and heat resistance, and slightly lowers the compatibility between the resin component and the aromatic phosphate. The resin is a thermoplastic resin obtained by condensing phenols and aldehydes in the presence of an acid catalyst such as sulfuric acid or hydrochloric acid. Polyaddition ”p.437-
455 (Kyoritsu Shuppan Co., Ltd.) ".

An example of the production of a novolak resin is shown in the following formulas (6) and (7).

[0051]

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The above phenols include phenol, o-cresol, m-cresol, p-cresol, 2,5-
Dimethyl-, 3,5-dimethyl-, 2,3,5-trimethyl-, 3,4,5-trimethyl-, pt-butyl-, pn-octyl-, p-stearyl-, p-phenyl -, P- (2-phenylethyl)-, o-isopropyl-, p-isopropyl-, m-isopropyl-, p
-Methoxy- and p-phenoxyphenol, pyrocatechol, resorcinol, hydroquinone, salicylaldehyde, salicylic acid, p-hydroxybenzoic acid, methyl p-hydroxybenzoate, p-cyano-, and o-cyanophenol, p-hydroxybenzene Sulfonic acid, p-hydroxybenzenesulfonamide, cyclohexyl p-hydroxybenzenesulfonate, 4-
Hydroxyphenylphenylphosphinic acid, methyl 4
-Hydroxyphenylphenylphosphinate, 4-hydroxyphenylphosphonic acid, ethyl 4-hydroxyphenylphosphonate, diphenyl 4-hydroxyphenylphosphonate and the like.

The aldehydes include formaldehyde,
Acetaldehyde, n-propanal, n-butanal, isopropanal, isobutyraldehyde, 3-methyl-n-butanal, benzaldehyde, p-tolylaldehyde, 2-phenylacetaldehyde and the like.

In the present invention, if necessary, one or more compounds selected from saturated higher aliphatic carboxylic acids or metal salts thereof, carboxylic acid ester waxes, organosiloxane waxes, polyolefin waxes and polycaprolactone And (F) a release agent.

Among the above (F), one or more compounds selected from saturated higher aliphatic carboxylic acids and metal salts thereof are preferred.

The carboxylic acid of the saturated higher fatty acid is preferably a straight-chain saturated monocarboxylic acid having 12 to 42 carbon atoms. For example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid and the like can be mentioned. Examples of the metal of these metal salts include lithium, sodium, potassium, magnesium, calcium, aluminum, zinc and the like, and particularly preferred are zinc stearate, magnesium stearate, calcium stearate, and aluminum stearate.

The amount of (F) is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin component composed of (A) and (B). Preferably, it is 0.3 to 1 part by weight.

In the present invention, if necessary, one or more flame retardant aids (G) selected from triazine skeleton-containing compounds, metal-containing compounds, silicone resins, silicone oils, silica, aramid fibers, and polyacrylonitrile fibers are blended. can do.

The amount of (G) is preferably from 0.001 to 4 based on 100 parts by weight of the resin component (A) and (B).
0 parts by weight, more preferably 1 to 20 parts by weight, most preferably 5 to 10 parts by weight.

The compound having a triazine skeleton as (G) is a component for further improving the flame retardancy as a flame retardant aid of a phosphorus-based flame retardant. Specific examples thereof include melamine, melam represented by the following formula (8), melem represented by the following formula (9), melon (a product obtained by deammonating three to three molecules of melem at 600 ° C. or higher), and the following formula: (1
0) Melamine cyanurate represented by the following formula (11)
Melamine phosphate, succinoguanamine, adipoguanamine, methylglutalogamine represented by the following formula (12), melamine resin represented by the following formula (13), BT resin represented by the following formula (14), etc. Although melamine cyanurate is particularly preferable from the viewpoint of low volatility.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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The metal-containing compound as (G) is a metal oxide and / or metal powder. The metal oxide is aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide,
It is a simple substance such as tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, or a composite (alloy) thereof, and the metal powder is aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, It is a simple substance of chromium, nickel, copper, tungsten, tin, antimony or the like, or a composite thereof.

The silicone resin (G) is made of SiO
₂ , a silicone resin having a three-dimensional network structure formed by combining structural units of RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. Here, a silicone resin containing a vinyl group is particularly preferable.

Such a silicone resin can be obtained by co-hydrolyzing and polymerizing an organohalosilane corresponding to the above structural unit.

The silicone oil as (G) is a polydiorganosiloxane, particularly preferably a vinyl-containing silicone oil, and comprises a chemical bond unit represented by the following formula (15).

[0072]

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R in the above formula is a C1-8 alkyl group, C
It is one or more substituents selected from aryl groups of 6 to 13 and vinyl-containing groups represented by the following formulas (16) and (17), and particularly contains a vinyl group in the molecule.

[0074]

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[0075]

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The vinyl-containing silicone oil has a viscosity of 600 to 1,000,000 centistokes (25
C.), more preferably 90000 to 150 ° C.
000 centistokes (25 ° C.).

The silica as (G) is an amorphous silicon dioxide, particularly preferably a silica coated with a hydrocarbon compound, the surface of which is treated with a hydrocarbon compound silane coupling agent. The hydrocarbon compound-coated silica contained is preferred.

The silane coupling agent may be a vinyl such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Group-containing silane, epoxy silane such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N
Aminosilane such as -phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit similar in structure to the thermoplastic resin is particularly preferable. For example, p-styryltrimethoxysilane is preferable for a styrene-based resin.

The treatment of the silica surface with the silane coupling agent is roughly classified into a wet method and a dry method. The wet method is a method in which silica is treated in a silane coupling agent solution and then dried.The dry method is a method in which silica is charged into a high-speed stirring device such as a Henschel mixer and stirred. This is a method in which a silane coupling agent solution is slowly dropped while performing a heat treatment.

The aramid fiber as (G) preferably has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. Isophthalamide or polyparaphenylene terephthalamide is converted to an amide polar solvent or sulfuric acid. And solution spinning by a wet or dry method.

The polyacrylonitrile fiber (G) has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 500 μm.
It is preferably 10 mm, and the polymer is dissolved in a solvent such as dimethylformamide and the like, and dry spinning is performed by dry spinning in an air stream at 400 ° C., or wet spinning is performed by dissolving the polymer in a solvent such as nitric acid and wet spinning in water. It is manufactured by the method.

In the present invention, if necessary, a copolymer resin comprising an aromatic vinyl unit and an acrylic ester unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic alcohol, or a metal One or two or more fluidity improvers (H) selected from soaps can be blended.

The amount of (H) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the resin component composed of (A) and (B). Preferably, it is 1 to 5 parts by weight.

The aromatic vinyl unit of the copolymer resin as (H) is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene And the like, and styrene is most preferred, but the above-mentioned other aromatic vinyl monomer may be copolymerized mainly with styrene. The acrylate unit is an acrylate ester having an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate and butyl acrylate.

Here, the content of the acrylate unit in the copolymer resin is preferably 3 to 40% by weight.
5-20% by weight is preferred. Also, the solution viscosity (MEK of 10% by weight of resin) which is an index of the molecular weight of the copolymer resin is used.
(Solution, measurement temperature 25 ° C.) is preferably 2 to 10 cP (centipoise). If the solution viscosity is less than 2 cP, the impact strength decreases, while if it exceeds 10 cP, the effect of improving the fluidity decreases.

The aliphatic hydrocarbon-based processing aid as (H) includes liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, or fluorides and chlorides.

The higher fatty acids as (H) include saturated fatty acids other than those described in the section of (F) mold release agent, and unsaturated fatty acids such as ricinoleic acid, ricinberidic acid and 9-oxy-12-octadecenoic acid. It is.

The higher fatty acid ester as (H) is a monohydric alcohol ester of a fatty acid such as methyl phenylstearate or butyl phenylstearate, or a monohydric alcohol ester of a polybasic acid such as diester of phthalic acid of diphenylstearyl phthalate. And sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, sorbitan triolate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate , Sorbitan esters such as polyoxyethylene sorbitan monooleate, monoglyceride stearate,
Fatty acid esters of glycerin monomers such as oleic acid monoglyceride, capric acid monoglyceride, behenic acid monoglyceride, polyglycerin fatty acid esters such as polyglycerin stearate, polyglycerin oleate, polyglycerin laurate, and polyoxyethylene mono Fatty acid esters having a polyalkylene ether unit such as laurate, polyoxyethylene monostearate and polyoxyethylene monooleate; and neopentyl polyol fatty acid esters such as neopentyl polyol distearate.

The higher fatty acid amides as (H) include monoamides of saturated fatty acids such as phenylstearic acid amide, methylolstearic acid amide, methylolbehenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, and coconut oil fatty acid diethanolamide. And N, N′-substituted monoamides such as oleic acid diethanolamide and the like.
Saturated fatty acid bisamides such as (hydroxyphenyl) stearamide, ethylenebis (stearic acid amide), ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-hydroxyphenyl) stearic acid amide, and m-xylylenebis (12
-Hydroxyphenyl) stearic acid amide and the like.

The higher aliphatic alcohol as (H) is
Monohydric alcohols such as stearyl alcohol and cetyl alcohol; polyhydric alcohols such as sorbitol and mannitol; and polyoxyethylene dodecylamine and polyoxyethylene bactadecylamine. Allylated ethers having an alkylene ether unit, polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene Polyoxyethylene alkyl phenyl ether such as ethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether;
Polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A
It is a dihydric alcohol having a polyalkylene ether unit such as ether or polyoxyethylene polyoxypropylene glycol ether.

The metal soap as (H) is a metal salt of a higher fatty acid such as stearic acid described above, such as barium, calcium, zinc, aluminum or magnesium.

In the present invention, a thermoplastic elastomer (I) can be blended, if necessary, such as a polystyrene-based, polyolefin-based, polyester-based, polyurethane-based, 1,2-polybutadiene-based, or polyvinyl chloride-based. And the like, and a polystyrene-based thermoplastic elastomer is particularly preferable.

The amount of (I) is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, and most preferably 100 parts by weight of the resin component (A) and (B). , 2 to 5 parts by weight.

The above-mentioned polystyrene-based thermoplastic elastomer is a block copolymer composed of an aromatic vinyl unit and a conjugated diene unit, or a block copolymer in which the conjugated diene unit is partially hydrogenated.

The aromatic vinyl monomer constituting the block copolymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromobenzene. Styrene is the most preferable, and styrene is most preferable. However, other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

The conjugated diene monomer constituting the block copolymer includes 1,3-butadiene, isoprene and the like.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or a partially hydrogenated unit thereof is represented by B. When displaying with,
SB, S (BS) n (where n is an integer of 1 to 3), S
(BSB) n, where n is an integer of 1 to 2
A block copolymer or (SB) nX (where n is 3 to 6)
Integer. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound. It is preferable to use a star-shaped (star) block copolymer having a B-part as a bonding center. Above all, SB type 2 and SBS 3
And SBSB type 4 linear block copolymers are preferred.

In the present invention, when light resistance is required, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, a halogen scavenger, a light shielding agent, a metal deactivator, or a quencher may be used, if necessary. One or more lightfastness improvers (J) selected from agents can be blended.

The amount of (J) is preferably 0.05 to 20 parts by weight per 100 parts by weight of the resin component comprising (A) and (B).
Parts by weight, more preferably 0.1 to 10 parts by weight, most preferably 1 to 5 parts by weight.

The method for producing the resin composition of the present invention includes:
(A) First, the styrene resin and (B) are melted,
After adding (C) and (D) and melt-kneading with the same extruder, or (A) after producing a styrene-based resin, (B) or, if necessary, a master batch containing (C), There is a method of kneading the masterbatch and the remaining styrene resin or the remaining (C) or (D).

Regarding the twin-screw extruder used in the production of the flame-retardant resin composition of the present invention, especially when polyphenylene ether is contained, the ratio L / D of the screw length L to the cylinder inner diameter D is 20 to 20. 50, and has two or more supply openings of a main feed opening and a side feed opening which are different in the distance from the tip of the twin-screw extruder. It is preferable that a kneading portion is provided between the portions and between the distal end portion and the supply opening portion at a short distance from the distal end portion, and the length of the kneading portion is 3D to 10D, respectively.

Examples of preferred compositions of the flame-retardant resin composition of the present invention include the following. Consisting of a rubber-modified styrene resin and a rubber-unmodified styrene resin,
(C) aromatic phosphate 5 per 100 parts by weight of a resin component composed of 10 to 90% by weight of styrene resin (A) and 90 to 10% by weight of polyphenylene ether (B).
To 15 parts by weight, (D) polytetrafluoroethylene 0.1.
01 to 0.09 parts by weight, (E) 1 to 5 parts by weight of novolak resin.

In the case of the above composition, excellent balance of flame retardancy, especially drop-type flame retardancy, appearance, continuous moldability, moldability (fluidity), impact resistance and heat resistance.

The composition thus obtained is, for example,
It can be continuously molded for a long time using an injection molding machine or an extrusion molding machine, and the obtained molded product has excellent flame retardancy (drop-type flame retardancy), fluidity, heat resistance and impact resistance ing.

[0105]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention.

The measurements in the examples and comparative examples were performed using the following methods or measuring instruments.

(1) Reduced viscosity of rubber-modified styrene resin and polyphenylene ether ηsp / C
and a mixed solvent of methanol and 2 ml of methanol.
Shake for 5 hours and centrifuge at 18000 rpm for 30 minutes at 5 ° C. The supernatant was taken out and the resin component was precipitated with methanol and then dried.

0.1 g of the resin thus obtained was
In the case of rubber-modified polystyrene, it is dissolved in toluene, and in the case of rubber-modified acrylonitrile-styrene copolymer resin, it is dissolved in methyl ethyl ketone to obtain a solution having a concentration of 0.5 g / dl. 10 ml of this solution is placed in a Canon-Fenske viscometer, The solution falling time T1 (second) was measured at 30 ° C. On the other hand, the falling time T ₀ (second) of pure toluene or pure methyl ethyl ketone was measured separately using the same viscometer, and calculated by the following formula.

Ηsp / C = (T ₁ / T ₀ −1) / C C: polymer concentration (g / dl) On the other hand, regarding the reduced viscosity ηsp / C of polyphenylene ether, 0.1 g was dissolved in chloroform and the concentration was reduced. 0.
A solution of 5 g / dl was prepared and measured in the same manner as above.

(2) Analysis of Flame Retardant 5 g of the resin composition was dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge (20,000 rpm).
m, 1 hour). Then, the supernatant obtained by separation was added with 2
A double amount of methanol was added to precipitate a resin component, and the solution portion and the resin portion were separated using an ultracentrifuge. For the solution part, use GPC (gel permeation chromatography) [manufactured by Tosoh Corporation, Japan;
HLC-8020; column, manufactured by Tosoh Corporation, two G1000HXL; mobile phase, tetrahydrofuran; flow rate, 0.8 ml / min; pressure, 60 kg
f / cm ² ; temperature INLET 35 ° C, OVEN 4
0 ° C., RI 35 ° C .; sample loop 100 ml; injected sample amount 0.08 g / 20 ml], and the area ratio of each component on the chromatogram is assumed to be the weight fraction of each component, and the phosphate ratio is determined from the area ratio. And residual aromatic vinyl monomer and dimer and 3 of aromatic vinyl monomer
The composition and amount of the monomer were determined. On the other hand, regarding the above resin portion, a Fourier transform nuclear magnetic resonance apparatus (proton-FT-
NMR), the ratio of the integral value of the aromatic proton or the aliphatic proton was determined, and the amounts of the rubber-modified styrene resin and the thermoplastic resin such as polyphenylene ether were determined.

(3) Volatility evaluation (thermogravimetric balance test: TG
Method A) Using a Shimadzu thermal analyzer DT-40 manufactured by Shimadzu Corporation of Japan, the temperature was raised at 40 ° C./min under a nitrogen stream, and the 1% by weight temperature was used as a measure of volatility.

(4) Izod Impact Strength Measured at 23 ° C. by a method according to ASTM-D256.

(V Notch, 1/8 inch Test Specimen) (5) Vicat Softening Temperature Measured by a method in accordance with ASTM-D1525 and used as a measure of heat resistance.

(6) Melt flow rate (MFR) The melt flow rate was measured by a method in accordance with ASTM-D1238 as an index of melt fluidity. It was determined from the extruded amount per 10 minutes (g / 10 minutes) under the conditions of a load of 5 kg and a melting temperature of 200 ° C.

(7) Flame retardancy and fire-dropping fire spreadability VB (Vertical Bur) conforming to UL-94
(1/16 inch test piece).

Further, in order to evaluate the dropping fire spreadability of the fire, a metal plate was placed at a distance of 12 ″ from the lower part of the test piece, and the extinction time of the dropped fire was measured.

The following components were used in Examples and Comparative Examples.

(A) Styrene resin Rubber-modified styrene resin (HIPS) polybutadiene (weight ratio of cis 1,4 bond / trans 1,4 bond / 1 vinyl 1,2 bond = 95/2/3) (Nippon Zeon ( Co., Ltd., brand name Nipol 122 OSL)｝
Was dissolved in the following mixture to give a uniform solution.

Polybutadiene 10.5% by weight Styrene 74.2% by weight Ethylbenzene 15.0% by weight α-methylstyrene dimer 0.27% by weight t-butylperoxyisopropyl carbonate 0.03% by weight Is continuously supplied to a series four-stage reactor equipped with a stirrer, and the first stage has a stirring speed of 190 rpm and 126 rpm.
° C, the second stage is 50 rpm, 133 ° C, the third stage is 20 rpm
m, 140 ° C., and polymerization was performed at 20 rpm and 155 ° C. in the fourth stage. Subsequently, the polymerization liquid having a solid content of 73% was led to a devolatilizer to remove unreacted monomers and a solvent to obtain a rubber-modified aromatic vinyl resin (referred to as HIPS-1). As a result of analyzing the obtained rubber-modified aromatic vinyl resin, the rubber content was 12.1% by weight, and the weight average particle diameter of the rubber was 1.5 μm.
m, and the reduced viscosity ηsp / c was 0.53 dl / g.

Further, rubber-modified styrene resins having different reduced viscosities ηsp / c were produced by adjusting the amounts of the polymerization initiator, the polymerization temperature and the amount of the chain transfer agent. The results are shown in Table 2.

In the examples and comparative examples, the following HIPS
Was used. (Tables 1 and 2) HIPS-1: polybutadiene rubber, rubber content is 12.
The weight average particle diameter of the rubber was 1.5 μm, and the reduced viscosity ηsp / c was 0.53 dl / g.

HIPS-2: polybutadiene rubber, rubber content: 12.1% by weight, rubber weight average particle diameter: 1.5 μm
m, reduced viscosity ηsp / c is 0.79 dl / g.

HIPS-3: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, and reduced viscosity ηsp / c is 0.60 dl / g.

HIPS-4: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 0.58 dl / g.

HIPS-5: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 0.40 dl / g.

HIPS-6: rubber content: 12.1% by weight, rubber weight average particle size: 1.5 μm, reduced viscosity ηs
p / c is 0.35 dl / g.

Rubber-unmodified styrene resin (GPPS) Polystyrene having a weight average molecular weight of 200,000 (produced by Asahi Kasei Kogyo Co., Ltd.) was used (referred to as GPPS).

(B) Polyphenylene ether (PPE)
After the inside of a stainless steel reactor having an oxygen inlet at the bottom of the reactor and having a cooling coil and stirring blades inside was sufficiently replaced with nitrogen, 54.8 g of cupric bromide, di-n-
1110 g of butylamine and 20 liters of toluene,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into the reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was performed for 90 minutes while controlling the internal temperature to 30 ° C. After completion of the polymerization, the precipitated polymer was separated by filtration. A mixed solution of methanol / hydrochloric acid was added thereto to decompose the remaining catalyst in the polymer, further sufficiently washed with methanol, and dried to obtain a powdery polyphenylene ether (referred to as PPE-1). The reduced viscosity ηsp / C was 0.41 dl / g.

Further, polyphenylene ethers having different reduced viscosities ηsp / c were produced by adjusting the amount of catalyst or controlling the polymerization time in the production of polyphenylene ether. Table 3 shows the results.

(C) Phosphorus-based flame retardant (1) 1,3-phenylene bis (diphenyl phosphate) (FR-1) A commercially available resorcinol-derived aromatic condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd.) Trade name CR733S (hereinafter referred to as FR-1) was used. In addition, according to GPC analysis, the aromatic condensed phosphoric acid ester is composed of a TPP dimer (n = 1) represented by the following formula (18) and TP
P oligomer (n ≧ 2), and the weight ratio was 65/35, respectively.

[0131]

Embedded image

(2) 1,3-phenylene bis (di 2,6
Preparation of -dimethylphenyl phosphate) (FR-2) 244 parts by weight of 2,6-xylenol, 20 parts by weight of xylene, and 1.5 parts by weight of magnesium chloride were added to a reactor,
Heat and mix. When the temperature of the reaction solution reached 120 ° C., 153 parts by weight of phosphorus oxychloride was added dropwise over 2 hours. The hydrochloric acid gas generated at this time was led to a water scrubber. After the addition of phosphorus oxychloride was completed, the temperature of the reaction solution was gradually raised to 180 ° C. over 2 hours to complete the reaction. The yield of the obtained intermediate di (2,6-xylyl) phosphorochloride was 99.7%. Then, the obtained intermediate 45
Parts by weight, 55 parts by weight of resorcinol, aluminum chloride
5 parts by weight were added to the reactor, mixed by heating, and the temperature of the reaction solution was gradually raised to 180 ° C. over 2 hours to perform a dehydrochlorination reaction. After aging for 2 hours at the same temperature, 20
The reaction was further aged for 2 hours under reduced pressure of 0 mmHg to complete the reaction. Xylene 50 was added to the reaction solution thus obtained.
0 parts by weight and 200 parts by weight of a 10% hydrochloric acid aqueous solution were added to remove remaining catalyst and the like, and washing with water was repeated. The purified reaction solution was cooled to room temperature with stirring to crystallize, washed with methanol, and dried at 100 ° C. under reduced pressure to obtain the following formula (1)
1,3-phenylenebis (di2,6-dimethylphenyl phosphate) (hereinafter referred to as FR-2) represented by 9) was obtained.

[0133]

Embedded image

(3) Production of tris (nonylphenyl) phosphate (FR-3) 431.0 parts by weight of nonylphenol (3.0 by mole),
0.87 parts by weight of aluminum chloride (molar ratio 0.01) was placed in a flask, and 100 parts by weight of phosphorus oxychloride (molar ratio 1.0) was added dropwise at 90 ° C. over 1 hour. In order to complete the reaction, the temperature was gradually raised and finally raised to 180 ° C. to complete the esterification. Next, the reaction product was cooled and washed with water to remove the catalyst and chlorine, thereby obtaining tris (nonylphenyl) phosphate (hereinafter, referred to as FR-3).

The average of the total number of carbon atoms of the substituent is 2
7.0.

(4) Bisphenol A bis (diphenyl phosphate) (FR-4) Commercially available aromatic condensed phosphoric acid ester derived from bisphenol A (trade name: CR741 manufactured by Daihachi Chemical Industry Co., Ltd.) ｝) Was used. In addition, according to GPC analysis, the aromatic condensed phosphate ester is a TPP-A-dimer represented by the following formula (20) (n = 1)
And TPP-A-oligomer (n ≧ 2) and triphenyl phosphate (TPP).
4.7 / 13.0 / 2.3.

[0137]

Embedded image

(5) Triphenyl phosphate (FR-
5) A commercially available aromatic phosphate ester monomer [trade name TPP (hereinafter referred to as FR-5) manufactured by Daihachi Chemical Industry Co., Ltd.] was used.

(D) Fluorinated resin Commercially available polytetrafluoroethylene [trade name: Teflon 6J (manufactured by Mitsui Dupont Fluorochemicals Co., Ltd.)
TFE)] was used.

(E) Novolak resin Commercially available phenol novolak resin [Asahi Organic Materials Co., Ltd.
SP1006N (hereinafter referred to as NK)].

Examples 1-4, Comparative Examples 1-3 HIPS-1 / GPPS / PPE-1 / FR-1 / PT
FE / NK were mixed at the weight ratio shown in Table 1 and a twin-screw extruder capable of side feeding (Werner Pfleid) was used.
Melt extrusion was carried out using Zerk (ZSK-40 mmφ manufactured by erer). That is, GPPS / PP in the front stage of the extruder
E-1 was melted at 300 ° C., and while the remaining components were side-fed in the subsequent stage, the rotation speed was 295 rpm and the discharge amount was 80 kg.
/ H was melt-kneaded at a subsequent stage temperature of 240 ° C.

A test piece was prepared from the pellet thus obtained using an injection molding machine (Model IS80A, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 60 ° C., and the MFR and Izod impact strength were measured. The Vicat softening temperature,
The appearance and the flame retardancy were evaluated. Table 1 shows the results.

[0143]

[Table 1]

According to Table 1, PTFE was 0.001 to
Only when the content is 0.09 parts by weight, it can be seen that a molded article having no fire and no spread of fire and excellent in appearance can be obtained.
It was also found that the addition of the novolak resin improved the fluidity and heat resistance.

Examples 5 to 19, Comparative Example 4 HIPS having different reduced viscosities ηsp / C shown in Tables 2 and 3,
PPE was mixed at the composition ratios shown in Tables 2 and 3, and the same experiment as in Example 1 was performed for evaluation. The results are shown in Tables 2 and 3.

According to Tables 2 and 3, ηsp / C of HIPS
Is in the range of 0.4 to 0.6, fluidity, impact strength, and excellent flame retardancy balance characteristics, and,
The presence of PPE improves the balance of heat resistance, flame retardancy and impact strength.
0 to 25% by weight, and the reduced viscosity ηsp / C is 0.1%.
It can be seen that when the ratio is 3 to 0.6, the balance characteristics of fluidity, heat resistance, impact strength and flame retardancy are further improved.

[0147]

[Table 2]

[0148]

[Table 3]

Examples 20 to 25 Using the (C) aromatic phosphate ester described in Table 4 below,
The mixture was mixed at the described composition ratio, and the same experiment as in Example 1 was performed to evaluate. The results are shown in Table 4.

[0150]

[Table 4]

[0151]

The present invention relates to a styrenic resin composition containing a fluororesin and having drop-type flame retardancy.

The composition of the present invention can be used for home appliance housings such as VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio cassettes, video cassettes, video disc players, air conditioners, humidifiers, electric warm air machines, etc. , Chassis or parts, CD-RO
OA of M mainframe (mechanical chassis), printer, fax, PPC, CRT, word processor copier, electronic cash register, office computer system, floppy disk drive, keyboard, type, ECR, calculator, toner cartridge, telephone, etc. Equipment housing, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable condenser,
AC adapter, FBT high pressure bobbin, FBT case,
IFT coil bobbin, jack, volume shaft,
Suitable for electronic and electrical materials such as motor parts, and automotive materials such as instrument panels, radiator grills, clusters, speaker grills, louvers, console boxes, defroster garnishes, ornaments, fuse boxes, relay cases, connector shift tapes, etc. And play a large role in these industries.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71/12 C08L 71/12 // (C08L 25/04 71:12 27:12 61:06) (C08L 51/04 71: 12 27:12 61:06)

Claims (4)

[Claims] (A) 1 to 99 parts by weight of a styrene resin,
(B) 100 parts by weight of a resin component comprising 99 to 1 parts by weight of polyphenylene ether, and (C) 1 to 10 parts by weight of a flame retardant
A fluororesin-containing drop-type flame-retardant resin composition comprising 0 parts by weight and (D) 0.001 to 0.09 parts by weight of a fluororesin. 2. A drop-type flame-retardant resin composition containing a fluorine-based resin, wherein the flame retardant (C) is an aromatic phosphate ester. 3. The drop-type flame-retardant resin composition containing a fluororesin according to claim 1, further comprising 0.1 to 50 parts by weight of (E) a novolak resin based on 100 parts by weight of the resin component. 4. The method according to claim 1, wherein (A) is a reduced viscosity ηsp / C of the resin portion.
Is a rubber-modified styrene resin having a reduced viscosity of 0.4 to 0.6, and (B) contains a polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6. Such a fluororesin-containing dripping flame-retardant resin composition.