JPH09183886A - Drip type flame retardant styrene-based resin composition excellent in flowability and impact strength - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a drip type flame retardant styrene-based resin composition without generating mold deposits even when a continuous molding is carried out for a long time and excellent in flowability and impact strength by containing a specific rubber-modified styrene-based resin and a specific rate of an aromatic phosphate. SOLUTION: (A) 100 pts.wt. rubber modified styrene-based resin having 250,000-100,000 weight average molecular weight and containing <=15wt.% resin having <=40,000 molecular weight is blended with (B) 1-50 pts.wt. aromatic phosphate of the formula [(a), (b) and (c) are each 1-3; R<1> to R<3> are each H or a 1-30C hydrocarbon] such as triphenyl phosphate and preferably (C) 1-40 pts.wt. polyphenylene ether such as poly(2,6-dimethyl-1,4-phenylene-ether).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dripping type styrene-based flame retardant resin composition. More specifically, the dropping-type styrene-based flame-retardant resin composition has excellent fluidity and impact strength, and when a specific aromatic phosphate ester is used, mold deposit does not occur even after continuous molding for a long period of time. It is about.

[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, when using a halogen-based flame retardant, there are also problems such as the environment, and phosphorus-based,
When an inorganic flame retardant is used, impact strength, molding process fluidity and heat resistance are not always satisfactory, and mold contamination due to volatile organic phosphorus during molding, so-called mold deposit occurs. There is a problem that productivity is lowered, or mold contaminants are transferred to a molded product to cause stress cracks, which narrows industrial use.

Conventionally, as a method for improving the flame retardancy of styrene resins, for example, a resin composition comprising a styrene resin, a nitrogen compound such as melamine, a polyol, and an organic phosphate ester (Japanese Patent Laid-Open No. 4-117442). ), A self-extinguishing dripping type self-extinguishing styrene-based resin composition comprising a rubber-modified styrene resin having a specific average rubber particle diameter and a halogen-based flame retardant (Japanese Patent Publication No. 6-43542), polyphenylene ether / polystyrene / red phosphorus. (US Patent 3
663654), polyphenylene ether / phosphate ester / thermoplastic elastomer (US Pat. No. 468468).
2), polyphenylene ether / polystyrene / organic phosphorus compound (JP-A-57-153035), and polyphenylene ether / polystyrene / organic phosphorus compound /
A resin composition comprising a triazine compound (European Patent No. 311909) is disclosed. However, the resin composition of the publication is not necessarily satisfactory in flame retardancy, molding fluidity and impact strength, and has not been put into practical use.

As a technique for improving volatility, a resin composition for a laminate comprising a phenol 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 target of the flame retardant of this publication is a thermosetting resin, which is different from the styrene resin composition of the present invention.

Further, an antistatic agent composed of a sulfonate and a phosphoric acid ester such as dinonylphenylphenylphosphate (JP-A-3-64368), and a triarylphosphate such as a polyol ester and bisnonylphenylphenylphosphate. (US Pat. No. 4,780,229), which is not a flame retardant composition but is essentially different from the present invention.

[0007] Then, polycarbonate, ABS resin,
Resin composition composed of halogenated phosphate and polytetrafluoroethylene (WO9106598), resin composition composed of polycarbonate, AAS resin, phosphate and polytetrafluoroethylene (EP53429)
7), a resin composition (DE4309142) composed of polycarbonate, ABS resin, phosphate ester, and polytetrafluoroethylene; a resin composition composed of polycarbonate, ABS resin, aromatic phosphate ester, and metal salt of aromatic sulfonic acid (JP-A-Hei. 6-299060),
Polycarbonate, polyester-polycarbonate,
A resin composition (EP482451) comprising an ABS resin, a phosphate ester, and polytetrafluoroethylene, and a resin composition (DE4016417) comprising a polycarbonate, an ABS resin, a phosphate ester, and a polycarbonate-siloxane block copolymer are known. Since the phosphoric acid ester used in the above polycarbonate resin composition does not use a phosphoric acid ester monomer having a specific substituent, the phosphoric acid ester has poor volatility-resistant and flame-retardant balance characteristics.

Next, a flame retardant comprising a phosphate comprising a phenyl group, an isopropylphenyl group and an alkyl-substituted phenyl group having 4 to 12 carbon atoms (Japanese Patent Laid-Open No. 2-7)
No. 92, EP324716, the same corresponding application), a flame-retardant resin composed of polyphenylene ether / styrene resin / tris (isopropylphenyl) phosphate (JP-A-1-48844), polystyrene / t-butylphenyl phenyl phosphate / Functional fluid composition comprising polyol ester (functioniona)
l fluid composition) (USP4
645615). According to the definition of the present invention, the number-average carbon number of the substituent of the phosphate in the publication is less than 12, and thus the volatility is not sufficient.

Further, tris (4-phenylphenyl)
Flame-retardant resin compositions containing phosphates in which the substituents R ¹ , R ² and R ³ of the present application are aromatic hydrocarbons, such as phosphate and tris (benzylphenyl) phosphate (DE 4016417, EP 534297, EP 534)
297) is disclosed. Although the flame retardant composition containing the above-mentioned phosphate is excellent in heat resistance, it is inferior in fluidity and flame retardancy.

A flame-retardant resin composition comprising a polyphenylene ether, a styrene resin, a metal salt of phosphoric acid, and a phosphate such as tris (nonylphenyl) phosphate as a flame-retardant technique for a styrene resin (Japanese Patent Laid-Open No. 63- Thirty
No. 5161), a polyphenylene ether resin composition (EP5502) comprising polyphenylene ether and high molecular weight polyethylene as essential components and, if necessary, a phosphate such as tris (nonylphenyl) phosphate.
04), an aromatic polycarbonate, an ABS resin, an AS resin, a phosphate such as tris (nonylphenyl) phosphate, an aromatic sulfonate, and a fibrous reinforcing material (JP-A-6-299060). Gazette). The resin composition of the above-mentioned 3 gazette has low flame retardancy because it contains a phosphate such as tris (nonylphenyl) phosphate, and it is heat resistant when a large amount of the phosphate is added in order to improve the flame retardancy. Sex significantly decreases. Also, tris (nonylphenyl)
By combining a specific amount of phosphate with bis (nonylphenyl) phenyl phosphate and nonylphenyl diphenylphosphate, flame retardancy, fluidity,
It is not disclosed that the balance characteristics of heat resistance, impact strength, and water gloss retention are remarkably improved.

As another flame-retardant technique, carbon number of 4 to 2
Production of a phosphoric acid triester comprising a hydrocarbon group selected from an alkyl group having 2 to 12 carbon atoms, an alkenyl group having 12 to 22 carbon atoms, a phenyl group, and an alkylphenyl group having 7 to 15 carbon atoms (alkyl group having 1 to 9 carbon atoms). Method (JP-A-3-29
No. 4284) is disclosed. Not only is the publication different in that it is a manufacturing method, but the publication uses a specific substituent-containing aromatic phosphate ester monomer to maintain flame retardancy, particularly in styrene resins. At the same time, it is not disclosed or even implied that the continuous formability (volatility resistance) is significantly improved.

Finally, a phosphate monomer containing a plurality of isopropyl groups and a flame retardant composition thereof (GB202).
7712, US4370281, JP-B-63-6131
3, the same corresponding application). According to the definition of the present invention, the total number average carbon number of the phosphate substituents in the publication is as wide as 6 to 47 according to the definition of the present invention. Is not disclosed. In addition, by having a specific substituent of the present invention, flame retardancy, especially not only that the drip-type flame retardancy is improved, it is not described,
Not even implied.

[0013]

In view of the above situation, the present invention does not have the above-mentioned problems, that is, has excellent fluidity and impact strength, and uses a specific aromatic phosphate ester. In this case, it is an object of the present invention to provide a drop-type styrene-based flame-retardant resin composition that does not cause mold deposit even after continuous molding for a long period of time.

[0014]

Means for Solving the Problems As a result of intensive studies on a technique for improving fluidity and impact strength, the present inventors have found that when a resin having a specific weight average molecular weight and a specific molecular weight is present in a specific amount, impact It has been found that it becomes possible to dramatically improve the fluidity while maintaining the strength. And, by using an aromatic phosphoric acid ester monomer containing a specific substituent as the aromatic phosphoric acid ester, surprisingly, while suppressing the mold deposit, the flame retardancy of the styrene resin is improved. The present invention has been completed by finding that it can be dramatically improved.

That is, according to the present invention, 100 parts by weight of the rubber-modified styrenic resin is used and 1 to 50 aromatic phosphates are added.
A styrene-based resin composition containing 1 to 40 parts by weight of polyphenylene ether as an essential component, and a weight average molecular weight of the resin portion of the rubber-modified styrene-based resin is 250,000 to 100,000. And a dropping-type flame-retardant styrene resin composition having excellent fluidity and impact strength, characterized in that the weight of the resin having a molecular weight of 40,000 or less in the resin portion is 15% by weight or less, and particularly aromatic A flame-retardant styrene-based resin composition in which the group phosphate is represented by the following formula (1).

[0016]

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(Where a, b, and c are 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or a hydrocarbon 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 25 on average in the entire compound. Here, in the case of being composed of a plurality of aromatic phosphates having different substituents, the substituent R ¹ of the above aromatic phosphates,
The total number of carbon atoms of R ² and R ³ is represented by a number average, and is represented by the weight fraction of each aromatic phosphate ester component in the aromatic phosphate ester and the total number of carbon atoms of the substituents of each component. It is the sum of products. Hereinafter, the present invention will be described in detail.

The dropping-type flame-retardant styrene resin composition of the present invention is a rubber-modified styrene resin (A) having a specific molecular weight.
Component), and optionally polyphenylene ether (B component) and aromatic phosphate ester (C component).

The above-mentioned component A constitutes the main component of the molding resin composition and plays a role of maintaining the strength of the molded product. The component B is a component that improves the heat resistance and flame retardancy of the component A, and the component C is a flame retardant and acts as a drip accelerator during combustion.

Here, the weight average molecular weight of the resin portion of the component A is 250,000 to 100,000, and the molecular weight of the component A is 4
It is essential that the weight of ten thousand or less of the resin is 15% by weight or less. When the weight average molecular weight exceeds 250,000, the impact strength is excellent, but the fluidity is poor. On the other hand, when the weight average molecular weight is less than 100,000, the impact strength is significantly reduced. The resin having a molecular weight of 40,000 or less in the component A is an aromatic vinyl-based resin containing an aromatic vinyl monomer and a dimer or trimer of the aromatic monomer, and the weight thereof is 15 When it exceeds the weight%, the impact strength is remarkably reduced.

Further, when 1 to 40 parts by weight of polyphenylene ether is further contained with respect to 100 parts by weight of the rubber-modified styrene resin, the heat resistance is improved.

In the case of a specific alkyl group-substituted aromatic phosphate ester as the aromatic phosphate ester,
A drop-type styrene-based flame-retardant resin composition that does not cause mold deposit even after continuous molding for a long period of time is obtained.

It is important that the aromatic phosphate ester is a monomer, not a condensate. Since it is a monomer, it vaporizes efficiently at the beginning of combustion. In particular, in the case of a drip-type flame-retardant styrene-based resin, since it is a monomer, the plasticity of the styrene-based resin is promoted, and the dripping property during combustion is improved.

Next, the substituents R ¹ , R ² and R ³ of the aromatic phosphate ester monomer are hydrogen or an alkyl group having 1 to 30 carbon atoms, and the substituent R ¹ ,
The number average of the total carbon numbers of R ² and R ³ is preferably 12 to 25. When the number average of the total number of carbon atoms is less than 12, flame retardancy is excellent, but volatility is high, while 25
It has been found that the flame retardancy is deteriorated when it exceeds.

The aromatic phosphoric acid ester satisfying the above requirements has a weight loss at 300 ° C. of 0 to 10% by weight and a temperature of 400 ° C. in a heating test in nitrogen (heating rate of 40 ° C./min). 30 to 100% by weight, preferably 5
0 to 100% by weight. That is, the weight loss at 300 ° C is 1
Since the content is 0% by weight or less, no mold deposit is generated in the molding of the styrene resin, and on the other hand, at 400 ° C. in the initial stage of combustion, rapid vaporization causes flame retardancy due to the gas phase effect. Furthermore, they found that the presence of a specific substituent group improves the compatibility with the styrene-based resin, so that the dropping property is significantly promoted, and the present invention has been completed.

The rubber-modified styrene-based resin (component A) used in the dropping type flame-retardant styrene-based resin composition of the present invention comprises a rubber-modified styrene-based resin alone or a rubber-modified styrene-based resin and a rubber-unmodified styrene-based resin. There is no particular limitation as long as it is compatible or evenly dispersed with the components B, C. 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. It can be obtained by adding a monomer and, if necessary, a vinyl monomer copolymerizable therewith, and subjecting the monomer mixture to known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization.

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

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), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers, chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like, and a diene rubber is particularly preferable.

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 styrene resin. 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 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. Particularly, α-methylstyrene and butyl acrylate are excellent in dropping type flame retardancy. 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. Furthermore, the rubber particle diameter of the styrene 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 weight average molecular weight of the resin portion of the rubber-modified styrenic resin is 250,000 to 100,000, and means for satisfying the above requirements regarding the weight average molecular weight are as follows: the amount of polymerization initiator, the polymerization temperature, the amount of chain transfer agent. Can be mentioned. For example, in order to increase the weight average molecular weight, the polymerization initiator, the chain transfer agent are reduced, or the polymerization temperature is lowered.

The weight of the resin having a molecular weight of 40,000 or less in the resin portion of the rubber-modified styrene resin is 15% by weight or less.
For that purpose, for example, in continuous solution polymerization, polymerization is carried out at a uniform temperature in a complete mixing polymerization vessel, or by using a polymerization initiator in a star tube polymerization vessel.

In the dropping type flame-retardant styrene resin composition of the present invention, another thermoplastic resin can be mixed with the rubber-modified styrene resin. For example, a polyphenylene ether type, a polyamide type, a polyester type, a polyphenylene sulfide type, a polycarbonate type, a polymethacrylate type, etc. may be used alone or in combination of two or more. Here, a polyphenylene ether-based or polycarbonate-based thermoplastic resin is particularly preferable as the thermoplastic resin that can be added to the styrene-based resin.

Polyphenylene ether (component B) which can be blended with the rubber-modified styrene resin is represented by the following formula:
It is a homopolymer and / or a copolymer composed of the bonding unit represented by (2).

[0038]

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However, R ¹ , R ² , R ³ , and R ⁴ are each selected from the group consisting of hydrogen, hydrocarbons, and substituted hydrocarbon groups, and may be the same or different from each other. As specific examples of the polyphenylene ether, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like are preferable. Among them, poly (2,6-dimethyl-1,4-phenylene ether) is preferable. The method for producing such a polyphenylene ether is not particularly limited, and 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 is used. Can be easily produced by oxidative polymerization of the above compounds. In addition, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, and Japanese Patent Publication 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.

The amount of polyphenylene ether is preferably 1 to 100 parts by weight of the rubber-modified styrene resin.
40 parts by weight, more preferably 1 to 10 parts by weight, most preferably 3 to 8 parts by weight.

The aromatic phosphate ester (component C) used in the dropping type flame-retardant styrene resin composition of the present invention is, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, phenyl neo. Pentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate, ethyl pyrocatechol phosphate,
Examples thereof include dipyrocatechol hyposiphosphate, tetraphenylresorcin diphosphate, tetraphenylbisphenol A diphosphate, tetracresyl bisphenol A diphosphate and the like.

Among these, the aromatic phosphate ester monomer represented by the following formula (1) is particularly preferable.

[0043]

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(Where a, b, and c are 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or a hydrocarbon 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 25 on average in the entire compound. Here, in the case of being composed of a plurality of aromatic phosphates having different substituents, the substituent R ¹ of the above aromatic phosphates,
The total number of carbon atoms of R ² and R ³ is represented by a number average, and is represented by the weight fraction of each aromatic phosphate ester component in the aromatic phosphate ester and the total number of carbon atoms of the substituents of each component. It is the sum of products. ) Here, among the aromatic phosphate ester monomers, the number average of the total carbon numbers of the substituents R ¹ , R ² , and R ³ is preferably 14 to 22, more preferably 16 to 20, and 17 to 19
Is most preferred.

Specific examples of the substituent include a butyl group such as nonyl group and t-butyl group, t-amyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, tridecyl group. , A tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an otadecyl group, a nonadecyl group, an octadodecyl group, etc., and one or a plurality of substituents on one aromatic ring at any position of ortho, meta, and para. , But para-substitutes are preferred. The total number of carbon atoms of the alkyl group substituted by one phosphate ester monomer is 12 to
Most preferably in the range of 25, but there are more than one aromatic ring substituted with one alkyl group than in a phosphate ester monomer having only one aromatic ring substituted with one long chain alkyl group. The phosphoric acid ester monomer which it has is superior in 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.

Among the aromatic phosphoric acid ester monomers, a phosphoric acid ester monomer in which at least one of R ¹ , R ² and R ³ is a nonyl group is preferable, and R ¹ and R ² are nonyl groups. And an aromatic phosphoric acid ester monomer [bis (nonylphenyl) phenyl phosphate] in which R ³ is hydrogen is most preferable. 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.

From the viewpoint of volatile resistance, the total number of carbon atoms of the substituents must satisfy the requirements of the present invention, but the proportion of the total number of carbon atoms of the substituents is less than 12 is 20% by weight or less. In some cases, even better volatility resistance is developed.

From the viewpoint of the thermal stability of the aromatic phosphoric acid ester monomer, particularly the heat discoloration resistance, the acid value defined in JIS-K6751 as an index of the residual acidic substance is 1 m.
gKOH / g or less, more preferably 0.5 mgKOH / g, and / or alkylphenol is preferably 1% by weight or less, more preferably 0.5% by weight or less, and aluminum, magnesium, sodium, antimony is 100% or less.
It is more preferably 0 ppm or less. Moreover, the hindered phenolic antioxidant is 1 to 1000 in the flame retardant.
When the content is ppm by weight, thermal stability is dramatically improved.

Next, from the viewpoint of light resistance, the substituents R ¹ , R ² and R ³ are not aryl groups, and even in the case of an alkyl group, it is preferable that the alkyl group has less branching, particularly straight chain or branching. A single alkyl group is particularly preferred. Even at the same branch, the light resistance of the alkyl group having 5 or less carbon atoms is poor, and the light resistance of the phosphate ester monomer having an isopropyl group is poor.

Further, the number of substituents substituting 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 preferable combination of aromatic phosphate ester monomers is nonylphenyldiphenylphosphate (NPDP), bis (nonylphenyl) phenylphosphate (BNPP), tris (nonylphenyl).
Phosphate (TNPP), the substituent R ¹ ,
The number average of the total carbon numbers of R ² and R ³ is 12 to 25, preferably 14 to 22, and more preferably 16 to 2.
0, with 17-19 being most preferred. In order to satisfy the above number average of the total number of carbon atoms, for example, NPDP is 1 to
80% by weight, preferably 1 to 50% by weight, more preferably 1 to 30% by weight, most preferably 1 to 10% by weight, and BNPP is 1 to 98% by weight, preferably 20 to 90% by weight, more preferably 30% by weight. -80% by weight, most preferably 40-80% by weight, TNPP is 1-98% by weight, preferably 1-70% by weight, more preferably 5-6%.
It is in the range of 0% by weight, most preferably 5 to 50% by weight. The aromatic phosphate ester monomer of such a combination is particularly excellent in flame retardancy, fluidity, heat resistance, impact strength, water gloss retention, and balance characteristics of surface hardness of the obtained molded product. . A specific effect is exhibited by mixing a specific amount of aromatic phosphate ester monomers having different nonyl group substitution numbers. NPDP has a high plasticizing effect and acts not only as a fluidity improver but also a very high flame retardancy improving effect. TNPP not only has a high volatility- and heat-resistance-imparting effect, but is also extremely excellent in water gloss retention. BNP
P is excellent in the balance characteristics of the above characteristics, but when the three are blended in specific amounts, the balance characteristics not obtained by themselves are exhibited. In particular, improvements in water-resistant gloss retention and surface hardness of the molded product cannot be predicted by conventional knowledge.

Such aromatic phosphate ester monomers are disclosed in JP-A-1-95149 and JP-A-3-2942.
It can be produced by a known method disclosed in Japanese Patent Publication No. 84 and the like. For example, a method of reacting alkylphenol, phosphorus oxychloride, and anhydrous aluminum chloride as a catalyst under heating, or oxidizing a phosphite triester with oxygen,
There is a method of converting to the corresponding aromatic phosphate ester.

In the dropping type flame-retardant styrene resin composition of the present invention, 100 parts by weight of the rubber-modified styrene resin is added.
It is preferable to contain 1 to 50 parts by weight of the aromatic phosphate ester, more preferably 1 to 20 parts by weight, and most preferably 3 to 8 parts by weight.

The dropping type flame-retardant styrenic resin composition of the present invention contains a polyorganosiloxane (D component), if necessary.
Can be compounded, whereby the orientation of the rubber-modified styrene resin is relaxed. When molding with high shear force,
Orientation remains in the obtained molded body, which hinders the dropping of fire species. Then, by blending a polyorganosiloxane having a specific kinematic viscosity, the slippage of the molecular chains is exhibited, whereby the orientation is suppressed, and as a result, the resin composition molded article is promoted with easy dripping. The polyorganosiloxane has a kinematic viscosity (25 ° C.) of preferably 30 to 20000 CS, and 4
0 to 1000 CS is more preferable, most preferably 50
~ 100 CS. If the kinematic viscosity is less than 30CS, the volatility is high and the mold is contaminated during molding.
If it exceeds CS, the orientation relaxation property of the styrene resin is deteriorated.

As the component D, polydimethylsiloxane, so-called silicone oil, is particularly preferable.

The amount of polyorganosiloxane is preferably 0.1% based on 100 parts by weight of the rubber-modified styrene resin.
01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, most preferably 0.3 to 3 parts by weight.

The dropping-type flame-retardant styrene resin composition of the present invention contains a flame-retardant agent (component E) other than the above-mentioned flame-retardant agent, if necessary.
As the component, an organic phosphorus compound other than the component C, red phosphorus, an inorganic phosphate, an inorganic flame retardant or the like can be added.

The amount of the E component is the rubber-modified styrene resin 1
100 parts by weight, preferably 1 to 40 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 5 to 1 part by weight.
0 parts by weight.

Examples of the organophosphorus compound as the E component include phosphine, phosphine oxide, biphosphine,
Examples include phosphonium salts, phosphinates, and phosphites. More specifically, it is methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, dineopentyl hypophosphite, phenylpyrocatechol phosphite and the like.

The red phosphorus as the E component is, in addition to ordinary red phosphorus, the surface thereof is previously coated with a film of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. Treated, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, treated with a coating consisting of a metal hydroxide selected from titanium hydroxide and a thermosetting resin, aluminum hydroxide, magnesium hydroxide, For example, a metal hydroxide selected from zinc hydroxide and titanium hydroxide may be doubly coated with a thermosetting resin film.

The inorganic phosphate as the E component is typically ammonium polyphosphate.

As the inorganic flame retardant as the E component, aluminum hydroxide, magnesium hydroxide, dolomite,
Hydrate of inorganic metal compounds such as hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, hydrate of tin oxide, zinc borate, zinc metaborate, barium metaborate, carbonic acid zinc,
Magnesium carbonate, mu calcium, calcium carbonate,
Barium carbonate and the like can be mentioned. These may be used alone or in combination of two or more. Among them, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate,
The one selected from the group consisting of hydrotalcite has a good flame retardant effect and is economically advantageous.

The dropping type flame-retardant styrenic resin composition of the present invention is, if necessary, a triazine skeleton-containing compound, a novolac resin, a metal-containing compound, a silicone resin, a vinyl-containing silicone oil, silica, an aramid fiber, a fluorine-based compound. One or more flame retardant aids (F component) selected from resin and polyacrylonitrile fiber can be blended.

The amount of F component is the rubber-modified styrene resin 1
The amount is preferably 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 5 to 10 parts by weight with respect to 00 parts by weight.

The triazine skeleton-containing compound as the component F 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 (the following formula (3)), melem (the following formula (4)), melon (a product of deammonification of 3 molecules of melem at 600 ° C or higher), melamine cyanurate. (The following formula
(5)), melamine phosphate (the following formula (6)), succinoguanamine (the following formula (7)), adipoguanamine, methylglutaloganamin, melamine resin (the following formula (8)), BT resin (the following) Formula (9)) and the like can be mentioned, but melamine cyanurate is particularly preferable from the viewpoint of volatile resistance.

[0066]

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[0067]

[Chemical 6]

[0068]

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[0069]

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[0070]

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The novolak resin as the F component is a flame retardant aid and, when used in combination with a hydroxyl group-containing aromatic phosphate, also serves as 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 production of novolac resin is shown in the following formulas (10) and (11).

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The above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol and 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 the component F is a metal oxide and / or a 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 as the component F is SiO 2
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 silicone resin can be obtained by co-hydrolyzing and polymerizing the organohalosilane corresponding to the above structural unit.

The vinyl-containing silicone oil as the F component is a polydiorganosiloxane having a chemical bond unit represented by the following formula (12).

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R in the above formula is C1-8 alkyl group, C
6 to 13 aryl groups, and one or more substituents selected from vinyl-containing groups represented by the following formulas (13) and (14), in which a vinyl group is particularly contained in the molecule.

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The viscosity of the vinyl-containing silicone oil is preferably 600 to 1,000,000 centipoise (25 ° C.), more preferably 90,000 to 150,000.
It is a centipoise (25 ° C.).

The silica as the component F is amorphous silicon dioxide. Particularly, silica coated with a hydrocarbon compound, the surface of which is treated with a silane coupling agent of a hydrocarbon compound, is preferable. Hydrocarbon compound-coated silica 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
An 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 silane coupling agent on the silica surface 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 the F component 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 into an amide polar solvent or sulfuric acid. It can be manufactured by dissolving and solution spinning by a wet or dry method.

The fluorine-based resin as the component F is a flame-retardant aid, and is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer.
If necessary, the fluorine-containing monomer may be used in combination with a copolymerizable monomer so long as the drip resistance is not impaired.

The polyacrylonitrile fiber as the component F 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 then dry-spun in which the polymer is dry-spun in an air stream at 400 ° C, or the polymer is dissolved in a solvent such as nitric acid and wet-spun in water. It is manufactured by a spinning method.

The dropping-type flame-retardant styrene resin composition of the present invention comprises 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 ester, if necessary. One or more fluidity-improving agents (component G) selected from fatty acid amides, higher aliphatic alcohols, or metal soaps can be added.

The amount of G component is the rubber-modified styrene resin 1
0.1 to 20 parts by weight with respect to 00 parts by weight,
More preferably, it is 0.5 to 10 parts by weight, most preferably 1 to 5 parts by weight.

The aromatic vinyl unit of the copolymer resin as the component G includes, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like. Styrene is most preferred, but other aromatic vinyl monomers described above 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 the G component include liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides, fluorides and chlorides thereof.

The higher fatty acids as the G component include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid and ferric acid, and ricinoleic acid, lysine veridic acid, 9-oxy12 octadecenoic acid and the like. Unsaturated fatty acids and the like.

The higher fatty acid ester as the G component 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 stearate of diphenylstearyl phthalate. Yes, further, 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, stearic acid monoglyceride,
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.

Higher fatty acid amides as the G component 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'-2-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
An aromatic bisamide such as -hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohol as the G component 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 the G component is a metal salt of a higher fatty acid such as stearic acid, such as barium, calcium, zinc, aluminum or magnesium.

The dropping-type flame-retardant styrene resin composition of the present invention may contain a thermoplastic elastomer (H component), if necessary. For example, polystyrene type, polyolefin type, polyester type, polyurethane type, 1,2
-Polybutadiene type, polyvinyl chloride type, etc., and polystyrene type thermoplastic elastomer is particularly preferable.

[0104] The amount of the H component is determined according to 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 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 above block copolymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromo. Styrene and the like are preferable, and styrene is the most preferable, but styrene as a main component and other aromatic vinyl monomer may be copolymerized.

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) linear block copolymer, (SB) _n X (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.

The dropping type styrene resin composition of the present invention is
When light resistance is required, one or two selected from an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, a halogen scavenger, a light shielding agent, a metal deactivator, or a quencher, if necessary. More than one type of light resistance improver (component I)
Can be blended.

The amount of the component I is the rubber-modified styrene resin 1
It is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and most preferably 1 to 5 parts by weight with respect to 00 parts by weight.

The ultraviolet absorber as the component I absorbs light energy and becomes a keto-type molecule by intramolecular proton transfer (benzophenone, benzotriazole type), or by cis-trans isomerization ( (Cyanoacrylate-based), a component for releasing as heat energy and detoxifying. Specific examples are 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as hydroxy-4-methoxybenzophenone) and 2- (2′-hydroxy-
5'-methylphenyl) benzotriazole, 2-
(2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′,
5′-di-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3′-t-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′- 2- (2 ′) such as methylenebis (4-t-octyl-6-benzotriazolyl) phenol
-Hydroxyphenyl) benzotriazoles, phenyl salicylate, resorcinol monobenzoate,
2,4-di-t-butylphenyl-3 ′, 5′-di-t
Benzoates such as -butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyl Substituted oxanilides such as oxanilide; and cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

The hindered amine-based light stabilizer as the component I decomposes hydroperoxide generated by light energy to give stable N--O. Radicals, N--OR and N.
It is a component for generating and stabilizing —OH. Specific examples thereof include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl Methyl-4-piperidyl benzoate, bis (2,
2,6,6-tetramethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) -1,2,2
3,4-butanetetracarboxylate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3 ', 5'-
Di-t-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-
Tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis ( 2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-t-octylamino-s-triazine polycondensate, 1,6-bis (2,2,6, 6-tetramethyl-4
-Piperidylamino) hexane / 2,4-dichloro-6
-Morpholino-s-triazine polycondensate and the like.

The antioxidant as the component I is for stabilizing peroxide radicals such as hydroperoxy radicals generated during thermoforming or by exposure to light, or for decomposing the generated peroxides such as hydroperoxide. Is a component of. Examples are hindered phenolic antioxidants and peroxide decomposers. The former serves as a radical chain inhibitor, and the latter decomposes the peroxide generated in the system into more stable alcohols to prevent autoxidation.

Specific examples of the hindered phenolic antioxidant as the antioxidant include 2,6-di-t-butyl-4-methylphenol, styrenated phenol and n-octadecyl-3- (3. , 5-Di-t-butyl-4-hydroxyphenyl) propionate, 2,2 ′
-Methylenebis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-
Di-t-pentylphenyl) ethyl] -4,6-di-t
-Pentylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-t-butylphenol),
4,4′-thiobis (3-methyl-6-t-butylphenol), alkylated bisphenol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3 , 9-
Bis [2- [3- (3-t-butyl-4-hydroxy-
5-methylphenyl) -propionyloxy] -1,1-
Dimethylethyl] -2,4,8,10-tetraoxyspiro [5.5] undecane.

Specific examples of the peroxide decomposing agent as the antioxidant include trisnonylphenyl phosphite,
Triphenyl phosphite, tris (2,4-di-t-
Organic phosphorus peroxide decomposers such as butylphenyl) phosphite or dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipro Pionate,
It is an organic sulfur peroxide decomposer such as pentaerythrityltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole and the like.

The halogen scavenger as the component I is a component for scavenging free halogen generated during thermoforming or light exposure. Specific examples thereof include basic metal salts such as calcium stearate and zinc stearate, hydrotalcite, zeolite, magnesium oxide, organotin compounds, and organic epoxy compounds.

The hydrotalcite as the halogen scavenger is a water-containing basic carbonate or anhydrous basic carbonate of magnesium, calcium, zinc, aluminum, bismuth and the like, and includes natural products and synthetic products. Examples of natural products include those having a structure of Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. In addition, as a synthetic product, Mg _0.7 Al
_0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂ O, Mg _4.5 Al
₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, Mg _4.2 Al ₂ (OH) _12.4
CO ₃ , Zn ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Ca ₆ Al
₂ (OH) ₁₆ CO ₃ · 4H ₂ O, Mg ₁₄ Bi ₂ (OH) _29.6 ·
4.2H ₂ O, and the like.

Examples of the zeolite include Na ₂ O.Al ₂
O ₃ · 2SiO can be mentioned zeolite substituted by a metal containing at least one metal selected from A-type zeolites or the Periodic Table Group II and Group IV metal, represented by ₂ · H ₂ O . And as a substitution metal, it is Mg, Ca, Zn, Sr, Ba, Zr, Sn, etc., and especially Ca, Zn, Ba is preferred.

The organic epoxy compound as the halogen scavenger is epoxidized soybean oil, tris (epoxypropyl) isocyanurate, hydroquinone diglycidyl ether, terephthalic acid diglycidyl ester, 4,4 ′.
-Sulfobisphenol / polyglycidyl ether, N
-Glycidyl phthalimide or hydrogenated bisphenol A glycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexylspiro [5,5] -3,4-epoxy ) Cyclohexane-m-
Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4
-Epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-
3,4-Epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene epoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4- Epoxy cyclohexane carboxylate), Dioctyl epoxy hexahydrophthalate, Di-hexahexahydrophthalate
Alicyclic epoxy compounds such as 2-ethylhexyl;

The light-shielding agent as the I component is a component for preventing light from reaching the inside of the polymer. Specific examples thereof include rutile-type titanium oxide (TiO ₂ ), zinc oxide (ZnO), chromium oxide (Cr ₂ O ₃ ), and cerium oxide (CeO ₂ ).

The metal deactivator as the component I is a component for forming a chelate compound and deactivating heavy metal ions in the resin in the chelate compound. Specific examples thereof include an acid amine derivative, benzotriazole, and derivatives thereof.

The quencher as the component I is a component for deactivating the photoexcited functional groups such as hydroperoxide and carbonyl group in the polymer by energy transfer, and organic nickel and the like are known.

The method for producing the resin composition containing the low volatility flame retardant for the styrene resin of the present invention is as follows. First, the rubber-modified styrene resin and another thermoplastic resin are melted, and then the flame retardant of the present invention is used. A method of melt-kneading with the same extruder, or a rubber-modified styrenic resin, another thermoplastic resin, or after producing a masterbatch containing the flame retardant of the present invention, if necessary, with the above masterbatch. There is a method of kneading the remaining rubber-modified styrene resin or the remaining flame retardant of the present invention or other flame retardant. Here, the following method is particularly preferable as a method when polyphenylene ether is used as the thermoplastic resin.

In the dropping type flame-retardant styrenic resin composition of the present invention, one of the methods for producing a resin composition containing polyphenylene ether as an essential component is to divide a rubber-modified styrenic resin into two parts, first of which 50% by weight is used. The resin component containing the rubber-modified styrenic resin and polyphenylene ether contained above is adjusted, and 250 to 35 is added in the front stage of the twin-screw extruder.
13. The remaining components of the rubber-modified styrenic resin which do not melt in the latter stage of the twin screw extruder after melting at 0 ° C.
2. A method for producing a resin composition, which comprises melt-extruding any one of the flame retardants at 200 to 300 ° C.

First, it is important that the resin component having a rubber-modified styrenic resin and polyphenylene ether that melts in the preceding stage of the twin-screw extruder contain 50% by weight or more of polyphenylene ether. If the content of polyphenylene ether is less than 50% by weight, an unmelted polyphenylene ether is formed because no shear force is applied.

Next, it is preferable to separate the resin component and the flame retardant. When the resin component is melted in the presence of the flame retardant, an unmelted substance is produced because the difference in viscosity between the two is large. Specifically, a rubber-modified styrene resin containing 50% by weight or more of polyphenylene ether and a resin component having polyphenylene ether are melted at 250 to 350 ° C., and then the remaining resin component and the flame retardant of the present invention are mixed with 200 ~ 300
Melts at ° C.

When the resin component containing polyphenylene ether is melted at less than 250 ° C., an unmelted product of polyphenylene ether is produced, while when it exceeds 350 ° C., decomposition of the styrene resin begins. When the flame retardant of the present invention is melted at less than 200 ° C., the compatibility between the resin component and the flame retardant is lowered, so that the flame retardant is phase-separated and stable extrusion becomes difficult. On the other hand, if the melting temperature of the flame retardant exceeds 300 ° C, the flame retardant may volatilize or decompose, which is not preferable.

In the method for producing the dropping type flame-retardant styrene resin composition of the present invention, the ratio of the screw length (L) to the cylinder inner diameter (D) (L /
D) is 20 to 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. A kneading portion between the opening 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 1 respectively.
It is preferably 0D.

First of all, the above L / D is 20 to 5
It is preferably 0. If the L / D is less than 20, the melt-kneading state is poor, and unmelted polyphenylene ether is generated. On the other hand, if the L / D exceeds 50, the residence time of the resin composition in the extruder becomes longer, and May deteriorate.

Secondly, it is preferable to have two or more supply openings having different distances from the tip of the twin-screw extruder. At one supply opening, phase separation occurs between the polyphenylene ether having a high melt viscosity and the flame retardant of the present invention having a low melt viscosity. Therefore, it is preferable to provide two or more supply openings, melt the resin component in the main feed opening, and then feed the flame retardant of the present invention from the side feed opening.

Thirdly, a kneading portion is provided between the main feed opening portion and the side feed opening portion and between the extruder tip portion and the side feed opening portion, and the kneading portions have respective lengths. It is preferably 3D to 10D. If the length of the kneading portion is less than 3D, the melt-kneading state is poor, venting occurs, or unmelted material such as polyphenylene ether is generated. On the other hand, if it exceeds 10D, the residence time of the resin composition in the extruder is exceeded. Becomes longer,
The resin deteriorates. When there are a plurality of side feed openings, the requirement of the above kneading portion is also required between the main feed opening and the side feed opening, between different side feed openings, and between the tip end and the side feed opening. Need to meet.

Fourth, the kneading part of the twin-screw extruder is a part for improving kneading and mixing,
It is composed of at least one of (1) a full flight screw portion having a special mixing element, (2) a reverse screw portion, and (3) a kneading disc or a kneading block.

The above-mentioned (1) the full flight screw portion having the special mixing element is a mixing element such as a dullage screw, a fluted mixing screw, a unimelt screw, a spiral barrier screw, a pin screw, a pineapple mixer, a cavity transfer mixer and the like. .

The (2) reverse threaded portion has a function of suppressing the flow of resin and generating a back pressure, and has a large kneading ability.

The mixing part called the kneading disc or kneading block (3) is formed by inclining a disc which is an oval plate little by little. The combination inclining by 90 ° has no propulsion force, but has good kneading ability. The combination in which the screws are inclined at an angle of 30 ° to the forward screw side has a propulsive force but a small kneading ability. In addition, the disks are thick and thin, and the thick ones have low propulsion and low mixing ability, but have good kneading or shearing ability. On the other hand, a thin one has a large propulsive force and a large mixing ability, but the kneading ability is poor.

Regarding the shape of the kneading disc,
There is a triangular conical type three-way disc and two-way disc. 3
Since the strip disk has a shallow groove, the shearing force is excessive, but since there are many opportunities for separation and merging at the meshing portion, the distribution and mixing properties are excellent. The double disk has a smaller shear force than the double disk.

Mixing / kneading of the kneading disk can be controlled by the shape, angle, number of disks, thickness, etc. of the disk.

Fifth, the twin-screw extruder may be a twin-screw co-rotating extruder or a twin-screw different-direction rotating extruder. Also,
For screw engagement, non-engaging type,
There are a partial meshing type and a full meshing type, and any type may be used. In order to obtain a uniform resin at a low temperature by applying a low shearing force, a different direction rotation / partial engagement screw is preferable. When slightly large kneading is required, a co-rotating / completely meshing screw is preferable. When even greater kneading is required, a co-rotating and fully meshing screw is preferred.

The most preferable method for producing the dropping type flame-retardant styrene resin composition of the present invention is a master batch of a resin component consisting of polyphenylene ether and an aromatic phosphoric acid ester, or the above resin component as an essential component, and rubber-unmodified Method for producing a resin composition in which a master batch of a resin composition containing a styrene resin and / or a rubber-modified styrene resin is produced, and then the remaining components of the final resin composition are added to the master batch and melt-extruded In the above, the glass transition temperature (Tg) of the masterbatch is 70 to 1
The method for producing a resin composition is characterized in that the temperature is 00 ° C.

Here, it is preferable to produce the above masterbatch. If all of the above components are melt-extruded at the same time without producing the above masterbatch, polyphenylene ether and aroma are first added in an extruder comprising a plurality of zones. Group phosphoric acid ester, and a resin composition comprising a rubber-modified styrenic resin, or a resin composition comprising a polyphenylene ether or an aromatic phosphoric acid ester is melted, and then the remaining rubber-modified styrene-based resin or an aromatic phosphoric acid ester is added. Even in the case of melt extrusion, unmelted polyphenylene ether having a high melt viscosity may be generated, or the aromatic phosphate ester, which is easily phase-separated, may be blown out from the extruder to reduce the extrusion stability. Therefore, the above problems are solved by first masterbatching the polyphenylene ether having a high melt viscosity, the aromatic phosphoric acid ester having a low melt viscosity, and optionally the rubber-modified styrene resin.

Next, the glass transition temperature (Tg) of the masterbatch is preferably 70 to 100 ° C.
If the Tg exceeds 100 ° C., the master batch cannot be sufficiently melted in the presence of the rubber-modified styrene resin having a low melt viscosity and the aromatic phosphoric acid ester, so that an unmelted polyphenylene ether is produced. , Impact strength decreases. In particular, the impact strength depends on the kneading conditions. On the other hand, when Tg is less than 70 ° C., when the masterbatch is fed to the extruder, the hopper is clogged or the extrudability is lowered. By producing a specific master batch as described above, even if the phase separation of the flame retardant is suppressed and the discharge amount is increased in the subsequent melt extrusion, the extrusion stability is maintained, high productivity, impact strength, and heat resistance are maintained. It is possible to improve the fluidity, fluidity of molding process and appearance.

The following can be given as an example of a preferable composition of the dropping type flame-retardant styrene resin composition of the present invention. Polyphenylene ether (component B) 3 to 8 relative to 100 parts by weight of rubber-modified styrene resin (component A) consisting of 30 to 70 parts by weight of rubber-modified styrene resin and 70 to 30 parts by weight of rubber-unmodified styrene resin. Parts by weight,
3 to 8 parts by weight of an alkyl group-substituted aromatic phosphoric acid ester monomer (component C) consisting of NPDP, BNPP and TNPP,
0.1 to 2 parts by weight of polydimethylsiloxane (component D).

In the case of the above composition, the flame retardancy, especially the drop-type flame retardancy, the continuous moldability, the moldability (fluidity), the impact resistance, the heat resistance, the surface hardness of the molded article and the water gloss retention resistance. Has excellent balance characteristics.

The resin composition obtained by using the low volatility flame retardant for the styrene resin of the present invention is obtained by, for example, melt-kneading the above-mentioned components in a commercially available single-screw extruder or a twin-screw extruder. At that time, antioxidants such as hindered phenols, UV absorbers such as benzotriazole and hindered amines, tin heat stabilizers, other inorganic and halogen flame retardants, lubricants such as stearic acid and zinc stearate. A filler, a reinforcing agent such as glass fiber, a coloring agent such as a dye or a pigment, and the like can be added as necessary.

The composition thus obtained is, for example,
It is possible to perform continuous molding for a long time using an injection molding machine or an extrusion molding machine, and the obtained molded article has excellent flame retardancy (drop-type flame retardancy), heat resistance and impact strength.

[0146]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

In Examples and Comparative Examples, various measurements were carried out using the following measuring methods or measuring machines.

(1) Analysis of Resin Part of Rubber-Modified Styrenic Resin 5 g of the resin composition is dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge. (20,000r
Then, the supernatant obtained by separation was dissolved in tetrahydrofuran, and GPC (gel permeation chromatography) [manufactured by Tosoh Japan Co., Ltd., apparatus body (with RI refractive index detector) HLC- 8020;
Column Tosoh Corporation, GMHXL 2; mobile phase tetrahydrofuran; flow rate 1.0 ml / min; pressure 35
kgf / cm ² ; temperature INLET 35 ° C, OVEN
40 ° C., RI 35 ° C .; sample loop 100 ml; injected sample amount 0.08 g / 20 ml], the weight average molecular weight and the weight fraction of the resin having a molecular weight of 40,000 or less were determined from the area ratio for the main peak. Here, the peak of the oligomer region of the styrene resin following the main peak of GPC was excluded. The residual monomers and oligomers of the styrene resin were determined by gas chromatography. That is, 1 g of the resin composition is dissolved in 10 ml of chloroform, 10 ml of methanol is added to precipitate the resin component, and the resin component is separated using an ultracentrifuge. (20,000 rp
Then, the supernatant obtained by the separation was dissolved in tetrahydrofuran and subjected to gas chromatography [Shimadzu Japan Co., Ltd., 1 m column of packing material silicon DC, 140 ° C. to 240 ° C. 12 ° C. The temperature was raised at a rate of 1 / min and the injection temperature was 260 ° C.]. The weight of the resin having a molecular weight of 40,000 or less is the sum of the above weight measured by GPC and the weight of residual monomers and oligomers of the styrene resin measured by gas chromatography.

(2) Composition Analysis of Aromatic Phosphate Ester 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;
I with refractive index detector) HLC-8020; column Tosoh Corp., G1000HXL 2; mobile phase tetrahydrofuran; flow rate 0.8 ml / min; pressure 60 kgf
/ cm ² ; temperature INLET 35 ° C., OVEN 40
℃, RI 35 ℃; sample loop 100 ml; injection 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 phosphate ester and residual The composition and amount of the aromatic vinyl monomer and the dimer and trimer of the aromatic vinyl monomer were determined. On the other hand, regarding the resin portion, the Fourier transform nuclear magnetic resonance apparatus (Proton-FT-N
MR) was used to determine the ratio of the integrated values of the aromatic protons or the aliphatic protons, and the amounts of the rubber-modified styrene resin and the thermoplastic resin such as aromatic polycarbonate and polyphenylene ether.

(3) Weight average particle diameter of rubber The weight average particle diameter of the rubber-modified styrene polymer is the rubber particle (butadiene polymer particle) in the transmission electron micrograph of the resin composition taken by the ultrathin section method. Calculate the diameter by the following formula.

Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Di represents the measured particle diameter of the butadiene-based polymer particles, and Ni represents the measured butadiene-based weight, which is the particle diameter Di). (4) Number of coalesced particles.) (4) Reduced viscosity ηsp / c of polyphenylene ether 20 ml of chloroform was added to 1 g of polyphenylene ether, and the mixture was shaken at 25 ° C. for 2 hours, 5 ° C., 18,000 rp.
Centrifuge for 30 minutes at m. The supernatant was taken out and the resin component was precipitated with methanol and then dried.

0.1 g of the resin thus obtained is
A solution having a concentration of 0.5 g / dl was dissolved in chloroform, 10 ml of this solution was put into a Canon-Fenske viscometer, and the solution dropping time T ₁ (second) was measured at 30 ° C. On the other hand, the falling time T ₀ (seconds) of pure chloroform was separately measured with the same viscometer and calculated by the following mathematical formula.

Ηsp / c = (T ₁ / T ₀ -1) / C C: Polymer concentration (g / dl) (5) Izod impact strength It was measured at 23 ° C. according to ASTM-D256.

(V notch, 1/8 inch test piece) (6) Surface impact strength The surface impact strength was measured at 23 ° C. by a method similar to ASTM-D1709. Specifically, a DuPont impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used, and the hammer tip diameter was 6.4 mmR,
A dart having a length of 5.2 mm (weight 200 g) was formed on the pedestal with a pedestal diameter of 9.5 mm and a hole depth of 4.0 mm (70
mm square, 2 mm thick molded body) Fixed in contact with the surface and dropped from the height of 50 cm to the molded body, and 50% of the molded body is destroyed by 50% load And the drop load was multiplied to calculate the 50% breaking energy. This 50% breaking energy was defined as surface impact strength. The unit is kgcm.

(7) Vicat Softening Temperature Measured by the method according to ASTM-D1525, and used as a scale of heat resistance.

(8) Melt Flow Rate (MFR) The melt flow rate was measured by a method according to ASTM-D1238. It was determined from the extrusion rate (g / 10 minutes) per 10 minutes under the conditions of a load of 5 kg and a melting temperature of 200 ° C.

(9) Flame retardance VB (Vertical Bur) conforming to UL-Subject 94
ning) method (using a 1/8 inch test piece).

Regarding the method described in UL-Subject 94, reference can be made to, for example, US Pat. No. 4,966,814.

(10) Volatility of Resin Composition (Thermogravimetric Balance Test: TGA Method) Using a Shimadzu Thermal Analyzer DT-40 manufactured by Shimadzu Corporation of Japan, the mixture was allowed to stand at 250 ° C. for 30 minutes in a nitrogen stream. Was used as a measure of volatility.

The following components were used as the components used in Examples and Comparative Examples.

(A) Rubber-modified styrene resin (HIP
S) Polybutadiene {(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2/3) (manufactured by Nippon Zeon Co., Ltd., trade 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 Then, the above mixed liquid Was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage had a stirring rate of 190 rpm and 126
° C, the second stage is 50 rpm, 133 ° C, the third stage is 20 rpm
rpm, 140 ° C, 4th stage is 20rpm, 155 ° C
Was polymerized. 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. The obtained rubber-modified aromatic vinyl resin (referred to as HIPS-1) was analyzed, and as a result, the rubber content was 12.1% by weight and the weight average particle diameter of the rubber was 1.5 μm. The weight average molecular weight was 137,000, the number average molecular weight was 62,000, the weight of the resin having a molecular weight of 40,000 or less was 15.2%, and the weight of the oligomer was 0.2%.

By adjusting the amount of the polymerization initiator, the polymerization temperature, and the amount of the chain transfer agent, the rubber-modified styrene-based resins having different weight average molecular weights, number average molecular weights, resin weights of 40,000 or less, and oligomer weights of the resin portion can be used. A resin was produced.

(B) Rubber-unmodified polystyrene styrene 80.0 parts by weight, ethylbenzene 20 parts by weight, and 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane as an initiator
0.02 parts by weight of the mixed solution was continuously fed to a coil type complete mixing type reactor at a rate of 2.5 liters / hour,
130 ° C, average residence time 2 hours, polymer solid content concentration 48
Polymerization was carried out under the condition of%. Continue to add this polymerization liquid to 23
It was led to a devolatilization apparatus at 0 ° C., unreacted monomer and solvent were removed, and polystyrene was obtained. The weight average molecular weight of the obtained polystyrene was 195,000, and the number average molecular weight was 83,000.
The weight of the resin having a molecular weight of 40,000 or less was 9.9%, and the weight of the oligomer was 0.2%. Further, the weight average molecular weight, the number average molecular weight, the weight of the resin having a molecular weight of 40,000 or less, the weight of the resin, and the oligomer weight of the resin portion are different by adjusting the amount of the polymerization initiator, the polymerization temperature, and the amount of the chain transfer agent. A rubber-unmodified styrenic resin was produced. For example, in the production of the above polystyrene, higher molecular weight polystyrene is produced by reducing the solvent ethylbenzene or lowering the polymerization temperature, while n-dodecyl mercaptan is added as a chain transfer agent or the polymerization temperature is increased. This produced a lower molecular weight polystyrene.

(C) 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 powdered polyphenylene ether (referred to as PPE). Reduced viscosity ηSP is 0.41dl
/ G.

(D) Aromatic Phosphate Ester (1) Triphenyl Phosphate (TPP) Uses a commercially available aromatic phosphate ester monomer [trade name TPP (TPP) manufactured by Daihachi Chemical Industry Co., Ltd.] I was there.

The average total carbon number of the substituents is 0.
And the phosphorus content is 9.5% by weight.

(2) Preparation of Alkyl Group Substituted Aromatic Phosphate Ester 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 total carbon number of the substituents 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, the aromatic phosphoric acid ester monomer mixture (FR-1) was distilled and further fractionated by liquid chromatography to obtain BNPP.

(3) Production of Alkyl Group Substituted Aromatic Phosphate Ester Monomers In the production of FR-1, commercially available alkylphenol or "ENCYCLOPEDIA OF CHEMIC" is used.
AL TECHNOLOGY "ThirdEditi
on VOLUME 2 [ALKYLPHENOL
S ”p. 72-96 (A WILEY-INTER
SCIENCE PUBLICATION John W
Iley & Sons New York 1978) was used to synthesize various alkylphenols by controlling the molar ratio with phosphorus oxychloride. The purification method was carried out by the above-mentioned water washing, distillation or preparative fractionation by liquid chromatography. Table 3 shows various alkylphenols.

Examples 1 to 8 Comparative Examples 1 to 6 The resin compositions shown in Tables 1 and 2 were mechanically mixed and side-fed by a twin-screw extruder (Werner Pflei).
Melt extrusion was performed using ZSK-40mmΦ manufactured by Derer. That is, when PPE is used, PPE / GPPS is melted at 320 ° C in the former stage of the extruder, and the remaining resin component and BNPP are side-fed in the latter stage, and the rotation speed is 295 rpm and the discharge rate is 80 kg / h at 240 ° C. It was melt-kneaded. On the other hand, when PPE is not used, BNP
Feed all components except P to the main feeder 24
Melt kneading was carried out in the same manner at 0 ° C.

Using the pellets thus obtained, an injection molding machine (model IS80A manufactured by Toshiba Machine Co., Ltd.) was used to prepare a test piece under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the MFR and Izod impact strength were measured. Then, the surface impact strength, the Vicat softening temperature and the flame retardancy were evaluated. The results are shown in Tables 1 and 2.

[0174]

[Table 1]

[0175]

[Table 2]

According to Tables 1 and 2, the weight average molecular weight of the resin portion of the styrene resin is 250,000 to 100,000, and the weight of the resin having a molecular weight of 40,000 or less in the resin portion is 15
It can be seen that the fluidity and the impact strength are excellent when the content is less than the weight%.

Examples 9 to 13 Comparative Examples 7 to 12 In Example 1, the aromatic phosphoric acid esters are shown in Tables 3 and 4.
The test piece was prepared in the same manner as in Example 1 and evaluated for flame retardancy and volatility resistance. The results are shown in Table 4 and FIG.

[0178]

[Table 3]

[0179]

[Table 4]

According to Table 4 and FIG. 1, when the total number of carbon atoms of the substituents of the aromatic phosphoric acid ester is in the range of 12 to 25 on average, the flame-retardant and volatility-resistant balance characteristics are excellent. I understand that.

[0181]

The dropping-type flame-retardant styrene resin of the present invention is
The dropping type styrene-based flame-retardant resin composition has excellent fluidity and impact strength, and when a specific aromatic phosphate ester is used, mold deposit does not occur even after continuous molding for a long period of time.

This resin composition is used in a home electric appliance housing such as a VTR, a distribution board, a television, an audio player, a condenser, a household outlet, a radio cassette player, a video cassette, a video disc player, an air conditioner, a humidifier, and an electric warm air machine. 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.

[Brief description of the drawings]

FIG. 1 is an average value of the total number of carbon atoms of substituents of an aromatic phosphate ester monomer and 2 in a thermogravimetric balance test (TGA method).
Volatile amount of the resin composition of Table 4 after holding at 50 ° C. for 30 minutes,
It is the figure which showed the relationship with the flame retardancy (flame-extinguishing time: second) of the resin composition of Table 4.

Claims (3)

[Claims] 1. A styrene-based resin composition containing 1 to 50 parts by weight of an aromatic phosphate ester to 100 parts by weight of a rubber-modified styrene-based resin, wherein the weight of the resin portion of the rubber-modified styrene-based resin is 1. An average molecular weight of 250,000 to 100,000, and the weight of the resin having a molecular weight of 40,000 or less in the resin portion is 15% by weight or less. Styrenic resin composition. 2. The dropping type flame-retardant styrene resin composition according to claim 1, which further comprises 1 to 40 parts by weight of polyphenylene ether with respect to 100 parts by weight of the rubber-modified styrene resin. 3. The dropping type flame-retardant styrene resin composition according to claim 1, wherein the aromatic phosphate ester is represented by the following formula (1). Embedded image (In the formula, a, b and c are 1 to 3, R ¹ , R ² and R ³ are hydrogen or a hydrocarbon having 1 to 30 carbon atoms, and as a whole compound, the substituents R ¹ , R ² and R are The total number of carbon atoms of ³ is on average 12 to 25. Here, in the case of comprising a plurality of aromatic phosphates having different substituents, the substituents R ¹ and R of the above aromatic phosphates are ² , the total carbon number of R ³ is represented by a number average, and is the product of the weight fraction of each aromatic phosphate ester component in the aromatic phosphate ester and the total carbon number of the substituents of each component. Is the sum of.)