JPH1045946A - Lowly volatile flame retardant for thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a lowly volatile flame retardant for thermoplastic resins which does not allow mold deposit to occur even after a long-term continuous molding and can give a flame-retardant resin compsn. excellent in impact strength, heat resistance, and flowability, and to obtain a resin compsn. contg. the same. SOLUTION: This retardant is represented by the general formula and contains at least one metal selected from among aluminum, magnesium, sodium, and antimony in a total atom wt. of 1-1,000ppm. In the formula, (a), (b), and (c) are each 1-3; and R<1> , R<2> , and R<3> are each H or a 1-30C hydrocarbon group provided the total number of carbon atoms of R<1> , R<2> , and R<3> of the compd. as the whole is on average 25.1-40. Here, when the retardant is a mixture of arom. phosphoric esters having different substituents, the total number be carbon atoms of R<1> , R<2> , and R<3> is expressed on the number-average basis and is the sum of the products of the wt. fractions of respective arom. phosphoric esters in the retardant and the total numbers of carbon atoms of all the substituents of respective esters.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-volatile flame retardant for a thermoplastic resin. More specifically, the present invention relates to a low volatility flame retardant of a thermoplastic resin which does not generate mold deposits even after continuous molding for a long period of time, and a resin composition containing this agent.

[0002]

2. Description of the Related Art Thermoplastic resins are used in various fields including automobile parts, home electric parts, OA equipment parts and the like because of their excellent moldability and excellent impact resistance. In addition, the flammability of thermoplastic resins limits their use.

As a method for making a thermoplastic resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic-based flame retardant to the thermoplastic resin. I have. However, when a halogen-based flame retardant is used, there are also environmental problems, and when a phosphorus-based or inorganic flame retardant is used, impact strength, molding fluidity and heat resistance are not necessarily satisfied. Not, and
There is a problem that mold contamination due to volatile organophosphorus during molding, so-called mold deposit, reduces productivity, or mold contaminants are transferred to molded products and cause stress cracks. Is narrowed.

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

Further, an antistatic agent comprising a sulfonate and a phosphate such as dinonylphenylphenylphosphate (Japanese Patent Laid-Open No. 3-64368), a polyol ester and a triarylphosphate such as bisnonylphenylphenylphosphate. (US Pat. No. 4,780,229) are disclosed, but the agents in the publication are not flame retardants and are substantially different from the present invention.

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 phosphate ester used in the polycarbonate resin composition does not use a phosphate ester monomer having a specific substituent, the balance between volatility resistance and flame retardancy is poor.

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.

As a technique for flame retarding a styrene resin, 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 (Japanese Patent Application Laid-Open No. 63-163). 30
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 three publications does not use a phosphate such as tris (nonylphenyl) phosphate of a specific purity, so that the flame retardancy is low, and a large amount of the above phosphate is added to improve the flame retardancy. Then, heat resistance is significantly reduced.

As another flame retardant technique, carbon number of 4 to 2 is used.
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. The publication is not only different in that it is a production method, but also uses a specific substituent-containing aromatic phosphate monomer to maintain flame retardancy particularly in a styrene resin. It does not disclose or even imply that it significantly improves continuous formability (volatility resistance).

Finally, a phosphate monomer containing a plurality of isopropyl groups and a flame retardant composition (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,
Since it contains a plurality of isopropyl groups as substituents, the viscosity is high, which is not only a problem in handling but also a problem in practical use due to poor light resistance.

On the other hand, as a prior art of a resin composition using an organic phosphorus compound having a prescribed metal content, Japanese Patent Application Laid-Open No.
No. 1121 discloses a flame-retardant resin composition which does not generate gas during molding by mixing a phosphate ester condensate having a magnesium content of 50 ppm or less with a polyphenylene ether-based resin or a resin comprising the same and a styrene-based resin. It discloses that it is possible. However, the above publication is limited to a phosphate ester condensate, and further discloses that excellent flame retardancy is exhibited by the presence of a specific amount of a specific metal with respect to the phosphate ester monomer of the present invention. Nor is it even implied.

[0013]

SUMMARY OF THE INVENTION In view of the above situation, the present invention does not have the above-mentioned problems, that is, it does not generate a mold deposit even after long-term continuous molding (low volatility). An object of the present invention is to provide a flame retardant for a resin and a resin composition using the agent.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a technique for preventing mold deposits, which is one indicator of volatility, and as a result, found that aromatic phosphoric acid containing a specific substituent as a flame retardant. Surprisingly, it has been found that the use of an ester monomer makes it possible to dramatically improve the flame retardancy of a thermoplastic resin while suppressing mold deposition, and has reached the present invention.

That is, the present invention provides a flame retardant represented by the following formula (1), wherein the flame retardant comprises one or more selected from aluminum, magnesium, sodium and antimony in an amount of 1 to 1000 ppm in total atomic weight. An object of the present invention is to provide a low-volatility flame retardant for a thermoplastic resin characterized by containing the resin and a resin composition containing the same.

[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 25.1 to 40 on average as the whole compound. Here, when it comprises a plurality of aromatic phosphates having different substituents, the total number of carbon atoms of the substituents R ¹ , R ² , R ³ of the flame retardant is represented by a number average, It is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituent of each component. Hereinafter, the present invention will be described in detail.

The low volatility flame retardant (component A) of the styrenic resin of the present invention contains an aromatic phosphate ester monomer having a specific substituent.

It is important that the aromatic phosphate ester monomer 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.

[0020] Next substituents R ¹ of the aromatic phosphoric acid ester monomer, R ^2, R ³ is an alkyl group having 1 to 30 is hydrogen or carbon atoms, as a whole compound, the substituents R ^1,
It is important that the number average of the total number of carbon atoms of R ² and R ³ is 25.1 to 40.

It has been found that when the number average of the total number of carbon atoms is less than 25.1, the flame retardancy is excellent, but volatilizes during high-temperature molding, whereas when it exceeds 40, the flame retardancy decreases.

The flame retardant must contain one or more selected from aluminum, magnesium, sodium, and antimony in an amount of 1 to 1000 ppm in total atomic weight, and further have an acid value specified in JIS-K6751. When 0.01 to 1 mgKOH / g and / or the alkylphenol is 0.001 to 1% by weight, it has been found that excellent flame retardancy is exhibited, and the present invention has been completed.

The aromatic phosphate ester monomer constituting the low volatility flame retardant (component A) of the thermoplastic resin of the present invention comprises:
It is represented by the following equation (1).

[0024]

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(Where a, b, and c are from 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 25.1 to 40 on average as the whole compound. Here, when it comprises a plurality of aromatic phosphates having different substituents, the total number of carbon atoms of the substituents R ¹ , R ² , R ³ of the flame retardant is represented by a number average, It is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituent of each component. Among the aromatic phosphate ester monomers of the present invention, the number average of the total number of carbon atoms of the substituents R ¹ , R ² , and R ³ is preferably 26 to 35, more preferably 26 to 30, and more preferably 26 to 30. 27
Is most preferred.

Specific substituents include butyl such as nonyl and t-butyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, decyl, undecyl, dodecyl and tridecyl. , A tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an otadecyl group, a nonadecyl group, an octadodecyl group, and the like. Can be substituted, but a para-substituted product is preferable. The total number of carbon atoms in the alkyl group substituted by one phosphate ester monomer is 25.
It is essential to be in the range of 1 to 40, rather than a phosphate ester monomer having only one aromatic ring substituted by only one long-chain alkyl group, the aromatic ring substituted by only one alkyl group The phosphate ester monomer having a plurality of groups is superior in heat resistance and water resistance.

Among the flame retardants of the present invention, in particular, R ¹ , R ² ,
A phosphate ester monomer in which at least one of R ³ is a nonyl group is preferred, and particularly a phosphate ester monomer mainly containing tris (nonylphenyl) phosphate and containing [bis (nonylphenyl) phenylphosphate] Is most preferred. The phosphoric acid ester monomer is excellent in fire dropping properties, and is extremely excellent as a flame retardant of rank V-2 according to UL-94 flame retardancy standards.
This fact was not previously known.

Further, from the viewpoint of volatility resistance, the total number of carbon atoms of the substituents must satisfy the requirements of the present invention, but the ratio of those having a total number of carbon atoms of the substituents of less than 25.1 is 20% by weight. In the case of the following, more excellent volatility is exhibited.

From the viewpoint of light resistance, the substituents R ¹ , R ² , and R ³ are not aryl groups, and even when they are alkyl groups, it is preferable that the alkyl groups have few branches. One alkyl group is particularly preferred. Even at the same branch, the light resistance of an alkyl group having 5 or less carbon atoms is poor, and the light resistance of a phosphate monomer having an isopropyl group is extremely poor.

Next, 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 monomer increases,
In addition to handling problems, purification is difficult due to high viscosity, and the above-mentioned impurities remain, resulting in light resistance,
The heat discoloration resistance decreases.

The most preferred combination of aromatic phosphate ester monomers in the present invention comprises bis (nonylphenyl) phenyl phosphate (BNPP) and tris (nonylphenyl) phosphate (TNPP), and has a substituent R ¹ , R ² and R ³ have a number average of 2
5.1 to 40, preferably 26 to 35, more preferably 26 to 30, and most preferably 26 to 27.

The aromatic phosphate ester monomer of the present invention comprises
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.

Here, aluminum, magnesium, sodium, and antimony are metal atoms derived from the catalyst used in the production of the above-mentioned aromatic phosphate ester monomer, and the total atomic weight in the aromatic phosphate ester monomer is 1 to
Contains 1000 ppm. The unpurified aromatic phosphate ester monomer obtained by the above production method is purified by washing with water, distillation, or fractionation by liquid chromatography. At this time, the total atomic weight is controlled by changing the degree of purification.

In the present invention, the thermoplastic resin is, for example,
Styrene resin, polyphenylene ether, polyamide, polyester, polyphenylene sulfide,
Polycarbonate, polymethacrylate and the like can be used alone or in combination of two or more. Here, styrene-based resins, polyphenylene ether-based, and polycarbonate-based thermoplastic resins are particularly preferred.

In the present invention, one styrene resin (component B) of the thermoplastic resin is a rubber-modified styrene resin and / or a non-rubber-modified styrene resin, which is compatible with or homogeneously dispersed with the component A. There are no special restrictions. In particular, as the B component, a rubber-modified styrene-based resin alone or a composition comprising a rubber-modified styrene-based resin and a rubber-unmodified styrene-based resin is preferable. 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), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene copolymer). Propylene rubber-styrene copolymer).

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

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

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

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

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

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

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

In the present invention, one polyphenylene ether (component C) of the thermoplastic resin is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula (2).

[0045]

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However, R ¹ , R ² , R ³ , and R ⁴ are each selected from the group consisting of hydrogen, hydrocarbon, and substituted hydrocarbon groups, and may be the same or different.

Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,3-dimethylphenol.
A copolymer with 6-trimethylphenol is preferred,
Among them, poly (2,6-dimethyl-1,4-phenylene ether) is preferred. The method for producing the polyphenylene ether is not particularly limited. For example, a complex of a cuprous salt and an amine according to the method described in US Pat. No. 3,306,874 is used as a catalyst, and for example, 2,6-xylenol Can be easily produced by oxidative polymerization, and in addition, US Pat. No. 3,306,87
No. 5, U.S. Pat. No. 3,257,357,
U.S. Pat. No. 3,257,358 and JP-B-52
It can be easily produced by the methods described in JP-A-17880 and JP-A-50-51197. Reduced viscosity ηsp / c of the polyphenylene ether used in the present invention
(0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is preferably in the range of 0.20 to 0.70 dl / g, and more preferably in the range of 0.30 to 0.60 dl / g. Reduced viscosity η of polyphenylene ether
Means for satisfying the above requirements regarding sp / c include adjustment of the amount of a catalyst in the production of the polyphenylene ether.

When a resin composition is produced by adding a low-volatility flame retardant of the thermoplastic resin of the present invention, 1 to 100 parts by weight of the above-mentioned agent is added to 100 parts by weight of the thermoplastic resin in the composition. Preferably, more preferably 1 to 3
0 parts by weight, most preferably 3 to 20 parts by weight.

The thermoplastic resin in the present invention is most preferably a combination of the component B and the component C. The additive weight ratio of the component B / C in the thermoplastic resin is (1)
-99) / (99-1), more preferably (50-99) / (50-1), and even more preferably (7).
0-97) / (30-3), most preferably (90-
97) / (10-3).

The low-volatility flame retardant (A component) of the thermoplastic resin of the present invention may be optionally used depending on the resin composition.
As the flame retardant other than the component (component D), a halogen-based flame retardant, an organic phosphorus compound other than the component A, red phosphorus, an inorganic phosphate, an inorganic flame retardant, and the like can be blended.

The amount of the component D is preferably 1 to 40 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 5 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin.

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

As the phosphorus-based flame retardant in the component D,
Organic phosphorus compounds, red phosphorus, inorganic phosphates and the like can be mentioned.

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

In the component D, one of the phosphorus-based flame retardants, red phosphorus, has its surface previously selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide in addition to general red phosphorus. Those coated with a metal hydroxide coating, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, those coated with a coating made of a metal hydroxide and a thermosetting resin selected from titanium hydroxide, Aluminum hydroxide, magnesium hydroxide,
Examples thereof include those obtained by double-coating a thermosetting resin film on a metal hydroxide film selected from zinc hydroxide and titanium hydroxide.

In the component D, one of the inorganic phosphates of the phosphorus-based flame retardant is typically ammonium polyphosphate.

The inorganic flame retardant as the component D includes aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, and tin oxide. Hydrates of inorganic metal compounds such as hydrates, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, 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, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite have particularly good flame retardant effects and are economically advantageous.

The amount of the component D in the present invention is 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 100 parts by weight, based on 100 parts by weight of the thermoplastic resin.
-20 parts by weight, most preferably 5-15 parts by weight.

The low volatility flame retardant (component A) of the thermoplastic resin of the present invention may be, if necessary, a saturated higher aliphatic carboxylic acid or a metal salt thereof, a carboxylic acid ester wax, depending on the resin composition. One or more release agents (component E) selected from organosiloxane waxes, polyolefin waxes, and polycaprolactone can be blended.

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

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

The amount of the component E is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, and most preferably 0.3 to 1 part by weight based on 100 parts by weight of the thermoplastic resin.
Parts by weight.

In the present invention, if necessary, one or more flame retardants selected from triazine skeleton-containing compounds, novolak resins, metal-containing compounds, silicone resins, silicone oils, silica, aramid fibers, fluororesins, and polyacrylonitrile fibers. An auxiliary agent (F component) can be blended.

The amount of the component F 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 based on 100 parts by weight of the thermoplastic resin.
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 represented by the following formula (3), melem represented by the following formula (4), and melon (melem 3 at 600 ° C. or higher).
A product of deammonification of three molecules from a molecule), melamine cyanurate represented by the following formula (5), melamine phosphate represented by the following formula (6), succinoguanamine represented by the following formula (7), adipo Examples thereof include guanamine, methylglutaloganamine, a melamine resin represented by the following formula (8), and a BT resin represented by the following formula (9). Melamine cyanurate is particularly preferred from the viewpoint of volatility resistance.

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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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 the production of a novolak resin is represented by the following formula (1)
0) and (11).

[0075]

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

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

[0082]

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

[0084]

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[0085]

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

The silica as 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-
Aminosilane such as phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit similar in structure to the thermoplastic resin is particularly preferable. For example, p-styryltrimethoxysilane is preferable for a styrene-based resin.

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

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

The fluorine-based resin 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 a tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.

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 the like, and dry spinning is performed by dry spinning in an air stream at 400 ° C., or wet spinning is performed by dissolving the polymer in a solvent such as nitric acid and wet spinning in water. It is manufactured by the method.

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

The amount of the G component is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and most preferably 1 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin. It is.

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 acid as the component G is a releasing agent (E
And unsaturated fatty acids such as ricinoleic acid, ricinbereidic acid and 9-oxy-12-octadecenoic acid.

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
-Hydroxyphenyl) stearic acid amide and the like.

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.

In the present invention, if necessary, a thermoplastic elastomer (H component) can be blended. For example, polystyrene, polyolefin, polyester, polyurethane, 1,2-polybutadiene, polyvinyl chloride And a polystyrene-based 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 comprising an aromatic vinyl unit and a conjugated diene unit, or a block copolymer in which the conjugated diene unit is partially hydrogenated.

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

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

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

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

The amount of the component I 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 based on 100 parts by weight of the thermoplastic resin.
Parts by weight.

In the present invention, as a method for producing a resin composition using polyphenylene ether (component C), a styrene resin and a component C are first melted,
After adding the components and melt kneading with the same extruder, or after producing a masterbatch containing the styrene resin, the C component, or the A component as necessary, the masterbatch and the remaining styrene resin or There is a method of kneading the remaining A component.

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

In the present invention, in particular, V-94 regulated V
Preferred examples of the drop-type flame-retardant resin composition corresponding to the -2 ranking include the following.

The reduced viscosity ηsp / C of the resin portion is 0.4 to
90-97% by weight of a styrene-based resin comprising a rubber-modified styrene-based resin and a rubber-unmodified styrene-based resin having a weight of 0.6,
Thermoplastic resin 1 containing 10 to 3% by weight of polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6
With respect to 00 parts by weight, the flame retardants 3 to 2 represented by the formula (1)
0 parts by weight, one or more compounds selected from saturated higher aliphatic carboxylic acids and metal salts thereof 0.01
~ 5 parts by weight.

By satisfying the above-mentioned combination and the requirement of the reduced viscosity, the balance between the dripping property of fire and the impact strength is improved.

In the case of the above composition, flame retardancy, in particular, drop-type flame retardancy, mold release, continuous moldability, moldability (flowability),
Excellent balance of impact resistance and heat resistance.

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

[0118]

BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLES 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 the examples and comparative examples, various measurements were performed using the following measuring methods or measuring instruments.

(1) Analysis of 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
l; injection sample amount: 0.08 g / 20 ml], assuming that the area ratio of each component on the chromatogram is the weight fraction of each component, and from the area ratio, the phosphate ester and the remaining aromatic vinyl monomer In addition, the compositions and amounts of dimers and trimers of the aromatic vinyl monomer were determined. On the other hand, regarding the above resin portion, a Fourier transform nuclear magnetic resonance apparatus (proton-
Using FT-NMR), the ratio of the integral values of the aromatic protons or aliphatic protons was determined, and the amounts of the rubber-modified styrene resin and the thermoplastic resin such as aromatic polycarbonate and polyphenylene ether were determined.

B) Acid Value of Flame Retardant As a measure of the amount of residual acidic substance in the flame retardant, JIS-K6
The acid value was measured by the method based on No.751.

C) Residual amounts of aluminum, magnesium, sodium and antimony in the flame retardant "ENCYCLOPEDIA OF CHEMICAL"
TECHNOLOGY "Third Edition
n VOLUME 2 "Atomic Absorb"
Tion and Emission Spectro
scopy "p. 621-623, 591, 155, 1
56 (A WILEY-INTERSCIENCE P
UBLICATION John Wiley & Son
s New York 1978).

D) Volatility of flame retardant (thermogravimetric balance test: T
GA method) Using a Shimadzu thermal analyzer DT-40 manufactured by Shimadzu Corporation of Japan, the remaining amount after standing at 300 ° C. for 5 minutes under a nitrogen stream was used as a measure of volatility.

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

0.1 g of the resin thus obtained was
In the case of rubber-modified polystyrene, it is dissolved in toluene, and in the case of rubber-modified acrylonitrile-styrene copolymer resin, it is dissolved in methyl ethyl ketone to give a solution having a concentration of 0.5 g / dl. 10 ml of this solution is placed in a Canon-Fenske viscometer, The solution falling time T ₁ (second) was measured at 30 ° C. On the other hand, the falling time T ₀ (second) of pure toluene or pure methyl ethyl ketone was measured separately using the same viscometer, and calculated by the following formula.

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

(3) Izod impact strength Measured at 23 ° C. by a method according to ASTM-D256.

(V Notch, 1/8 inch Test Specimen) (4) Vicat Softening Temperature Measured by a method in accordance with ASTM-D1525 and used as a measure of heat resistance.

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

(6) Flame retardancy VB (Vertical Bur) conforming to UL-94
ning) method. (1/8 inch test piece) The following components were used for each component used in Examples and Comparative Examples.

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

Polybutadiene 10.5% by weight Styrene 74.2% by weight Ethylbenzene 15.0% by weight α-methylstyrene dimer 0.27% by weight t-butyl peroxyisopropyl carbonate 0.03% by weight Is continuously supplied to a series four-stage reactor equipped with a stirrer, and the first stage has a stirring speed of 190 rpm and 126 rpm.
° C, the second stage is 50 rpm, 133 ° C, the third stage is 20 rpm
rpm, 140 ° C, 4th stage is 20rpm, 155 ° C
The polymerization was carried out. Subsequently, the polymerization liquid having a solid content of 73% was led to a devolatilizer to remove unreacted monomers and a solvent to obtain a rubber-modified aromatic vinyl resin. As a result of analyzing the obtained rubber-modified aromatic vinyl resin (referred to as HIPS-1), the rubber content was 12.1% by weight, the weight average particle diameter of the rubber was 1.5 μm, and the reduced viscosity ηsp / c was 0.53 dl. / G
Met.

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

In Examples and Comparative Examples, the following HIPS
Was used. (Tables 2, 3) HIPS-1: polybutadiene rubber, rubber content is 12.
The weight average particle diameter of the rubber was 1.5 μm, and the reduced viscosity ηsp / c was 0.53 dl / g.

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

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

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

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

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

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

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

Further, polyphenylene ethers having different reduced viscosities ηsp / c were produced by adjusting the amount of catalyst or controlling the polymerization time in the production of polyphenylene ether. Table 4 shows the results.

(C) Phosphorus-based flame retardant Triphenyl phosphate (TPP) A commercially available aromatic phosphate ester monomer [trade name TPP (trade name: TPP) manufactured by Daihachi Chemical Industry Co., Ltd.] was used.
Further, the phosphorus content is 9.5% by weight.

Preparation of Alkyl-Substituted Aromatic Phosphate Monomer (FR-1) Nonylphenol 287.3 parts by weight (molar ratio 2.0),
0.87 parts by weight of aluminum chloride (molar ratio 0.01) was placed in a flask, and 100 parts by weight of phosphorus oxychloride (molar ratio 1.0) was added dropwise at 90 ° C. over 1 hour. 61.4 parts by weight of phenol (molar ratio 1.0) was added to the resulting intermediate, and further reacted. In order to complete the reaction, the temperature was gradually raised and finally raised to 180 ° C. to complete the esterification. Next, the reaction product was cooled and washed with water to remove the catalyst and chlorine, thereby obtaining a phosphoric ester mixture (hereinafter referred to as FR-1). This mixture was subjected to GPC (gel permeation chromatography, Tosoh Corporation).
Manufactured by HLC-8020 mobile phase tetrahydrofuran. ) And nonylphenol in a weight ratio of 77.8 / 11.3 / 8.4 /
2.5.

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

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

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

Examples 1 to 4 Comparative Examples 1 to 5 The various aromatic phosphate ester monomers shown in Table 1 were allowed to stand at 300 ° C. for 5 minutes in a nitrogen stream by a thermogravimetric balance test method, and the remaining amount was measured. I asked.

Next, HIPS-1 / GPPS-1 (7
9/100 parts by weight of an aromatic phosphate ester shown in Table 1 was mechanically mixed with 100 parts by weight of a styrene-based resin (0/30), and the melting temperature was 220 ° C. using a Labo Plastomill manufactured by Toyo Seiki Seisaku-sho. At 50 rpm for 5 minutes. From the resin composition thus obtained, a test piece having a thickness of 1/8 inch was prepared by a compression molding method, and the flame retardancy was evaluated. The results are shown in Table 1 and FIG. According to Table 1 and FIG. 1, the substituents R ¹ , R ² ,
The total number of carbon atoms of R ³ can be seen that excellent resistance to volatilization and flame retardancy in the range of average 25.1 to 40.

[0150]

[Table 1]

TPP: triphenyl phosphate NPDP: nonylphenyl diphenyl phosphate BNPP: bis (nonylphenyl) phenyl phosphate BONP: bis (octylphenyl) nonylphenyl phosphate BNOP: bis (nonylphenyl) octylphenyl phosphate TNPP: Tris (nonylphenyl) phosphate BNDP: bis (nonylphenyl) dodecylphenylphosphate BPDP: bis (pentadecylphenyl) decylphenylphosphate BPDPP: bis (pentadecylphenyl) dodecylphenylphosphate Examples 5-18 Comparative Example 6 -7 When purifying and separating FR-1, TNPP obtained under different purification conditions was used, and the composition was changed to HIPS-1 / G.
Test pieces were prepared in the same manner as in Example 1 except that PPS / TNPP was changed to 70/30/9 (weight ratio), and the flame retardancy was evaluated. Table 2 shows the results. Table 2
According to the graph, it is understood that excellent flame retardancy is exhibited when the total weight of the residual metal, the amount of nonylphenol as the raw material, and the acid value are in specific ranges.

[0152]

[Table 2]

Examples 19 to 24 Test pieces were prepared in the same manner as in Example 1 except that 9 parts by weight of TNPP were blended with 100 parts by weight of HIPS having a reduced viscosity ηsp / C shown in Table 3. Then, MFR, Izod impact strength, Vicat softening temperature, and flame retardancy were evaluated. Table 3 shows the results. According to Table 3, the reduced viscosity ηsp / C, which is an index of the molecular weight of HIPS,
Are smaller, the drip-type flame retardancy is better.
When p / C is in the range of 0.4 to 0.6, fluidity,
It can be seen that the balance between impact strength and flame retardancy is excellent.

[0154]

[Table 3]

Examples 25 to 34 HIPS-1 / GPPS / TNPP / PPE described in Table 4
Were mixed in the weight ratios shown in Table 4 and a side-feedable twin-screw extruder (Werner Pfleiderer) was used.
The melt extrusion was performed using a ZSK-40 mmφ manufactured by the company. That is, PPE / GPPS is set to 320 at the front stage of the extruder.
The mixture was melted at ° C, and the remaining resin component and TNPP were side-fed in the latter stage, and were melt-kneaded at 240 ° C at a rotation speed of 295 rpm and a discharge rate of 80 / h.

A test piece was prepared from the pellet thus obtained using an injection molding machine (Model IS80A, manufactured by Toshiba Machine Co., Ltd.) under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C.
The FR, Izod impact strength, Vicat softening temperature and flame retardancy were evaluated. Table 4 shows the results.

[0157]

[Table 4]

According to Table 4, the heat resistance is improved when PPE is present.
When the thermoplastic resin comprises 3 to 10% by weight of PPE and the reduced viscosity ηsp / C is 0.3 to 0.6, fluidity, heat resistance, rigidity, impact strength and flame retardancy It can be seen that the balance characteristic of the above is remarkably improved.

[0159]

By adding the low-volatility flame retardant of the thermoplastic resin of the present invention to the thermoplastic resin, the mold deposit is remarkably reduced even if continuous molding is performed for a long period of time.
In addition, a resin composition having excellent flame retardancy, impact resistance, heat resistance, and fluidity can be obtained.

The resin composition obtained by using the low-volatile flame retardant of the thermoplastic resin includes a VTR, a distribution board, a television, an audio player, a capacitor, a household outlet,
Household appliances such as boombox, video cassette, video disk player, air conditioner, humidifier, electric warm air machine, chassis or parts, CD-ROM main frame (mechanical chassis), printer, fax, PPC, CRT, word processor copier , Electronic cash register, office computer system, floppy disk drive, keyboard, type, ECR, calculator,
OA equipment housing such as toner cartridge, telephone, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable condenser, AC
Adapter, FBT high pressure bobbin, FBT case, IFT
Electronic and electrical materials such as coil bobbins, jacks, volume shafts, motor parts, and 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 shows the average value of the total number of carbon atoms of the substituents of an aromatic phosphate ester monomer and the average value of 3 in a thermogravimetric balance test (TGA method).
FIG. 4 is a graph showing the relationship between the residual amount of an aromatic phosphate monomer after holding at 00 ° C. for 5 minutes and the flame retardancy (extinguishment time: seconds) of a molded article of a resin composition using the same.

Claims (5)

[Claims] 1. A flame retardant represented by the following formula (1), wherein said flame retardant contains 1 to 1000 ppm in total atomic weight of one or more selected from aluminum, magnesium, sodium and antimony. Features A low-volatility flame retardant for thermoplastic resins. Embedded image (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 substituents R ¹ , R ² , R The total number of carbon atoms of ³ is an average of 25.1 to 40. Here, in the case of consisting 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
It is expressed as a number average, and is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituent of each component. ) 2. The low-volatile flame retardant of a thermoplastic resin according to claim 1, wherein the acid value specified in JIS-K6751 is 0.01 to 1 mgKOH / g and / or the alkylphenol is 0.001 to 1% by weight. 3. A bis (nonylphenyl) phenyl phosphate wherein R ¹ is hydrogen and R ² and R ³ are nonyl groups (BNP
Referred to as P)], tris (nonylphenyl) phosphate [R ^1, R ^2, R ³ is flame retardant according to claim 1 or 2, wherein consists nonyl (referred to as TNPP)]. 4. A resin composition comprising 1 to 100 parts by weight of the flame retardant of claim 1 based on 100 parts by weight of a thermoplastic resin. 5. The resin part has a reduced viscosity ηsp / C of 0.4.
1 to 99% by weight of a rubber-modified styrene resin having a reduced viscosity of 0.6 to 0.6 and 99 to 1% by weight of a polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6 based on 100 parts by weight of a thermoplastic resin. The drop-type flame-retardant resin composition according to claim 4, comprising 1 to 100 parts by weight of the flame retardant according to any one of claims 1 to 3.