JPH1036604A - Resin composition having dripping type flame retardancy and excellent mold release - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a styrene resin composition having markedly improved dripping-type flame retardancy and excellent mold release. SOLUTION: This composition comprises 100 pts.wt. styrene resin, 1-100 pts.wt. flame retardant and 0.01-5 pts.wt. mold release. The total content of an aromatic vinyl monomer, its dimer and its trimer remaining in the composition should be 1wt.% or below. This composition may further contain 1-100 pts.wt. polyphenylene ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition. More specifically, the present invention relates to a flame-retardant styrene-based resin composition having excellent release properties.

[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 halogen-based, phosphorus-based, and inorganic-based flame retardants to styrene-based resins, thereby achieving some degree of flame retardancy. However, many of the resin compositions to which the flame retardant has been added often cause the flame retardant to bleed on the surface of the molded product or a small amount of volatile components to generate an adhesive component on the surface of the mold, thereby causing the mold to separate from the mold. The moldability is remarkably reduced, and the appearance of the molded article may be impaired, which is a problem. As a countermeasure, a method of applying a mold release agent to the mold surface has been adopted, but the effect is obtained only up to a few shots. In the case of high-precision machines and large molded products, the problem that the draft angle cannot be made large and the size and position of the protruding pins are restricted by the complicated shape of the molded product have surfaced. Instead, an additive release agent has been demanded. Under such circumstances, an additive release agent was developed, and although the problem of the release property was solved to some extent, a new problem that flame retardancy was reduced by the addition of the release agent occurred.

[0004] As a prior art of an additive release agent, Japanese Patent Application Laid-Open No.
JP-A-48844 discloses a flame-retardant resin composition comprising polycarbonate, a styrene-based resin, a specific phosphorus-based flame retardant, polytetrafluoroethylene, a saturated fatty acid ester-based wax, and a polyethylene wax, which is excellent in releasability. ing. However, the above composition has excellent releasability, but poor flame retardancy. The above-mentioned publication discloses residual aromatic vinyl monomers and dimers and trimers of aromatic vinyl monomers.
It is neither disclosed nor implied that dropping flame retardancy is particularly improved by controlling the monomer to a specific amount or less.

Further, Japanese Patent Publication No. Hei 7-119347 discloses that styrene dimer and styrene trimer are 0.5% in total.
Hereinafter, a styrene-based resin composition comprising a rubber-modified styrene-based resin containing a total of 500 ppm or less of residual volatile components and a specific saturated higher aliphatic carboxylic acid and a metal salt thereof is disclosed. The above resin composition is excellent in the releasability of a composition without a flame retardant, but is inferior in the balance characteristic of the flame retardancy and the releasability of the flame retardant composition.

A phosphorus-based flame retardant, particularly an organic phosphorus compound, is used as a flame retardant in a styrene-based resin composition using polyphenylene ether. In general, the organic phosphorus compound has high volatility, and volatile organic compounds are formed during molding. There is a problem that mold contamination due to a phosphorus compound, so-called mold deposits, lowers productivity, or mold contaminants are transferred to molded products and cause stress cracks, and industrial use is narrowed. .

As a technique for improving volatility, a resin composition for a laminate comprising a phenolic resin and a specific alkyl group-substituted phosphate ester monomer (JP-A-1-95149, JP-A-1-242633, JP-A-1-242633) No. 193328)
Is disclosed. The subject of the flame retardant of this publication is a thermosetting resin, which is different from the flame retardant of the present invention intended for the styrenic resin.

Further, as a technique for flame retarding styrene-based resins, a flame-retardant resin composition comprising a polyphenylene ether, a styrene-based resin, a metal salt of phosphoric acid, and a phosphate such as tris (nonylphenyl) phosphate (Japanese Patent Laid-Open No. 63
JP-A-305161), a polyphenylene ether resin composition (EP5) comprising polyphenylene ether and high molecular weight polyethylene as essential components and, if necessary, a phosphate such as tris (nonylphenyl) phosphate.
50204), aromatic polycarbonate, ABS resin,
Flame retardant resin composition comprising an AS resin, a phosphate such as tris (nonylphenyl) phosphate, an aromatic sulfonate, and a fibrous reinforcing material (JP-A-6-29906)
No. 0) is disclosed. The above three publications do not disclose that specific resin compositions exhibit excellent resin properties such as fluidity, flame retardancy, and volatility.

[0009]

SUMMARY OF THE INVENTION In view of such circumstances, an object of the present invention is to provide a drip-type flame-retardant resin composition which does not have the above-mentioned problems, that is, has excellent releasability. Is what you do.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies on improving the releasability of a flame-retardant styrenic resin composition.
In a resin composition comprising (A) a styrene-based resin, (B) a flame retardant, and (C) a release agent, surprisingly, the volatile component derived from the aromatic vinyl monomer is limited to a specific amount or less. In particular, the present inventors have found that dripping flame retardancy is dramatically improved while maintaining the releasability, and the present invention has been achieved.

That is, the present invention relates to (A) a styrene resin 1
A resin composition comprising (B) 1 to 100 parts by weight of a flame retardant, (C) 0.01 to 5 parts by weight of a release agent,
And a releasability wherein the total content of the aromatic vinyl monomer and the dimer and trimer of the aromatic vinyl monomer remaining in the resin composition is 1% by weight or less. A flame-retardant resin composition having excellent releasability, wherein the composition further comprises (D) 1 to 100 parts by weight of polyphenylene ether,
In particular, the dropped flame-retardant resin composition having excellent releasability, wherein (C) is one or two or more compounds selected from saturated higher aliphatic carboxylic acids or metal salts thereof, and (A) ) Reduced viscosity ηsp / C of resin portion is 0.4 to
0.6 parts by weight of a rubber-modified styrenic resin,
(B) 1 to 100 parts by weight of a flame retardant represented by the following formula (1), and (C) one or more compounds 0.01 selected from saturated higher aliphatic carboxylic acids and metal salts thereof.
~ 5 parts by weight and (D) reduced viscosity ηsp / C is 0.3 ~
An object of the present invention is to provide a drop-type flame-retardant resin composition comprising 1 to 100 parts by weight of polyphenylene ether having an excellent release property of 0.6.

[0012]

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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. Hereinafter, the present invention will be described in detail.

The present invention relates to (A) a styrene resin, (B)
A flame-retardant resin composition comprising a flame retardant, (C) a release agent and, if necessary, a volatile component derived from an aromatic vinyl monomer in a specific amount or less in a composition comprising (D) polyphenylene ether. It is.

The above (A) is a main component of the molding resin composition and plays a role of maintaining the strength of the molded article, and (B) is a component for imparting flame retardancy to the styrene resin. C)
Is a component for imparting releasability to (A), and (D)
Is a component for imparting impact strength, heat resistance and flame retardancy to (A).

Here, it is important that the total content of the aromatic vinyl monomer remaining in the resin composition and the dimer and trimer of the aromatic vinyl monomer is 1% by weight or less. is there. When the total amount exceeds 1% by weight, it has been found that the compound volatilizes at the time of combustion and acts as a fuel, so that the drop-type flame retardancy is particularly reduced, and the present invention has been completed.

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).

Here, the rubber-like 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) and poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubbers, isoprene rubbers and chloroprene rubbers. , 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.

When it is necessary to lower the melt viscosity at the time of 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.

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

The halogen-based flame retardant (B) 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 (B),
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, particularly, as the organic phosphorus compound, an aromatic phosphate monomer represented by the following formula (2):
An aromatic phosphate condensate represented by the following formula (3) is 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, particularly, hydroxyl group-containing aromatic phosphate ester monomers such as tricresyl phosphate and triphenyl phosphate shown in the above formula (2) are exemplified. Phosphate ester monomers containing one or more phenolic hydroxyl groups or aromatic phosphate ester monomers represented by the following formula (1) 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. , A tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an otadecyl group, a nonadecyl group, an octadodecyl group, and the like. One or a plurality of substituents are in any position of ortho, meta, and para on one aromatic ring. Can be substituted, but a para-substituted product is preferable. The total number of carbon atoms of the alkyl group substituted by one phosphate ester monomer is 12 to
Most preferably, the number of aromatic rings substituted by only one alkyl group is more than that of the phosphate ester monomer having only one aromatic ring substituted by only one long-chain alkyl group. The phosphoric acid ester monomer has better heat resistance and water resistance. For example, even if the total number of carbon atoms of the alkyl group to be substituted is 18, bis (nonylphenyl) phenyl phosphate is preferable because of its higher heat resistance than octadecylphenyl diphenyl phosphate. In the present invention, among the organic phosphorus compounds, in particular at least one of R ^1, R ^2, R ³ is a phosphate ester monomer is preferably a nonyl group, R ^1, R ^2, R ³ is a nonyl group The aromatic phosphate ester monomer [tris (nonylphenyl) phenyl phosphate] is most preferred from the viewpoint of fluidity and volatility resistance. When the phosphoric acid ester monomer is contained in the flame retardant at 50% by weight or more, a particularly large flame retardant effect is exhibited. The phosphoric acid ester monomer is excellent in fire dropping properties, and is extremely excellent as a flame retardant of rank V-2 according to UL-94 flame retardancy standards. This fact was not previously known.

Further, from the viewpoint of volatility resistance, the total number of carbon atoms of the substituents must satisfy the requirements of the present invention, but the ratio of those having a total number of carbon atoms of the substituent of less than 12 is 1% by weight or less. In some cases, even better volatility is developed.

From the viewpoint of the thermal stability of the flame retardant, particularly from the viewpoint of heat discoloration resistance, JIS-K6
751 or less, more preferably 0.5 mgKOH / g, and / or the alkylphenol is preferably 1% by weight or less, more preferably 0.5% by weight or less. Is more preferably 1000 ppm or less. When the hindered phenolic antioxidant is contained in the flame retardant in an amount of 1 to 1000 ppm by weight, the thermal stability is remarkably improved.

Next, from the viewpoint of light resistance, the substituents R ¹ , R ² , and R ³ are not aryl groups, and even when they are alkyl groups, it is preferable that the alkyl groups have few branches. One alkyl group is particularly preferred.

Further, the number of substituents to be substituted on one aromatic ring of the aromatic phosphate ester is preferably one. The viscosity of an aromatic phosphate ester monomer in which one aromatic ring is substituted with a plurality of substituents is high, and the viscosity increases with the number of substituents. When the viscosity of the aromatic phosphate ester monomer becomes high, not only the handling problem but also the high viscosity makes purification difficult, and the above-mentioned impurities remain, thereby deteriorating the light resistance and heat discoloration resistance.

The most preferred combination of aromatic phosphate ester monomers in the present invention is mainly tris (nonylphenyl) phosphate (TNPP) and contains a small amount of bis (nonylphenyl) phenylphosphate (BNPP). The total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 20 to 27, preferably 25 to 27,
It is more preferably 26 to 27, and most preferably 26.5 to 27. In order to satisfy the above number average of the total number of carbon atoms, for example, BNPP is contained in an amount of 78 to 0% by weight, preferably 22 to 0% by weight, more preferably 11 to 0% by weight, and most preferably 5 to 0% by weight. Yes, TNPP is 22-1
00% by weight, preferably 78-100% by weight, more preferably 89-100% by weight, most preferably 95-1% by weight.
It is in the range of 00% by weight. The flame retardant of such a combination is particularly excellent in balance characteristics of flame retardancy, fluidity, heat resistance, impact strength, water gloss retention, and surface hardness of the obtained molded article. TNPP not only has a high volatility resistance and a high effect of imparting heat resistance, but also has excellent water gloss retention because it is structurally symmetric. As described above, TNPP exerts a specific effect and cannot be predicted by conventional knowledge.

The aromatic phosphate ester monomers used in the present invention are described in JP-A-1-95149 and JP-A-3-95149.
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 above aromatic phosphate ester condensates, bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate) and the like are particularly preferable.

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

The inorganic flame retardant (B) 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, (B) is added in an amount of 1 to 10 with respect to 100 parts by weight of the rubber-modified styrenic resin.
0 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 20 parts by weight, and most preferably 5 to 15 parts by weight.

In the present invention, the release agent used as (C) is selected from saturated higher aliphatic carboxylic acids or metal salts thereof, carboxylic ester waxes, organosiloxane waxes, polyolefin waxes, and polycaprolactone. One or more compounds.

Among the above (C), 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 (C) is preferably from 0.01 to 5 parts by weight, more preferably from 0.1 to 5 parts by weight, most preferably from 0.3 to 5 parts by weight, based on 100 parts by weight of the styrene resin.
1 part by weight.

In the present invention, the polyphenylene ether (D) is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula (4).

[0053]

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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), 2,6-dimethylphenol and 2,3,3-dimethylphenol.
A copolymer with 6-trimethylphenol is preferred,
Among them, 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, US Pat. No. 3,306,87
No. 5, U.S. Pat. No. 3,257,357,
U.S. Pat. No. 3,257,358 and JP-B-52
It can be easily produced by the methods described in JP-A-17880 and JP-A-50-51197. Reduced viscosity ηsp / c of the polyphenylene ether used in the present invention
(0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is preferably in the range of 0.20 to 0.70 dl / g, and more preferably in the range of 0.30 to 0.60 dl / g. Reduced viscosity η of polyphenylene ether
Means for satisfying the above requirements regarding sp / c include adjustment of the amount of a catalyst in the production of the polyphenylene ether.

In the present invention, (D) is added in an amount of 1 to 100 parts by weight, preferably 1 to 50 parts by weight, and more preferably 100 parts by weight of the styrene resin.
It is 3 to 20 parts by weight, most preferably 5 to 15 parts by weight.

In the present invention, in particular, UL-94 regulated V
(A) The reduced viscosity ηsp / C of the resin portion is 0.4 to 0.4.
0.6 parts by weight of a rubber-modified styrenic resin,
(B) 1 to 100 parts by weight of the flame retardant represented by the above formula (1), (C) one or more compounds selected from saturated higher aliphatic carboxylic acids and metal salts thereof 0.01
~ 5 parts by weight and (D) reduced viscosity ηsp / C is 0.3 ~
It can be achieved by combining 1 to 100 parts by weight of polyphenylene ether which is 0.6. By satisfying the requirement of the reduced viscosity of the present invention, the balance between the dropping property of fire and the impact strength is improved.

In the present invention, if necessary, one or more flame retardants selected from triazine skeleton-containing compounds, novolak resins, metal-containing compounds, silicone resins, silicone oils, silica, aramid fibers, fluororesins, and polyacrylonitrile fibers. Auxiliaries (E) can be included.

The amount of (E) is preferably 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 5 to 1 part by weight based on 100 parts by weight of the styrene resin.
0 parts by weight.

The triazine skeleton-containing compound as (E) is a component for further improving the flame retardancy as a flame retardant auxiliary of the phosphorus-based flame retardant. Specific examples thereof include melamine, melam represented by the following formula (5), melem represented by the following formula (6), melon (product of deammonification of three to three molecules of melem at 600 ° C. or more), Melamine cyanurate represented by (7), melamine phosphate represented by the following formula (8), succinoguanamine, adipoguanamine, methylglutaloganamin represented by the following formula (9), represented by the following formula (10) And a BT resin represented by the following formula (11), but melamine cyanurate is particularly preferred from the viewpoint of volatility resistance.

[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 novolak resin (E) is a flame retardant aid and, when used in combination with a hydroxyl group-containing aromatic phosphate, is also a fluidity and heat resistance improver. 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 represented by the following formula (1)
2) and (13).

[0070]

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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.

The metal-containing compound as (E) 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 (E) 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 is obtained by co-hydrolyzing and polymerizing an organohalosilane corresponding to the above structural unit.

The silicone oil (E) is a polydiorganosiloxane, particularly preferably a vinyl-containing silicone oil, which comprises a chemical bond unit represented by the following formula (14).

[0077]

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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 (15) and (16), and particularly contains a vinyl group in the molecule.

[0079]

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[0080]

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

The silica as (E) is amorphous silicon dioxide, particularly preferably 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 (E) 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 fluorine-based resin (E) is a flame-retardant auxiliary, and is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and a tetrafluoroethylene / hexafluoropropylene copolymer.
If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.

The polyacrylonitrile fiber (E) 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 acrylate unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty alcohol, or a metal One or two or more fluidity improvers (F) selected from soaps can be blended.

The amount of (F) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and most preferably 1 to 5 parts by weight based on 100 parts by weight of the styrene resin.
Parts by weight.

The aromatic vinyl unit of the copolymer resin (F) 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 aids as (F) include liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, or fluorides and chlorides.

The higher fatty acids as (F) include saturated fatty acids other than those described in the section of (C) 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 (F) 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 (F) 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 (F) 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 (F) 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, if necessary, a thermoplastic elastomer (G) can be blended. For example, polystyrene, polyolefin, polyester, polyurethane, 1,2-polybutadiene, polyvinyl chloride, etc. And the like, and a polystyrene-based thermoplastic elastomer is particularly preferable.

The amount of (G) is the same as that of the rubber-modified styrenic resin 1
For 0.5 parts by weight, preferably 0.5 to 20 parts by weight,
More preferably, 1 to 10 parts by weight, most preferably, 2 to 10 parts by weight.
-5 parts by weight.

The 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-tribromostyrene. 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 light resistance improvers (H) selected from the above agents can be blended.

The amount of (H) is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and most preferably 1 to 100 parts by weight based on 100 parts by weight of the styrene resin.
5 parts by weight.

(D) In the case of using a polyphenylene ether, the method for producing the resin composition of the present invention is as follows. First, a styrene resin and (D) are melted, and then (B) and (C) are added. A method of melt-kneading with an extruder, or a styrene resin, (D), or (B) if necessary
Is manufactured, and then the master batch and the remaining styrene resin or the remaining (B) or (C) are kneaded.

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. TNPP alone or TN based on 100 parts by weight of a styrene-based resin (A) consisting of 10 to 90 parts by weight of a rubber-modified styrene-based resin and 90 to 10 parts by weight of a rubber-unmodified styrene-based resin
5 to 15 parts by weight of an aromatic phosphate ester monomer mainly containing PP and containing BNPP, (C) 0.1 to 1 part by weight of a metal salt of a saturated higher fatty acid, (D) 3 to 10 parts by weight of polyphenylene ether Department.

In the case of the above composition, flame retardancy, especially drop-type flame retardancy, mold release, continuous moldability, moldability (flowability),
Excellent balance of 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.

[0111]

BEST MODE FOR CARRYING OUT THE INVENTION

[0112]

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 T0 (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, 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 is dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge. (20,000r
pm, 1 hour) Then, 2 ml was added to the supernatant obtained by separation.
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) Evaluation of Volatility of Phosphorus-Based Flame Retardant (Thermogravimetric Balance Test: TGA Method) 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. The weight loss at 300 ° C. or 400 ° C. was taken as a measure of volatility.

On the other hand, using the above apparatus, the residual amount after standing at 250 ° C. for 5 minutes in a nitrogen stream 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 according to 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 VB (Vertical Bur) conforming to UL-94
ning) method. (1/8 inch test piece) (8) Release Property A mold (see FIG. 1) in which a load cell is attached to an ejector pin is attached to an injection molding machine, and injection molding is performed after clamping.
The signal from the load cell when the cylindrical molded product is released from the mold by the ejector pin when the mold is opened is amplified by an amplifier and recorded on the memory recorder. The release property is determined by the maximum release force (k
The smaller the value evaluated in g), the better the releasability.

Molding conditions: cylinder temperature 200 ° C., mold temperature 40 ° C. Back pressure 10 kg 10 kg No holding pressure 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
rpm, 140 ° C, 4th stage is 20rpm, 155 ° C
The polymerization was carried out. 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. As a result of analyzing the obtained rubber-modified aromatic vinyl resin (referred to as HIPS-1), the rubber content was 12.1% by weight, the weight average particle diameter of the rubber was 1.5 μm, and the reduced viscosity ηsp / c was 0.53 dl. / G
Met.

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

In 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 size 1.5
μm, 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. The polymer was sufficiently washed with methanol and then 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 Triphenyl phosphate (TPP) A commercially available aromatic phosphate ester monomer [trade name TPP (trade name: TPP) manufactured by Daihachi Chemical Industry Co., Ltd.] was used.
The phosphorus content is 9.5% by weight.

Preparation of Alkyl-Substituted Aromatic Phosphate Monomer (FR-1) Nonylphenol 287.3 parts by weight (molar ratio 2.0),
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. 61.4 parts by weight of phenol (molar ratio 1.0) was added to the resulting intermediate, and further reacted. 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 a phosphoric ester mixture (hereinafter referred to as FR-1). This mixture was subjected to GPC (gel permeation chromatography, Tosoh Corporation).
Manufactured by HLC-8020 mobile phase tetrahydrofuran. ) And nonylphenol in a weight ratio of 77.8 / 11.3 / 8.4 /
2.5.

The average of the total number of carbon atoms of the substituent is 1
7.9, (18 × 0.778 + 27 × 0.113
+ 9 × 0.084 = 17.9) The phosphorus content is 5.5% by weight.

On the other hand, BNPP or TNPP was obtained by distilling the above aromatic phosphate ester monomer mixture (FR-1) and further fractionating by liquid chromatography.

Production of Various Alkyl-Substituted Aromatic Phosphate Monomers In the production of FR-1, commercially available alkylphenol or "ENCYCLOPEDIA OF CHEMIC" was used.
AL TECHNOLOGY "ThirdEditi
on VOLUME 2 [ALKYLPHENOL
S "p. 72-96 (A WILEY-INTER
SCIENCE PUBLICATION John
Wiley & Sons New York 1978)
Various alkylphenols were synthesized by controlling the molar ratio with phosphorus oxychloride using various alkylphenols obtained by the method described. The purification method was carried out by the above-mentioned water washing, distillation or preparative fractionation by liquid chromatography. Table 4 shows various alkyl group-substituted aromatic phosphate monomers.

(D) Release agent Commercially available zinc stearate (referred to as ZnST) was used.

Examples 1-2 Comparative Examples 1-3 Residual styrene monomers and oligomers (styrene dimer and styrene) were changed by changing the polymerization temperature and the amount of chain transfer agent.
Polystyrene containing a large amount of
-1 was mixed with HIPS obtained by purification to produce rubber-modified polystyrene having different amounts of residual styrene monomer and oligomer. Next, tris (nonylphenyl) phosphate [TNPP] and ZnST were added to 100 parts by weight of the styrene resin obtained by mixing the rubber-modified styrene resin and GPPS at a ratio of 70/30.
Are mixed in the amounts described in Table 1 and a twin-screw extruder capable of side-feeding (cylinder inner diameter D = 40 mmΦ, L / D = 46, length of the kneading portion between the main feed / first supply opening: 8.9 D, Melt extrusion was performed using the length of the kneading portion between the tip portion and the first supply opening: 12.5D). That is, HIPS-1 / GPPS / ZnST is fed from the main feeder at the former stage of the extruder (from the main feed opening to the first supply opening [side feeder]), melted at a barrel temperature of 230 ° C., and then TNPP Was fed from a side feeder and melted at a barrel temperature of 230 ° C.

The releasability of the thus obtained pellets was measured by an injection molding machine (Model IS80A, manufactured by Toshiba Machine Co., Ltd.) by the method described in the section of releasability measurement method. On the other hand, test pieces were prepared with the above molding machine under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the flame retardancy was evaluated. The results are shown in Table 1.

Table 1 shows that ZnST is excellent in the effect of improving the releasability, but reduces the flame retardancy. However, it can be seen that even when ZnST is present, the flame retardancy is greatly improved by reducing the residual styrene monomer and oligomer in the resin composition to 1% by weight or less.

[0146]

[Table 1]

Examples 3 to 18 HIPS having different reduced viscosities ηsp / C shown in Tables 2 and 3,
Using PPE, the residual styrene monomer, styrene dimer and trimer were mixed at the composition ratios shown in Tables 2 and 3 so that the total content of the trimers was 0.5% by weight. A similar experiment was performed and evaluated. However, when using PPE, HIPS / PPE was fed from the main feeder and melted at 300 ° C., and the remaining components were fed from the side feeder and melted at 230 ° C. in the same manner. The results are shown in Tables 2 and 3.

[0148]

[Table 2]

[0149]

[Table 3]

According to Tables 2 and 3, the total content of the residual styrene monomer and styrene dimer and trimer in the molded product is 1.0% by weight or less, and the ηsp / C of HIPS is 0% or less. .4 ~
When it is in the range of 0.6, the balance characteristics of fluidity, impact strength and flame retardancy are excellent, and when PPE is present, the balance characteristics of heat resistance, fluidity and impact strength are improved. In particular, when the reduced viscosity ηsp / C of the rubber-modified styrenic resin is 0.3 to 0.6, the balance characteristics of fluidity, heat resistance, impact strength and flame retardancy are further improved. I understand.

REFERENCE EXAMPLE Various aromatic phosphate ester monomers shown in Table 4 were allowed to stand at 250 ° C. for 5 minutes in a nitrogen gas flow by a thermogravimetric balance test method, and the residual amount was determined. The results are shown in Table 4.

[0152]

[Table 4]

Table 4 shows that the compounds as a whole exhibit excellent volatility when the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 12 or more on average.

Examples 19 to 29 In Example 1, the final resin composition was HIPS-1 / G
Except that the composition was changed to PPS / PPE-1 / aromatic phosphate described in Table 5 / ZnST = 70/30/3/7 / 0.5 (weight ratio), the production was performed in the same manner as in Example 10. And evaluated. Further, the temperature of the aromatic phosphate was raised at a rate of 40 ° C./min under a nitrogen stream by a thermogravimetric balance test method, and the relationship between the temperature and the weight loss was determined. Table 5 shows the results.

[0155]

[Table 5]

[0156]

Industrial Applicability The present invention relates to a flame-retardant styrene resin composition having excellent release properties.

The composition obtained by the method of the present invention comprises V
TR, distribution board, TV, audio player, condenser, household outlet, boombox, video cassette,
Video disk players, air conditioners, humidifiers, home appliances such as electric warm air machines, chassis or parts, CD-ROM main frames (mechanical chassis), printers, fax machines, PPCs, CRTs, word processing copiers, electronic cash register Machine, office computer system, floppy disk drive, keyboard, type, ECR, calculator, toner cartridge, OA equipment housing such as telephone, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable condenser, AC adapter, Electronic and electrical materials such as FBT high-pressure bobbins, FBT cases, IFT coil bobbins, jacks, volume shafts, motor parts, and instrument panels, radiator grilles, clusters, Kaguriru, louver, console box, is suitable for defroster garnish, ornament, fuse box, relay case, automobile materials such as connector shift tape or the like, the role is great to play in these industries.

[Brief description of the drawings]

FIG. 1 is a diagram showing a method for evaluating releasability. That is, a mold having a load cell mounted on an ejector pin is attached to an injection molding machine, injection molded after clamping, and a signal from the load cell when a cylindrical molded product is released by the ejector pin when the mold is opened. This shows an evaluation method of amplifying with an amplifier and recording on a memory recorder.

Claims (4)

[Claims] (A) 100 parts by weight of a styrene resin,
(B) 1 to 100 parts by weight of a flame retardant, (C) release agent 0.01
1 to 5 parts by weight, wherein the total content of the aromatic vinyl monomer and the dimer and trimer of the aromatic vinyl monomer remaining in the resin composition is 1 A drop-type flame-retardant resin composition having excellent releasability, wherein the composition is not more than 10% by weight. 2. The polyphenylene ether (D)
The drop-type flame-retardant resin composition according to claim 1, which is blended with 100 parts by weight. 3. The drop-type hard coating composition according to claim 1, wherein (C) is one or more compounds selected from saturated higher aliphatic carboxylic acids or metal salts thereof. Combustible resin composition. (A) 100 parts by weight of a rubber-modified styrenic resin having a reduced viscosity ηsp / C of 0.4 to 0.6 in a resin portion, (B) a flame retardant 1 to 1 represented by the following formula (1): 100
Parts by weight, (C) one or more compounds selected from saturated higher aliphatic carboxylic acids and metal salts thereof.
01 to 5 parts by weight and (D) reduced viscosity ηsp / C is 0.3
The drop-type flame-retardant resin composition according to claim 2, comprising 1 to 100 parts by weight of polyphenylene ether having a particle size of from 0.6 to 0.6. Embedded image (Where a, b, and c are 1 to 3, R ¹ , R ² , and R ³ are hydrogen or an alkyl group having 1 to 30 carbon atoms, and the substituents R ¹ , R ² , R The total number of carbon atoms of ³ is an average of 12 to 30. Here, when a plurality of aromatic phosphates having different substituents are used, the substituents R ¹ , R ² , R The total number of carbon atoms of ³ is represented by a number average and 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 substituents of each component.)