JPH09263675A - Lightfast styrene-based flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lightfast styrene-based flame retardant resin composition, excellent in light fastness, causing extremely rare mold deposits even when carrying out the continuous molding for a long period and good in balance characteristics among flame retardance, impact and heat resistances and fluidity. SOLUTION: This lightfast styrene-based flame retardant resin composition comprises (A) 100 pts.wt. rubber-modified styrene-based resin containing 2-25wt.% partially hydrogenated conjugated diene-based rubber in which 5-85% of the total double bonds in a conjugated diene-based rubber is hydrogenated; the content of the 1,2-vinyl bonds after hydrogenation is 0.5-12% and that of the 1,4-bonds after the hydrogenation is at least 10% and (B) 1-100 pts.wt. phosphorus-based flame retardant represented by the formula [(a), (b) and (c) are each 1-3; R<1> , R<2> and R<3> are each hydrogen or a 1-3C hydrocarbon; the sum total of the number of carbon atoms in the substituent groups R<1> , R<2> and<3> is 12-25 on the average as the whole compound].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a styrene-based flame retardant resin composition. More specifically, it relates to a styrene-based flame-retardant resin composition which is excellent in light resistance and does not cause mold deposit even after continuous molding for a long time.

[0002]

2. Description of the Related Art Styrenic resins are excellent in moldability and impact resistance, so that they can be used for automobile parts, home electric appliances, O
It is used in various fields including A equipment parts, but its flammability limits its further expansion. Therefore, a method for making the styrene resin flame-retardant has been developed, and it is known to add, for example, a halogen-based, phosphorus-based, or inorganic flame-retardant agent to the styrene-based resin.
However, although they achieve flame retardancy to some extent, there is a problem that the light resistance decreases.

With the recent spread of office automation equipment (office equipment, electronic information processing equipment) such as personal computers, facsimiles, word processors, etc., in addition to flame resistance and impact resistance as housing materials, light from fluorescent lamps or window glass is used. There is a strong demand for a material having excellent light resistance in which discoloration due to transmitted sunlight is reduced. Therefore, a method of improving the light resistance of a styrene-based resin or a polyphenylene ether-based resin has also been proposed. For example, JP-A 1-161051, JP-B-4-33305, and JP-B-63-8140, JP-B-62-60420 and JP-B-5-76502 disclose techniques for adding an ultraviolet absorber or a light stabilizer alone or in combination, or for increasing the amount of a colorant from the viewpoint of masking fading discoloration. Has been done.
However, the improvement of light resistance by these methods is not sufficient, and a more satisfactory light resistance improving technique is awaited.

On the other hand, rubber-modified styrene resin (HI
The polybutadiene used for PS) has an unsaturated bond and therefore has a problem that the light resistance of HIPS is significantly reduced. On the other hand, a rubber-modified styrene-based resin (JP-A-64-90208) using partially hydrogenated polybutadiene obtained by partially hydrogenating the double bond of polybutadiene is disclosed. However, in the above publication, there is no disclosure about a combination of a rubber-modified styrene-based resin and a phosphorus-based flame retardant, which dramatically improves light resistance while maintaining impact resistance, heat resistance and fluidity, Not even suggested.

Further, when a phosphorus-based flame retardant is used as the flame retardant, the impact strength, the fluidity of molding process and the heat resistance are not always satisfactory, and the mold is contaminated by volatile organic phosphorus during molding, so-called. There has been a problem that productivity is lowered due to generation of mold deposits, or mold contaminants are transferred to a molded product to cause stress cracks, so that industrial use has been narrowed.

As a technique for improving the volatility of such a phosphorus-based flame retardant, a resin composition for laminates comprising a phenol resin and a specific alkyl group-substituted phosphate ester monomer (JP-A-1-95149, Kaihei 1-2242633 and JP-A-1-193328) are disclosed. However, the target of the flame retardant in this publication is a thermosetting resin, which is different from the flame retardant for the styrene resin 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, but is essentially different from the present invention.

In addition, a resin composition composed of polycarbonate, ABS resin, halogenated phosphoric acid ester and polytetrafluoroethylene (WO9106598), a resin composition composed of polycarbonate, AAS resin, phosphoric acid ester and polytetrafluoroethylene (EP534).
297), a polycarbonate resin, an ABS resin, a phosphoric acid ester, a resin composition comprising polytetrafluoroethylene (DE 4309142), a polycarbonate resin, an ABS resin, an aromatic phosphoric acid ester, and a resin composition comprising an aromatic sulfonic acid metal salt (Japanese Patent Application Laid-Open No. H09-242, 6-299060),
Polycarbonate, polyester-polycarbonate,
A resin composition composed of an ABS resin, a phosphoric acid ester and polytetrafluoroethylene (EP482451), a resin composition composed of a polycarbonate, an ABS resin, a phosphoric acid ester and a polycarbonate-siloxane block copolymer (DE4016417) are also 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, it has poor balance between volatility resistance and flame retardancy.

Further, a flame retardant composed of a phosphate consisting of a phenyl group, an isopropylphenyl group and an alkyl group-substituted phenyl group having 4 to 12 carbon atoms (JP-A-2-79).
No. 2, JP 324716, same application), flame-retardant resin consisting of polyphenylene ether / styrene resin / tris (isopropylphenyl) phosphate (JP-A-1-48844), polystyrene / t-butylphenyl phenylphosphate / Functional fluid composition comprising polyol ester (functional)
fluid composition) (USP46)
45615) is disclosed. However, since the total number average carbon number of the substituents of the phosphate in the publication is less than 12 according to the definition of the present invention, the volatility resistance is not sufficient.

Further, tris (4-phenylphenyl)
Flame-retardant resin composition (DE4016417, EP534297, EP53) containing a phosphate 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.
4297) is disclosed. However, the above publication does not disclose a combination with a partially hydrogenated rubber-modified styrene resin.

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. On the other hand, it has not been disclosed or even suggested that the continuous moldability (volatility resistance) should be significantly improved. Therefore, it has not yet been possible to obtain a flame-retardant styrenic resin having excellent light resistance as described above and excellent impact resistance, heat resistance and fluidity.

[0012]

In view of the above situation, the present invention does not cause the above-mentioned problems, that is, the mold deposit does not occur even when continuous molding is performed for a long period of time, which is excellent in light resistance. It is intended to provide a (low volatility) styrene-based flame retardant resin composition.

[0013]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to a technique for preventing mold deposit, which is one of the indicators of light resistance and volatility resistance. As a result, as a specific rubber-modified styrene resin and flame retardant, Surprisingly, by using an aromatic phosphate ester monomer containing a specific substituent, it is possible to dramatically improve the light resistance and flame retardancy of the rubber-modified styrene resin while suppressing the mold deposit. The inventors have found that it is possible to achieve the present invention.

That is, in the present invention, 5 to 85% of all double bonds of the conjugated diene rubber (A) are hydrogenated, and 1,2-vinyl bonds after hydrogenation are 0.5 to 12%. 100 parts by weight of a rubber-modified styrenic resin containing 2 to 25% by weight of a partially hydrogenated conjugated diene rubber having at least 10% of 1,4-bonds after hydrogenation, and (B) a phosphorus-based compound represented by the following formula 1 A light-resistant styrene-based flame retardant resin composition comprising 1 to 100 parts by weight of a flame retardant,

[0015]

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, when it is composed of a plurality of aromatic phosphates having different substituents,
The total number of carbon atoms of the substituents R ¹ , R ² and R ³ of the flame retardant is represented by a number average, and the weight fraction of each aromatic phosphate ester component in the flame retardant and the substituent of each component It is the sum of products with the total number of carbon atoms. )

In the above composition, a light-resistant styrene-based flame-retardant resin composition containing 1 to 100 parts by weight of (C) polyphenylene ether per 100 parts by weight of the rubber-modified styrene-based resin (A), especially a resin The (A) rubber-modified styrene resin having a reduced viscosity ηsp / C of 0.4 to 0.6 and / or a reduced viscosity ηsp / C of 0.
It is intended to provide a light-resistant styrene-based dropping type flame-retardant resin composition which is (C) polyphenylene ether of 3 to 0.6.

Hereinafter, the present invention will be described in detail. The light-resistant styrene-based flame-retardant resin composition of the present invention comprises a specific (A) rubber-modified styrene-based resin, a specific (B) aromatic phosphate ester monomer having a substituent, and optionally (C). Contains polyphenylene ether.

The above-mentioned (A) rubber-modified styrene resin is obtained by hydrogenating a conjugated diene rubber, and the ratio of hydrogenation is called the hydrogenation rate. The hydrogenation rate of all double bonds of the conjugated diene rubber is 5 to 85% as an essential requirement, but preferably 7 to 70%, more preferably 9 to 60%.
It is. When the hydrogenation rate of the conjugated diene rubber is less than 5%, the light resistance and impact resistance are poor, while when it exceeds 85%, the light resistance is excellent, but the impact resistance is poor. Also, 1,2-vinyl bonds after hydrogenation are 0.5 to 12%
Is essential, but preferably 1 to 10%, more preferably 2 to 7%. When the 1,2-vinyl bond after hydrogenation is less than 0.5%, it becomes very difficult to crosslink the rubber phase in the production of the rubber-modified styrene resin, and the impact resistance is lowered. Further, the 1,4-bond must be at least 10%, and if it is less than 10%, it becomes difficult to crosslink the rubber phase and the impact resistance decreases.

It is important that the aromatic phosphate ester monomer (B) is not a condensate but a monomer. 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 have 1 to 30 carbon atoms.
A hydrocarbon group, as a whole compound, the substituents R ^1,
It is important that the number average of the total carbon numbers of R ² and R ³ is 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 2
It has been found that when the ratio exceeds 5, the flame retardancy is lowered, and the present invention has been completed.

In the present invention, the rubber-modified styrene-based resin (A) 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 uniformly dispersed with the components (B) and (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 impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer) and the like. Here, the rubber-like polymer needs to have a glass transition temperature (Tg) of −30 ° C. or less, and if it exceeds −30 ° C., the impact resistance decreases. Examples of such rubbery polymers include:
Diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene),
Examples thereof include rubbery polymers obtained by partially hydrogenating isoprene rubber, chloroprene rubber and the like, and partially hydrogenated conjugated diene rubber is particularly preferable.

Such a partially hydrogenated conjugated diene rubber can be obtained by partially hydrogenating the above conjugated diene rubber by a known hydrogenation method. For example, F. L.
Ramp, et al. Amer. Chem. So
c. , 83, 4672 (1961), hydrogenation method using triisobutylborane catalyst, Hung Y
u Chen, J .; Polym. Sci. Polym.
Letter Ed. , 15, 271 (1977), hydrogenation using toluenesulfonyl hydrazide, or hydrogen using the organic cobalt-organoaluminum catalyst or organic nickel-organoaluminum catalyst described in JP-B-42-8704. The method of adding may be mentioned. Here, a particularly preferable hydrogenation method is the method shown in JP-A-52-41890 using a catalyst capable of selectively hydrogenating a 1,2-vinyl bond prior to a 1,4-bond, or JP-A-59-133203 and JP-A-60-220 using a catalyst capable of hydrogenation under mild conditions of low temperature and low pressure.
This is the method disclosed in Japanese Patent Publication No. 147.

In addition, 1 of partially hydrogenated conjugated diene rubber
Mooney viscosity (ML) measured at 00 ° C. is 20 to 90,
Viscosity of 5 wt% styrene solution at 25 ° C (5% SV)
Is preferably in the range of 20 to 300 centipoise (cps). Particularly preferred range is 25 to 150 cp
s.

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

If desired, one or more monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component 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 reduce the melt viscosity at the time of blending, an acrylate ester composed of 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 rubber-like polymer in the rubber-modified styrenic resin is preferably 5 to 80% by weight, particularly preferably 1
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 reduced viscosity ηsp / c (0.5 g / dl, of the resin portion, which is a measure of the molecular weight of the rubber-modified styrenic resin,
Measurement at 30 ° C .: When the matrix resin is polystyrene, a toluene solution is used. When the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer, methyl ethyl ketone) is used.
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
Examples of means for satisfying the above requirement regarding / c include adjustment of the amount of polymerization initiator, polymerization temperature, and amount of chain transfer agent.

Here, the reduced viscosity ηsp / c is 0.40 to
The rubber-modified styrene-based resin having a content of 0.60 dl / g is generally excellent in fluidity and flame retardancy, particularly, drop-type flame retardancy, but impact strength may decrease. On the other hand, by using an organic peroxide having a high hydrogen abstraction ability to highly graft a vinyl aromatic monomer onto a conjugated diene polymer, the dispersed phase formed by the conjugated diene polymer can be specified. It is possible to produce a rubber-modified styrenic resin having the following particle size distribution and excellent impact strength and rigidity.

In the present invention, the aromatic phosphoric acid ester monomer constituting the phosphorus-based flame retardant (A) is represented by the formula 1.

[0032]

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, when it is composed of a plurality of aromatic phosphates having different substituents,
The total number of carbon atoms of the substituents R ¹ , R ² and R ³ of the flame retardant is represented by a number average, and the weight fraction of each aromatic phosphate ester component in the flame retardant and the substituent of each component It is the sum of products with the total number of carbon atoms. )

Among the aromatic phosphoric acid ester monomers of the present invention, the number average carbon number of the substituents R ¹ , R ² and R ³ is preferably 14-22, more preferably 16-20. Most preferred is 17-19.

Specific substituents include 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.

Most preferably, the total number of carbon atoms of the alkyl groups substituting one phosphoric acid ester monomer is in the range of 12 to 25, but one aromatic ring substituted with only one long chain alkyl group is used. Than the phosphate ester monomer that has only
A phosphate ester monomer having a plurality of aromatic rings substituted with only one alkyl group is superior in heat resistance and water resistance. For example, the total number of carbon atoms of the substituted alkyl group is 18
However, bis (nonylphenyl) phenyl phosphate is preferable because it has higher heat resistance than octadecylphenyl diphenyl phosphate.

Among the flame retardants of the present invention, especially R ¹ ,
A phosphoric acid ester monomer in which at least one of R ² and R ³ is a nonyl group is preferable, and an aromatic phosphoric acid ester monomer in which R ¹ and R ² are nonyl groups and R ³ is hydrogen [bis (Nonylphenyl) phenyl phosphate] is most preferable. The above phosphoric acid ester monomer is contained in the flame retardant in an amount of 5
When the content is 0% 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 volatility 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 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. Further, when the flame retardant contains the hindered phenol-based antioxidant in an amount of 1 to 1000 ppm by weight, the thermal stability is dramatically improved.

Next, from the viewpoint of light resistance, the substituents R ¹ , R ² and R ³ are preferably an alkyl group rather than an aryl group. Even in the case of an alkyl group, it is preferable that the alkyl group has less branching, and in particular Alkyl groups with one chain or branch are particularly preferred. The light resistance of an alkyl group having a carbon number of 5 or less is reduced even if the same branch is present at one location, and the light resistance of a phosphate ester monomer having an isopropyl group is poor.

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 preferable combination of aromatic phosphate ester monomers in the present invention is nonylphenyl diphenyl phosphate (NPDP), bis (nonylphenyl) phenyl phosphate (BNPP), tris (nonylphenyl) phosphate ( TNPP) and the number average carbon number of the substituents R ¹ , R ² and R ³ is 1
2 to 25, preferably 14 to 22, more preferably 16 to 20, and most preferably 17 to 19.

In order to satisfy the above number average of the total number of carbon atoms, for example, 1 to 80% by weight of NPDP is preferable, and 1 to 80% by weight is preferable.
50% by weight, more preferably 1 to 30% by weight, most preferably 1 to 10% by weight, BNPP is 1 to 98% by weight, preferably 20 to 90% by weight, more preferably 3%.
0-80% by weight, most preferably 40-80% by weight, TNPP of 1-98% by weight, preferably 1-70% by weight, more preferably 5-60% by weight, most preferably 5-50% by weight. In range.

The flame retardant 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. BNPP is excellent in the balance characteristics of the above characteristics, but by blending the three in specific amounts, balance characteristics that cannot be 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.

The aromatic phosphate ester monomer of the present invention is
JP-A-1-95149, JP-A-3-294284
And can be manufactured by a known method disclosed in Japanese Patent Application Laid-Open No. H10-209, etc. 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.

In the present invention, the phosphorus-based flame retardant (B) is contained in the composition in an amount of 1 to 100 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber-modified styrene resin.
0 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 3 to 10 parts by weight.

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

The most preferred (C) polyphenylene ether that can be added to the rubber-modified styrenic resin is
A homopolymer consisting of a bonding unit represented by the following formula 2 and /
Alternatively, it is a copolymer.

[0049]

Embedded image However, R ¹ , R ² , R ³ , and R ⁴ are each selected from the group consisting of hydrogen, a hydrocarbon, or a substituted hydrocarbon group, 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 such polyphenylene ether is not particularly limited, and for example, a complex of a cuprous salt and an amine obtained by the method described in US Pat. No. 3,306,874 is used as a catalyst. , 6-xylenol can be easily produced by oxidative polymerization. In addition, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358 Calligraphy and Japanese Patent Publication Sho 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 (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether used in the present invention is 0.20 to 0.70 dl /
g is preferably in the range of 0.30 to 0.60d
It is more preferably in the range of 1 / g. Examples of means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the polyphenylene ether include adjustment of the catalyst amount 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.
100 parts by weight, more preferably 1 to 40 parts by weight, and most preferably 3 to 10 parts by weight.

In the resin composition of the present invention, (D) polyorganosiloxane can be blended, if necessary, to relax the orientation of the rubber-modified styrene resin. When the molding is performed with a high shear force, the orientation remains in the obtained molded body, which hinders dripping of fire. 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 kinematic viscosity (25 ° C.) of the above polyorganosiloxane is 30 to 200.
00CS is preferred, 40-1000CS is more preferred, and 50-100CS is most preferred. When the kinematic viscosity is less than 30 CS, the volatility is high and the mold is contaminated during molding. On the other hand, when it exceeds 20,000 CS, the orientation relaxation property of the styrene resin is poor.

The polyorganosiloxane (D) is particularly preferably polydimethylsiloxane, so-called silicone oil. The amount of polyorganosiloxane is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the rubber-modified styrenic resin.
Parts by weight, most preferably 0.3 to 3 parts by weight.

In the resin composition of the present invention, if necessary, (E) an organic phosphorus compound as a flame retardant other than the above,
Red phosphorus, inorganic phosphates, inorganic flame retardants and the like can be blended. The amount of (E) 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 organic phosphorus compound (E) include phosphine, phosphine oxide, biphosphine,
Phosphonium salts, phosphinates, phosphates, phosphites and the like. More specifically, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite, dineopentyl hypophosphite. Phyto, phenylpyrocatechol phosphite, ethylpyrocatechol phosphate, and dipyrocatechol hypophosphite.

Further, an aromatic phosphoric acid ester condensate such as tetraphenyl / bisphenol A / polyphosphate may be blended to the extent that flame retardancy is not affected.
The red phosphorus as (E), in addition to general red phosphorus, has its surface previously coated with a metal hydroxide film selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. , Aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide coated with a metal hydroxide and a thermosetting resin, aluminum hydroxide, magnesium hydroxide, hydroxide For example, a metal hydroxide selected from zinc and titanium hydroxide may be doubly coated with a thermosetting resin film.

The inorganic phosphate as (E) is typically ammonium polyphosphate. As the inorganic flame retardant as (E), aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, hydrate of tin oxide, etc. Inorganic metal compound hydrate, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate and the like. 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 a good flame retarding effect and are economically advantageous.

In the resin composition of the present invention, 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 fluororesin, or a polyacrylonitrile fiber is used. One or more selected flame retardant aids (F) can be blended. The amount of (F) is preferably 0.00 based on 100 parts by weight of the rubber-modified styrene resin.
It is 1 to 40 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 5 to 10 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 aid for the phosphorus flame retardant. Specific examples thereof include melamine, melam (formula 3), melem (formula 4), and melon (600).
Product of deammonification of 3 to 3 molecules of melem above ° C), melamine cyanurate (formula 5), melamine phosphate (formula 6), succinoguanamine (formula 7), adipoguanamine, methylglutaloganamin , Melamine resin (formula 8), BT resin (formula 9), and the like, and melamine cyanurate is particularly preferable from the viewpoint of volatile resistance.

[0062]

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[0063]

[Chemical 6]

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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The novolak resin as the component (F) is a flame retardant auxiliary agent and, when used in combination with a hydroxyl group-containing aromatic phosphate ester, is also a flowability 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 manufacturing novolac resin is shown in (Formula 10).

[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 (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.

Silicone resin as (F) is SiO
₂ is a RSiO _3/2, R ₂ SiO, silicone resins having a three-dimensional network structure formed by combining structural units of 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 cohydrolyzing and polymerizing the organohalosilane corresponding to the above structural unit.
The vinyl-containing silicone oil as (F) has formula 11
It is a polydiorganosiloxane consisting of the chemical bond unit shown in.

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Embedded image R in the above formula is one or two or more substituents selected from a C1-8 alkyl group, a C6-13 aryl group, a vinyl-containing group represented by formula 12 and formula 13, and here, in particular, Contains a vinyl group 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 (F) is amorphous silicon dioxide, and in particular, a silica coated with a hydrocarbon compound which is treated with a silane coupling agent of a hydrocarbon compound on the surface of the silica is preferable. Hydrocarbon-based compound-coated silica contained is preferred.

Examples of the silane coupling agent include vinyl such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane. Group-containing silanes, epoxy silanes such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,

And N-β (aminoethyl) γ-aminopropyltrimethoxysilane N-β (aminoethyl) γ-
It is an aminosilane such as aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-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 (F) 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 used as an amide polar solvent or sulfuric acid. It can be produced by dissolving it in a solution and spinning the solution by a wet or dry method.

The fluorine-based resin as the F component is a flame retardant aid and is a resin containing fluorine atoms in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer.
If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.

The polyacrylonitrile fiber (F) has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to
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.

In the resin composition of the present invention, if necessary, a copolymer resin comprising an aromatic vinyl unit and an acrylic ester unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic One or more (G) fluidity improvers selected from alcohols and metal soaps can be blended. The amount of (G) is based on 100 parts by weight of the rubber-modified styrene resin.
Preferably 0.1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight.
5 to 10 parts by weight, most preferably 1 to 5 parts by weight.

The aromatic vinyl unit of the copolymer resin as (G) is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene. And the like, and styrene is most preferable, but styrene may be the main component and other aromatic vinyl monomers may be copolymerized. 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 from 3 to 40% by weight, and more preferably from 5 to 20% by weight. In addition, the solution viscosity, which is an index of the molecular weight of the copolymer resin (M of resin 10% by weight)
It is preferable that the EK solution and the measurement temperature of 25 ° C. are 2 to 10 cP (centipoise). If the solution viscosity is less than 2 cP, the impact strength decreases, while if it exceeds 10 cP, the effect of improving the fluidity decreases.

The aliphatic hydrocarbon-based processing aid as (G) is liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, fluorides, chlorides and the like.

Examples of the higher fatty acid (G) include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid and ferric acid, and ricino-acid, lysine veridic acid, 9-oxy-12. It is an unsaturated fatty acid such as octadecenoic acid.

The higher fatty acid ester as (G) is a monohydric alcohol ester of a fatty acid such as methyl phenylstearate or butyl phenylstearate, and a monohydric alcohol ester of a polybasic acid such as a diphenylstearyl phthalate diester. Furthermore, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate. , Sorbitan esters such as polyoxyethylene sorbitan monooleate,

Fatty acid ester of glycerin monomer such as stearic acid monoglyceride, oleic acid monoglyceride, capric acid monoglyceride, behenic acid monoglyceride, polyglycerin stearic acid ester, polyglycerin oleic acid ester, polyglycerin lauric acid ester and the like Fatty acid ester,
Examples thereof include fatty acid esters having a polyalkylene ether unit such as polyoxyethylene monolaurate, polyoxyethylene monostearate, and polyoxyethylene monooleate, and neopentyl polyol fatty acid esters such as neopentyl polyol distearate.

The higher fatty acid amides as (G) are monoamides of saturated fatty acids such as phenylstearic acid amide, methylol stearic acid amide, and methylol behenic 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,

Further, methylenebis (12-hydroxyphenyl) stearic acid amide, ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-
Saturated fatty acid bisamides such as hydroxyphenyl) stearic acid amide, and aromatic bisamides such as m-xylylenebis (12-hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohol as (G) is
Examples include monohydric alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols such as sorbitol and mannitol, and polyoxyethylene dodecylamine and polyoxyethylene boctadecylamine, and polyoxyethylene allylated ethers and the like. An allylated ether having an alkylene ether unit,

And polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, poly Polyoxyethylene alkyl phenyl ether such as oxyethylene nonyl phenyl ether,

It is a dihydric alcohol having a polyalkylene ether unit such as polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A ether, and polyoxyethylene polyoxypropylene glycol ether.

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

In the resin composition of the present invention, (H) a thermoplastic elastomer can be blended if necessary, and examples thereof include polystyrene type, polyolefin type, polyester type, polyurethane type, 1,2-polybutadiene type, Polyvinyl chloride type and the like, and polystyrene type thermoplastic elastomer is particularly preferable. The amount of (H) is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, and most preferably 2 to 5 parts by weight, based on 100 parts by weight of the rubber-modified styrene resin. .

The thermoplastic polystyrene-based 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 portion 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. Further, the conjugated diene monomer constituting the block copolymer,
Examples thereof include 1,3-butadiene and isoprene.

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 its partially hydrogenated unit 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 from 1 to 2
Block copolymer or (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.

When light resistance is required in the resin composition of the present invention, if necessary, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, a halogen scavenger, a light shielding agent, a metal inactive agent. One or more kinds of (I) light resistance improvers selected from agents and quenchers can be blended. The amount of (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 (I) absorbs light energy to become a keto-type molecule by intramolecular proton transfer (benzophenone, benzotriazole type), or by cis-trans isomerization. (Cyanoacrylate type), a component for releasing as heat energy and detoxifying.

Specific examples thereof are 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as

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-chlorobenzo Triazole, 2- (2'-hydroxy-3 '
-T-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-t-octyl- 6-benzotriazolyl)
2- (2′-hydroxyphenyl) benzotriazoles such as phenol,

Phenyl salicylate, resorcinol monobenzoate, 2,4-di-t-butylphenyl-
3 ', 5'-di-t-butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-
Benzoates such as hydroxybenzoate, 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4 '
-Substituted oxanilides such as dodecyl oxanilide, and cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate. is there.

The hindered amine-based light stabilizer as (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-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 (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-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 (I) stabilizes peroxide radicals such as hydroperoxy radicals generated during thermoforming or by exposure to light, or decomposes peroxides such as hydroperoxide generated. It is a component for. 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'-butylidene bis (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]
For example, -2,4,8,10-tetraoxyspiro [5.5] undecane and the like.

Specific examples of the peroxide decomposing agent as the antioxidant are 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 (I) is a component for scavenging free halogen produced 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 or 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. Also, as a synthetic product, Mg _0.7 A
l _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂ O, M
g _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.

As the zeolite, Na ₂ O.Al
Can be mentioned A-type zeolite or the Periodic Table Group II and zeolite substituted by a metal containing at least one metal selected from metals of IV, indicated by _{2 O 3 · 2SiO 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,

Alternatively, hydrogenated bisphenol A glycidyl ether, 3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate, 2-
(3,4-epoxycyclohexyl spiro [5,5]-
3,4-epoxy) cyclohexane-m-dioxane,
Bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexenedioxide, 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,
Alicyclic epoxy compounds such as ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate.

The light shielding agent as (I) 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 (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 (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. .

As the method for producing the resin composition of the present invention,
A method in which a rubber-modified styrene resin and another thermoplastic resin are first melted, and then (B) is added and melt-kneaded in the same extruder, or a rubber-modified styrene resin, another thermoplastic resin, or if necessary. Accordingly, there is a method of producing a masterbatch containing (B) accordingly and then kneading the masterbatch with the remaining rubber-modified styrene resin or the remaining (B) or other flame retardant.

The following can be mentioned as an example of a preferable composition of the resin composition of the present invention. (B) NPDP, BNP with respect to (A) 100 parts by weight of rubber-modified styrene-based resin, which is composed of 30 to 70 parts by weight of rubber-modified styrene-based resin and 70 to 30 parts by weight of rubber-unmodified styrene-based resin
3 to 8 parts by weight of alkyl group-substituted aromatic phosphate ester monomer composed of P and TNPP, 3 to 8 parts by weight of (C) polyphenylene ether, and (D) polydimethylsiloxane 0.1.
~ 2 parts by weight. In the case of the above composition, light resistance, flame retardancy, particularly drop type flame retardancy, continuous moldability, moldability (fluidity),
Excellent balance of impact resistance and heat resistance.

The resin composition of the present invention can be obtained by, for example, melt-kneading each of the above components with a commercially available single-screw extruder, a twin-screw extruder or the like. At that time, an antioxidant such as hindered phenol is used. , UV absorbers such as benzotriazole and hindered amine, tin-based heat stabilizers, other inorganic and halogen-based flame retardants, lubricants such as stearic acid and zinc stearate, fillers, reinforcing agents such as glass fibers, dyes and pigments Colorants 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 product has light resistance,
Excellent flame retardancy (dripping type flame retardancy), heat resistance and impact resistance.

[0126]

BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Examples,
In the comparative example, various measurements were carried out using the following measuring methods or measuring machines.

(1) Analysis of Conjugated Diene Rubber A Mooney viscosity (ML) L rotor is used to show a torque reading at 100 ° C. for 1 minute of remaining heat time and 4 minutes after driving. 5 wt% styrene solution viscosity (5% SV) Measured using a Canon Fenske viscometer. Unit: centipoise

Hydrogenation rate (%) It was measured by NMR according to the following procedure. First, polybutadiene rubber before hydrogenation is dissolved in heavy chloroform, and FT-N is added.
Chemical shift 4.7 at MR (270 mega, made by JEOL)
~5.2ppm proton by 1,2-vinyl of (a signal C0) (= CH _2), chemical shifts 5.2 to
5.8 ppm (the signals D0) vinyl protons (= CH ₂ -) from the integrated intensity of was calculated by the following equation. (V) = [0.5C0 / {0.5C0 + 0.5 (D0-
0.5C0)}] × 100

Next, the partially hydrogenated polybutadiene rubber was dissolved in deuterated chloroform, and similarly in FT-NMR, a hydrogenated compound having a chemical shift of 0.6 to 1.0 ppm (signal A1) was added. Methyl group proton (—CH ₃ ) due to 2 bond, chemical shift 4.7 to 5.2 ppm
Non-hydrogenated 1 and 2 (denoted as signal C1)
- Proton by vinyl (= CH _2), the chemical shift 5.
It was calculated from the integrated intensity of non-hydrogenated vinyl proton (= CH-) of 2 to 5.8 ppm (signal D1) by the following formula.

First, p = 0.5C0 / (0.5C1 + A
1/3) A11 = pA1, C11 = pC1, D11 = pD1, and the hydrogenation rate of the 1,2-vinyl bond portion (B) (B) = [(A11 / 3) / {A11 / 3 + C11 /
2}] × 100 1,4-Double bond portion hydrogenation rate (C) (C) = [{0.5 (D0-0.5C0) -0.5 (D
11-0.5C11)} / 0.5 (D0-0.5C
0)] × 100 Hydrogenation rate of the entire butadiene part (A) (A) = (V) × (B) / 100 + [100− (V)]
X (C) x 100

Microstructures Described below with the symbols defined above. 1,2-Vinyl bond after hydrogenation = (V) × (B) / 1
00 (%) 1,4 bond after hydrogenation = {100− (V)} × (C)
/ 100 (%) 1,2-vinyl bond after hydrogenation = (V) x {10-
(B)} / 100 (%) 1,4-bond after hydrogenation =
{100- (V)} × {100- (B)} / 100
(%)

(2) 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 particle diameter of the measured butadiene-based polymer particles, and Ni represents the measured particle size of the butadiene-based polymer particles. Indicates the number.)

(3) Reduced viscosity of rubber-modified styrene resin and polyphenylene ether ηsp / C 1 g of rubber-modified styrene resin and 18 g of methyl ethyl ketone
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 is
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, and 10 ml of this solution is put into a Canon-Fenske viscometer. This solution drop 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 = (T1 / T0-1) / 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 to obtain a concentration of 0.
A solution of 5 g / dl was prepared and measured in the same manner as above.

(4) Analysis of Phosphorus Flame Retardant and Resin Composition A) 5 g of the resin composition is dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge. (2000
0 rpm, 1 hour) Then, twice the amount of methanol was added to the supernatant obtained by separation to precipitate a resin component,
The solution part and the resin part were separated using an ultracentrifuge.
For the solution part, GPC (gel permeation chromatography) [manufactured by Tosoh Corporation, Japan; HLC-8020 main unit (with a RI refractive index detector); Column: Tosoh Corp., two G1000HXL; mobile phase
Tetrahydrofuran; flow rate 0.8 ml / min; pressure 6
0 kgf / cm ² ; temperature INLET 35 ° C, OVE
N 40 ° C, RI 35 ° C; sample loop 100m
1; injection sample amount 0.08 g / 20 ml], and assuming that the area ratio of each component on the chromatogram is the weight fraction of each component, the phosphate ester and residual aromatic vinyl monomer are calculated from the area ratio. The composition and amount of the dimer and trimer of the aromatic vinyl monomer were determined. On the other hand, regarding the above resin portion, a Fourier transform nuclear magnetic resonance apparatus (proton-
FT-NMR) 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 were determined.

B) Volatility of flame retardant (thermogravimetric balance test: T
GA method) Using a Shimadzu thermal analyzer DT-40 manufactured by Shimadzu Corporation of Japan, the temperature was raised at a rate of 40 ° C./min under a nitrogen stream to obtain a measure of the weight loss volatility at 300 ° C. or 400 ° C. On the other hand, using the above apparatus, the residual amount after standing at 250 ° C. for 5 minutes under a nitrogen stream was used as a measure of volatility.

(5) Izod impact strength It was measured at 23 ° C. by a method according to ASTM-D256. (V notch, 1/4 inch test piece unit: kgcm
/ Cm)

(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) Rigidity The flexural modulus was measured by the method according to ASTM-D790 and used as a measure of rigidity. Unit: kg / cm ² (8) Vicat softening temperature Measured by a method according to ASTM-D1525, and used as a scale of heat resistance. Unit: ° C

(9) 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. Unit: g / 10 minutes (10) Flame retardance VB (Vertic) in accordance with UL-Subject 94
Al Burning) method (1/8 inch test piece was used). Regarding the method described in UL-Subject 94, see, for example, US Pat. No. 4,966,814.
You can refer to the issue.

(11) Light Resistance of Molded Product The light resistance test was carried out by using ATLAS El as a light resistance tester.
electric Devices Co. ATLAS
Using CI35W Weatherometer, J
The test was performed by a method based on IS K7102. The irradiation conditions were: internal temperature of the tester, 55 ° C., humidity 55%, no rain, xenon light (wavelength 340 nm, energy 0.30
W / m ² ) Irradiation for 300 hours. Using a SM color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd. in Japan, a. b. Difference of the molded product before and after the test
Based on E, the change in color tone was evaluated. The smaller the change in color tone, the higher the light resistance.

The following components were used as the components used in Examples and Comparative Examples. (A) Production of partially hydrogenated conjugated diene rubber A butadiene / n-hexane solution (butadiene concentration 20% by weight) at a rate of 20 liters / hr was prepared by using a jacketed autoclave with an internal volume of 10 liters equipped with a stirrer. Then, an n-butyllithium / n-hexane solution (concentration 5% by weight) was introduced at 70 mil / hr,
Continuous polymerization of butadiene was carried out at a polymerization temperature of 110 ° C.
The obtained active polymer was deactivated with methanol (this polymer is referred to as polymer a), and 8 liters of the polymer solution was transferred to another reactor with a stirrer and a jacket having an internal volume of 10 liters and the temperature was 60 ° C. At the hydrogenation catalyst, di-p-tolyl bis (1-cyclopentadienyl) titanium /
Cyclohexane solution (concentration 1 milliliter / liter)
250 milliliters and n-butyllithium solution (concentration 5 milliliters / liter) 50 milliliters, 0
The mixture was added at 2 ° C. under a hydrogen pressure of ² kg / cm ² , and the mixture was reacted at a hydrogen partial pressure of 3 kg / cm ^{2 for} 30 minutes.
To the resulting partially hydrogenated polymer solution, 0.5 part of 2,6-ditert-butylhydroxytoluene was added as an antioxidant per polymer, and the solvent was removed. Table 1 shows the analytical values of the original polymer a and the partially hydrogenated polymer d obtained by sampling after deactivation of methanol.

The butadiene polymer obtained in the same manner as the polymer a is hydrogenated by changing the hydrogenation reaction conditions (hydrogenation pressure, hydrogenation temperature, time and amount of catalyst) to form partially hydrogenated polymers b and c. And ef were obtained. The structural analysis values of these polymers are also shown in Table 1.

(B) Rubber modified styrene resin (HIP
S) As a partially hydrogenated conjugated diene rubber, polymer a was dissolved in the following mixed solution to obtain a uniform solution. Polybutadiene 7.3% by weight Styrene 78.5% by weight Ethylbenzene 14.0% by weight α-Methylstyrene dimer 0.17% by weight t-Butylperoxyisopropyl carbonate 0.03% by weight

Next, the above mixed solution was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage had a stirring rate of 190 r.
pm, 126 ° C, the second stage is 50 rpm, 133 ° C,
The third stage is 20 rpm, 140 ° C, and the fourth stage is 20 rpm
m, at 155 ° C. The solid content is
3% of the polymerization liquid was introduced into a devolatilizer to remove unreacted monomers and solvent to obtain a rubber-modified aromatic vinyl resin [HIPS
(No). 1]. As a result of analyzing the obtained rubber-modified aromatic vinyl resin, the rubber content was 10% by weight, the weight average particle diameter of the rubber was 1.8 μm, and the reduced viscosity ηsp / c was 0.64 d.
1 / g. Further, the rubber-modified styrene-based resin [HIPS (No). 2-6] was manufactured.
The results are shown in Table 2.

(C) Rubber-unmodified styrene resin (GPP
S) Polystyrene having a weight average molecular weight of 200,000 (manufactured by Asahi Chemical Industry Co., Ltd.) was used (referred to as GPPS).

(D) Phosphorus Flame Retardant Triphenyl Phosphate (TPP) A commercially available aromatic phosphate ester monomer [trade name TPP (TPP), manufactured by Daihachi Chemical Industry Co., Ltd.] was used.
The average total carbon number of the substituents is 0, and the phosphorus content is 9.5% by weight.

Aromatic phosphoric acid ester condensate (fr-
1) Commercially available aromatic condensed phosphoric acid ester derived from bisphenol A [manufactured by Daihachi Chemical Industry Co., Ltd., trade name CR741 (f
r-1)]] was used. According to GPC analysis, the above-mentioned aromatic condensed phosphoric acid ester has TPP-A-dimer (n = 1) and TPP-A represented by the following formula 14:
Consisting of an oligomer (n ≧ 2) and triphenyl phosphate (TPP), in a weight ratio of 84.7 / 1 each
It was 3.0 / 2.3. And the phosphorus content is 9.4
% By weight.

[0149]

Embedded image

Production 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, BNPP was obtained by distilling the aromatic phosphoric acid ester monomer mixture (FR-1) and further preparative fractionation by liquid chromatography.

Production of Various 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
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 1 shows various alkylphenols.

(E) 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). The reduced viscosity ηsp / C is 0.4
It was 1 dl / g.

(F) Light resistance improver UV absorber A benzotriazole type UV absorber manufactured by Ciba-Geigy [trade name: Tinuvin P (UVA)] was used. Hindered piperidine-based light stabilizer manufactured by Ciba Geigy [Product name: TINUVIN 770 (HALS
)] Was used. Light-shielding agent Titanium oxide (TiO ₂ ) Commercially available titanium oxide powder [Ishihara Sangyo Co., Ltd. 0.2 μ
(Referred to as TiO ₂ ) was used.

[0155]

【Example】

Examples 1 to 5 and Comparative Examples 1 to 5 The resin compositions shown in Table 2 were mixed and melt-extruded using a twin-screw extruder (ZSK-40mmΦ manufactured by Werner Pfleiderer) capable of side feeding. That is, when using PPE, PP is used before the extruder.
E / GPPS is melted at 320 ° C, and the remaining resin component and BNPP are side-fed in the latter stage, and the rotation speed is 295 rp.
m and a discharge rate of 80 kg / h at 240 ° C.
On the other hand, when PPE was not used, components other than BNPP were melted in the former stage of the extruder, side-fed with BNPP in the latter stage, and melt-kneaded in the same manner.

Using the pellets thus obtained, an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model IS80A) 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 subjected to MFR and Izod impact. The strength, surface impact strength, flexural modulus, Vicat softening temperature, light resistance and flame retardancy were evaluated. Table 2 shows the results. According to Table 2, the rubber-modified styrenic resin using the partially hydrogenated conjugated diene rubber having the specific hydrogenation rate of the present invention has a physical property balance,
In particular, it can be seen that it enables a styrene-based flame-retardant resin having an excellent balance of light resistance and impact strength.

Reference Example Various aromatic phosphate ester monomers shown in Table 3 were allowed to stand for 5 minutes at 250 ° C. under a nitrogen stream by a thermogravimetric balance test method to determine the residual amount. The results are shown in Table 3 and FIG.
According to Table 3 and FIG. 1, it can be seen that the compound as a whole exhibits excellent volatility resistance when the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 12 or more on average.

Examples 6 to 10 and Comparative Examples 6 to 12 HIPS- / GPPS / aromatic phosphates listed in Table 3 were mechanically mixed at 70/30/7 (weight ratio),
Melting temperature 2 using a Labo Plastomill manufactured by Toyo Seiki
It was melted at 20 ° C. and a rotation speed of 50 rpm for 5 minutes. 1/8 of the resin composition thus obtained was obtained by compression molding.
Inch-thick test pieces were prepared and evaluated for flame retardancy.
Also, according to the thermogravimetric balance test method, under a nitrogen stream, at 40 ° C /
The temperature was raised in minutes and the relationship between the temperature and the amount of weight loss was determined. The results are shown in Table 4 and FIG.

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. Compared with the aromatic phosphate ester monomer, the aromatic phosphate ester condensate has 4
Flame retardancy is poor because the amount of volatilization at 00 ° C is small. Also,
A specific alkyl group-substituted aromatic phosphoric acid ester monomer is non-volatile at a molding temperature of 300 ° C. or lower, and volatilizes effectively in the early stage of combustion, and thus has excellent flame retardancy.

[0160]

[Table 1]

[0161]

[Table 2]

[0162]

[Table 3]

[0163]

[Table 4]

[0164]

[Table 5]

[0165]

The styrene-based flame retardant resin composition of the present invention comprises
It has excellent light resistance, remarkably small mold deposit even after continuous molding for a long time, and good balance characteristics of flame retardancy, impact resistance, heat resistance and fluidity.

This styrene-based flame-retardant resin composition has a VT
R, distribution board, television, audio player, condenser, household outlet, radio-cassette, video cassette, video disc player, air conditioner, humidifier, electric hot air machine, etc., home appliance housing, chassis or parts, CD-ROM main OA equipment housings such as frames (mechanical chassis), printers, fax machines, PPCs, CRTs, word processors, electronic cash registers, office computer systems, floppy disk drives, keyboards, types, ECRs, calculators, toner cartridges, telephones, etc., Chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable capacitor, AC adapter, FBT high voltage bobbin, FBT case, IFT coil bobbin, jack, volume shaft, module Suitable for electronic / electrical materials such as instrument parts, instrument panels, radiator grills, clusters, speaker grills, louvers, console boxes, defroster garnishes, ornaments, fuse boxes, relay cases, connector shift tapes, etc. Therefore, these industries play a large role.

[Brief description of drawings]

FIG. 1 is an average value of the total carbon numbers of the substituents of the aromatic phosphate ester monomers shown in Table 3 and a thermogravimetric balance test (TGA
Method) at 250 ° C. for 5 minutes, the residual amount of the aromatic phosphate ester monomer, and the flame retardancy (extinguishing time: seconds) of the molded product of the resin composition shown in Table 4 are shown. It is a figure.

Claims (3)

[Claims] 1. (A) 5 to 85% of all double bonds of the conjugated diene rubber are hydrogenated, and 1,2-
100 parts by weight of a rubber-modified styrenic resin containing 2 to 25% by weight of a partially hydrogenated conjugated diene rubber having a vinyl bond of 0.5 to 12% and a 1,4-bond after hydrogenation of at least 10%. B) A light-resistant styrene-based flame-retardant resin composition comprising 1 to 100 parts by weight of the phosphorus-based flame retardant 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, when it is composed of a plurality of aromatic phosphates having different substituents,
The total number of carbon atoms of the substituents R ¹ , R ² and R ³ of the flame retardant is represented by a number average, and the weight fraction of each aromatic phosphate ester component in the flame retardant and the substituent of each component It is the sum of products with the total number of carbon atoms. ) 2. A rubber-modified styrenic resin 100 of (A)
1 to 1 part by weight of (C) polyphenylene ether
The light-resistant styrene-based flame-retardant resin composition according to claim 1, containing 100 parts by weight. 3. The reduced viscosity ηsp / C of the resin portion is 0.4.
(A) rubber-modified styrenic resin and
Alternatively, the light-resistant styrene-based dropping type flame-retardant resin composition according to claim 1 or 2, which uses (C) polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6.