JPH1029238A - Production of low volatile styrenic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a styrenic resin compsn. made low in volatilization by a special melt extrusion method for a styrenic resin containing a liquid additive. SOLUTION: When a resin compsn. consisting of 100 pts.wt. of a styrenic resin A and 1-100 pts.wt. of a liquid additive (B) having viscosity of 100000 centistoke at 25 deg.C is extruded in a molten state, a vent to which a vacuum device is connected is provided to an extruder and the average vacuum degree of a vent port is set to 1-300Torr and the average temp. thereof is set to 150-300 deg.C. Especially, the additive (B) is a fire retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a styrene resin composition containing a liquid additive. More specifically, the present invention relates to a method for producing a styrene-based resin composition which can be made less volatile by a special melt extrusion method of a styrene-based resin having a liquid additive.

[0002]

2. Description of the Related Art Styrene-based resins have excellent fluidity, heat resistance and impact resistance, and are used in automobile parts, home electric parts,
It is used in a wide variety of fields including A equipment parts.

In recent years, various polymer additives have been used in such fields for higher functions. For example, it is common practice to add liquid paraphene (mineral oil) to improve processability, or to mix an organic phosphorus compound to impart flame retardancy. However,
Polymer additives are in liquid form and are often volatile.When molding styrenic resins containing liquid additives, they volatilize and reduce productivity due to mold contamination, so-called mold deposits. Or, there is a problem that mold contaminants are transferred to a molded article and cause stress cracks.

[0004] On the other hand, JP-A-8-67789 discloses a kneader connected to a specific deaerator for producing a resin composition comprising a styrene resin and an aromatic polycarbonate and / or an aromatic polyester. It is disclosed to manufacture at specific temperature conditions. The production method disclosed in the above publication is not only different from the present invention in that an aromatic polycarbonate and / or an aromatic polyester is an essential component, but also has a remarkable low volatilization by a specific melt extrusion of a liquid additive. It is not disclosed or even expected to be achieved.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention does not have the above-mentioned problems, that is, low volatility is achieved by a special melt extrusion method of a styrene resin having a liquid additive. It is an object of the present invention to provide a method for producing a styrenic resin composition that has been made possible.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the low volatility of a resin composition containing a liquid additive, and as a result, a liquid additive is produced by a specific melt extrusion method. As a result, surprisingly, the inventors have found that the volatility is dramatically improved, and have reached the present invention.

That is, the present invention relates to (A) a styrene resin
When extruding a resin composition consisting of 100 parts by weight and (B) a liquid additive having a viscosity at 25 ° C. of 100,000 centistokes or less, a vent connected to a vacuum device is provided to the extruder when melt-extruding a resin composition comprising 1 to 100 parts by weight. The average decompression degree of the vent port is 1 to 300 Torr, and the average temperature of the vent port is 1
A method for producing a low-volatile styrene-based resin composition characterized by a temperature of 50 to 300 ° C., in particular, a method for producing a low-volatile styrene-based resin composition in which (B) is a flame retardant, and (B) A method for producing the low-volatile styrenic resin composition, which is a flame retardant represented by the following formula (1):

[0008]

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(Where a, b, and c are from 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or an alkyl group having 1 to 30 carbon atoms, and the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 12 to 30 on average as the whole compound. Here, when it comprises a plurality of aromatic phosphates having different substituents, the total number of carbon atoms of the substituents R ¹ , R ² , R ³ of the flame retardant is represented by a number average, It is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituent of each component. And (A) the reduced viscosity ηsp / C of the resin portion is 0.4
100 parts by weight of a rubber-modified styrenic resin that is
(B) 1 to 100 parts by weight of a flame retardant, and (C) reduced viscosity η
An object of the present invention is to provide a method for producing a low-volatile styrene resin composition comprising 1 to 100 parts by weight of polyphenylene ether having an sp / C of 0.3 to 0.6.

Hereinafter, the present invention will be described in detail.

The present invention relates to (A) a styrene resin, (B)
This is a method for producing a resin composition comprising a specific liquid additive and, if necessary, (C) polyphenylene ether.

The above (A) constitutes the main component of the molding resin composition and plays a role in maintaining the strength of the molded article, and (B) imparts functionality such as flame retardancy and fluidity to the styrene resin. (C) is a component for imparting impact strength, heat resistance and flame retardancy to (A).

Here, when melt extruding the resin composition,
It is essential that the extruder is provided with a vent connected to a vacuum device, that the average depressurization degree of the vent port is 1 to 300 Torr, and that the average temperature of the vent port is 150 to 300 ° C. When the average degree of vacuum is less than 1 Torr or the average temperature is less than 150 ° C., the removal of low volatile components in the liquid additive is not sufficient, while the average degree of vacuum is 300 Torr.
When the average temperature is 300 ° C. or higher, the yield of the liquid additive in the obtained composition is extremely low. According to the above-mentioned melt extrusion conditions, a 1% weight loss temperature of 200 ° C. in a heating test in nitrogen (heating rate: 40 ° C./min)
The inventors have found that the following components are substantially removed and completed the present invention.

In the present invention, the styrene resin (A) is a rubber-modified styrene resin and / or a non-rubber-modified styrene resin, particularly a rubber-modified styrene resin alone or a rubber-modified styrene resin and a rubber-unmodified styrene resin. It is preferable that the resin is made of a resin and is not particularly limited as long as it is compatible with or homogeneously dispersed with (B) to (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), 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, chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate, and an ethylene-propylene-diene monomer terpolymer (EPDM). A diene rubber is particularly preferred.

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

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as components of the rubber-modified styrenic resin. 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.

The liquid additive used as (B) in the present invention has a viscosity of 100,000 centistokes or less at 25 ° C., and is a component (A) for imparting a special function to the styrene resin.

Here, the liquid additive includes a plasticizer, a stabilizer,
UV absorbers, antistatic agents, flame retardants (organic phosphorus compounds), coloring agents, foaming agents, lubricants, fragrances, antioxidants and the like.

The amount of (B) is 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the styrene resin (A). Most preferably, it is 5 to 15 parts by weight.

Examples of the plasticizer include phthalic acid esters such as dimethyl phthalate, diethyl phthalate and diisobutyl phthalate; phthalic acid mixed esters such as butyl benzyl phthalate; diisodecyl succinate and dioctyl adipate. Aliphatic dibasic acid esters, glycol esters such as diethylene glycol dibenzoate, aliphatic acid esters such as butyl oleate and methyl acetyl ricinoleate, epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil; Trioctyl melitate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, tributyl acetyl citrate, chlorinated paraffin, polypropylene adipate, polyethylene sebacate, triacetin, tributyrin, toluene sulfone N'amido, may be mentioned alkyl benzene, biphenyl, partially hydrogenated terphenyl, camphor and the like.

Examples of the stabilizer (B) include:
Metal soap, a lead stabilizer, an organic tin stabilizer, a composite stabilizer, an epoxy compound and the like can be mentioned.

Examples of the foaming agent include azo-based foaming agents such as azobisformamide, azobisisobutyronitrile, diazoaminobenzene, and the like, N, N'dimethyl N, N '
Examples thereof include N-nitroso-based blowing agents such as dinitrosoterephthalamide and N, N 'dinitrosopentamethylenetetramine, and sulfonyl hydrazides such as benzenesulfonyl hydrazide, toluene 4-sulfonyl hydrazide, and benzene 1,3 disulfonyl hydrazide.

Examples of the lubricant (B) include hydrocarbon lubricants such as liquid paraffin, fatty acid lubricants, fatty acid amide lubricants, alcohol lubricants, metal soaps and the like.

Examples of the organic phosphorus compound (B) include phosphine, phosphine oxide, biphosphine, phosphate, phosphite and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate,
Pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate, dineopentyl hypophosphite, phenyl pyrocatechol phosphate, ethyl pyrocatechol phosphate, dipyrocatechol hypophosphate.

Here, particularly, as the organic phosphorus compound, an aromatic phosphate monomer represented by the following formula (2):
An aromatic phosphate condensate represented by the following formula (3) is preferred.

[0032]

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[0033]

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(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , A
r ₅ and Ar ₆ represent a phenyl group, a xyenyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group,
An aromatic group selected from 4,4'-dioxydiarylalkane groups. N represents an integer of 0 to 3;
Represents an integer of 1 or more. Among the above aromatic phosphate ester monomers, particularly, a hydroxyl group-containing aromatic phosphate ester monomer such as tricresyl phosphate or triphenyl phosphate represented by the following formula (2): Phosphate ester monomers containing one or more phenolic hydroxyl groups or aromatic phosphate ester monomers represented by the following formula (1) are preferred.

[0035]

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

Specific substituents include butyl such as nonyl 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 of the alkyl group substituted by one phosphate ester monomer is 12 to
Most preferably, the number of aromatic rings substituted by only one alkyl group is more than that of the phosphate ester monomer having only one aromatic ring substituted by only one long-chain alkyl group. The phosphoric acid ester monomer has better heat resistance and water resistance. For example, even if the total number of carbon atoms of the alkyl group to be substituted is 18, bis (nonylphenyl) phenyl phosphate is preferable because of its higher heat resistance than octadecylphenyl diphenyl phosphate.

In the present invention, among (B) the flame retardants,
In particular R ^1, at least one of R ^2, R ³ is a phosphate ester monomer is preferably a nonyl group, R ^1, R ^2, R ³ is an aromatic phosphoric acid ester monomer is a nonyl group [tris (Nonylphenyl) phenyl phosphate] is most preferred from the viewpoint of fluidity and volatility resistance. When the phosphoric acid ester monomer is contained in the flame retardant at 50% by weight or more, a particularly large flame retardant effect is exhibited. The phosphoric acid ester monomer is excellent in fire dropping properties, and is extremely excellent as a flame retardant of rank V-2 according to UL-94 flame retardancy standards. This fact was not previously known.

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

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

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

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

The most preferred combination of the aromatic phosphate ester monomers in the present invention contains mainly tris (nonylphenyl) phosphate (TNPP) and a small amount of bis (nonylphenyl) phenylphosphate (BNPP). And the number average of the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 20 to 27, preferably 25 to 27, more preferably 26 to 27, and most preferably 26.5 to 27. . In order to satisfy the above number average of the total number of carbon atoms, for example, BNPP is 78 to 0% by weight, preferably 2% by weight.
2 to 0% by weight, more preferably 11 to 0% by weight, most preferably 5 to 0% by weight, and TNPP of 22 to 10% by weight.
0% by weight, preferably 78-100% by weight, more preferably 89-100% by weight, most preferably 95-10% by weight.
It is in the range of 0% by weight. The flame retardant of such a combination is particularly excellent in balance characteristics of flame retardancy, fluidity, heat resistance, impact strength, water gloss retention, and surface hardness of the obtained molded article. TNPP not only has a high volatility resistance and a high effect of imparting heat resistance, but also has excellent water gloss retention because it is structurally symmetric. As described above, TNPP exerts a specific effect and cannot be predicted by conventional knowledge.

The aromatic phosphate monomer used in the present invention is described in JP-A-1-95149 and JP-A-3-95149.
It can be produced by a known method disclosed in, for example, JP-A-294284. For example, there is a method of reacting an alkylphenol, phosphorus oxychloride, and anhydrous aluminum chloride as a catalyst under heating, or a method of oxidizing a phosphite triester with oxygen to convert it to a corresponding aromatic phosphate.

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

In the present invention, another thermoplastic resin can be further blended with the styrene resin. For example, a polyphenylene ether-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, or a mixture of two or more of them can be used. 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 polyphenylene ether (C) which can be added to the styrene resin is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula (4).

[0048]

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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.

The amount of (C) is 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the styrene resin (A). Most preferably, it is 5 to 15 parts by weight.

In the present invention, in particular, UL-94 regulated V
(A) The reduced viscosity ηsp / C of the resin portion is 0.4 to 0.4.
0.6 parts by weight of a rubber-modified styrenic resin,
(B) achieved by combining 1 to 100 parts by weight of the flame retardant represented by the formula (1) and (C) 1 to 100 parts by weight of a polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6. can do. By satisfying the requirement of the reduced viscosity of the present invention, the balance between the dropping property of fire and the impact strength is improved.

In the present invention, if necessary, (D) a polyorganosiloxane can be blended 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 polyorganosiloxane is preferably from 30 to 20,000 CS, more preferably from 40 to 1,000 CS, and most preferably from 50 to 100 CS. If the kinematic viscosity is less than 30 CS, it is highly volatile and causes mold contamination during molding.
If it exceeds 20,000 CS, the orientation relaxation property of the styrene resin is inferior.

Here, the polyorganosiloxane used as (D) is particularly preferably polydimethylsiloxane, so-called silicone oil.

The amount of the polyorganosiloxane is preferably 0.01 to 1 based on 100 parts by weight of the styrene resin.
0 parts by weight, more preferably 0.1 to 5 parts by weight, most preferably 0.3 to 3 parts by weight.

In the present invention, if necessary, (E) a solid organic phosphorus compound other than (B), red phosphorus, an inorganic phosphate, an inorganic flame retardant, etc. may be blended as a flame retardant other than the above flame retardant. can do.

The amount of (E) 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 styrene resin.

The solid organic phosphorus compound as (E) is, for example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate ester, phosphite ester and the like.

An aromatic phosphate condensate such as tetraphenyl / bisphenol A / polyphosphate can be blended to such an extent that flame retardancy is not affected.

The red phosphorus as (E) is, in addition to general red phosphorus, coated on its surface with a coating of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. Coated, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, metal hydroxide selected from titanium hydroxide, and coated with thermosetting resin, aluminum hydroxide, magnesium hydroxide , Zinc hydroxide, titanium hydroxide, and a double coat of a thermosetting resin film on a metal hydroxide film.

The inorganic phosphate as (E) is typically ammonium polyphosphate.

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

In the present invention, a triazine skeleton-containing compound, a novolak resin, a metal-containing compound, a silicone resin, a vinyl-containing silicone oil, silica,
One or more (F) flame retardant aids selected from aramid fibers, fluororesins, and polyacrylonitrile fibers can be blended.

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

The compound having a triazine skeleton as (F) is a component for further improving the flame retardancy as a flame retardant aid of the phosphorus-based flame retardant. Specific examples thereof include melamine, melam represented by the following formula (5), melem represented by the following formula (6), 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 (7), melamine phosphate represented by the following formula (8), succinoguanamine represented by the following formula (9), adipate Examples thereof include guanamine, methylglutaloganamine, a melamine resin represented by the following formula (10), and a BT resin represented by the following formula (11). Melamine cyanurate is particularly preferable 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 (F) 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)
2) and (13).

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

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

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

The vinyl-containing silicone oil (F) is a polydiorganosiloxane comprising a chemical bond unit represented by the following formula (14).

[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 (15) and (16), 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 (F) is amorphous silicon dioxide, particularly preferably silica coated with a hydrocarbon compound, the surface of which is treated with a hydrocarbon compound silane coupling agent. The hydrocarbon compound-coated silica contained is preferred.

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

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

The aramid fiber as (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 converted to an amide polar solvent or sulfuric acid. And solution spinning by a wet or dry method.

The fluorine-based resin (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 (F) has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 500 μm.
The thickness 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 the polymer is dissolved in a solvent such as nitric acid and wet spinning is performed in water. It is manufactured by a spinning 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 more (G) fluidity improvers selected from soaps can be blended.

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

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

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

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

The higher fatty acids as (G) include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid, and ferronic acid, and ricinoleic acid, lysinberidic acid, and 9-oxy-12-octadecenoic acid. And the like.

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

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

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

In the present invention, if necessary, (H) a thermoplastic elastomer can be blended. Examples thereof include polystyrene, polyolefin, polyester, polyurethane, 1,2-polybutadiene, and polyvinyl chloride. And the like, and a polystyrene-based 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 styrene resin. is there.

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

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

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

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

In the present invention, 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 (I) lightfastness improvers selected from agents can be blended.

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

The method for producing the resin composition of the present invention includes:
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 There is a method of kneading the masterbatch and the remaining rubber-modified styrene resin or the remaining (B) after manufacturing a masterbatch containing (B) accordingly.

In the present invention, one of the methods for producing a resin composition containing the component (B) and polyphenylene ether is as follows: a styrene resin is divided into two parts. Is adjusted to 250 to 3 at the front stage of the twin-screw extruder.
It is melted at 50 ° C., and the remaining unmelted component of the styrenic resin and the component (B) in the subsequent stage of the twin-screw extruder are 200 to
This is a method for producing a resin composition that is melt-extruded at 300 ° C.

First, it is important that the resin component having a styrene-based resin and polyphenylene ether melted at the front stage of the twin-screw extruder contains 50% by weight or more of polyphenylene ether. If the content of polyphenylene ether is less than 50% by weight, an unmelted polyphenylene ether is formed because no shear force is applied.

Next, it is preferable to separate the resin component and the component (B). When the resin component is melted in the presence of the component (B), an unmelted product is generated due to a large difference in viscosity between the two. Specifically, polyphenylene ether is 50% by weight.
The rubber-modified styrenic resin and the resin component containing polyphenylene ether contained above are melted at 250 to 350 ° C., and the remaining resin component and the component (B) are subsequently melted for 200 minutes.
Melts at ~ 300 ° C.

When the resin component containing polyphenylene ether is melted at a temperature lower than 250 ° C., an unmelted product of the polyphenylene ether is formed. On the other hand, when the temperature exceeds 350 ° C., the decomposition of the styrene resin starts. When the component (B) of the present invention is melted at a temperature lower than 200 ° C., the compatibility between the resin component and the component (B) is reduced, so that the component (B) undergoes phase separation,
Stable extrusion becomes difficult. On the other hand, if the melting temperature of the component (B) exceeds 300 ° C., the component (B) may volatilize or decompose, which is not preferable.

In the method for producing a resin composition of the present invention,
A twin-screw extruder is preferable as the extruder, and the ratio of the screw length (L) to the cylinder inner diameter (D) (L /
D) is 20 to 50, and has two or more supply openings of a main feed opening and a side feed opening which are different in the distance from the tip of the twin-screw extruder. A kneading portion between the opening portions and between the distal end portion and the supply opening portion at a short distance from the distal end portion, and the length of the kneading portion is 3D to 1 respectively.
It is preferably 0D.

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

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

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

Fourth, the kneading portion of the twin-screw extruder is a portion for improving kneading and mixing properties, and includes a full flight screw portion having a special mixing element, a reverse screw portion, and a kneading portion. It is composed of at least one of a mixing part called a disc and a kneading block.

The full flight screw portion having the special mixing element is a mixing element such as a dalmage screw, a fluted mixing screw, a unimelt screw, a spiral barrier screw, a pin screw, a pineapple mixer, and a cavity transfer mixer.

The reverse screw portion has a function of suppressing resin flow and generating back pressure, and has a large kneading ability.

The mixing portion called the kneading disk or kneading block is assembled by gradually tilting an elliptical disk. 9
When combined at an angle of 0 °, there is no propulsion,
Has good kneading ability. The combination in which the screws are inclined at an angle of 30 ° to the forward screw side has a propulsive force but a small kneading ability. In addition, the disks are thick and thin, and the thick ones have low propulsion and low mixing ability, but have good kneading or shearing ability. On the other hand, thinner ones have higher thrust,
Although the mixing ability is large, the kneading ability is inferior.

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

Mixing and kneading of kneading disks can be controlled by the shape, angle, number, thickness and the like of the disks.

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

Examples of preferred compositions of the resin composition obtained by the production method of the present invention include the following. Consisting of 10 to 90 parts by weight of rubber-modified styrenic resin and 90 to 10 parts by weight of rubber-unmodified styrenic resin,
(A) 100 parts by weight of styrene resin, (B) T
5 to 15 parts by weight of an aromatic phosphate ester monomer containing NPP alone or TNPP and mainly BNPP, and (C) 3 to 10 parts by weight of polyphenylene ether.

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

The resin composition of the present invention can be obtained by, for example, melt-kneading the above components with a commercially available single-screw extruder or twin-screw extruder or the like, in which case 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 And the like can be added as necessary.

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.

[0131]

BEST MODE FOR CARRYING OUT THE INVENTION

[0132]

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

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

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

0.1 g of the resin thus obtained was
In the case of rubber-modified polystyrene, it is dissolved in toluene, and in the case of rubber-modified acrylonitrile-styrene copolymer resin, it is dissolved in methyl ethyl ketone to obtain a solution having a concentration of 0.5 g / dl. 10 ml of this solution is placed in a Canon-Fenske viscometer, The solution falling time T1 (second) was measured at 30 ° C. On the other hand, the falling time T0 (second) of pure toluene or pure methyl ethyl ketone was measured separately using the same viscometer, and calculated by the following formula.

Ηsp / C = (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 0.1.
A solution of 5 g / dl was prepared and measured in the same manner as above.

(2) Viscosity of Liquid Additive Brookfield Engineering La
borateries, INC (Stoughton,
Brook made by Massachusettes USA)
The viscosity (centistokes) at 25 ° C. was measured using a field type viscometer.

(3) Analysis of Liquid Additives 5 g of the resin composition was dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge. (20,000r
pm, 1 hour) Then, 2 ml was added to the supernatant obtained by separation.
A double amount of methanol was added to precipitate a resin component, and the solution portion and the resin portion were separated using an ultracentrifuge. For the solution part, use GPC (gel permeation chromatography) [manufactured by Tosoh Corporation, Japan;
HLC-8020; column, manufactured by Tosoh Corporation, two G1000HXL; mobile phase, tetrahydrofuran; flow rate, 0.8 ml / min; pressure, 60 kg
f / cm ² ; temperature INLET 35 ° C, OVEN 4
0 ° C., RI 35 ° C .; sample loop 100 ml; injected sample amount 0.08 g / 20 ml], and the area ratio of each component on the chromatogram is assumed to be the weight fraction of each component. The composition and amount of the components were determined.

(4) Analysis of Phosphorus Content of Phosphorus-Based Flame Retardant (Liquid Additive) A flat plate having a thickness of 3 mm was prepared from the resin composition by a compression molding method, and an X-ray fluorescence analyzer (SXF manufactured by Shimadzu Corporation) −
1100) was used to determine the fluorescent X-ray intensity of phosphorus Kα radiation. On the other hand, a calibration curve of the X-ray intensity and the phosphorus content of a sample with a known phosphorus content was separately prepared, and the phosphorus content of the unknown sample was determined.

(5) Volatility evaluation of liquid additive (thermogravimetric balance test: TGA method) Using a Shimadzu thermal analyzer DT-40 manufactured by Shimadzu Corporation, Japan, the temperature was raised at a rate of 40 ° C./min under a nitrogen stream. The weight loss at 300 ° C. or 400 ° C. was used as a measure of volatility.

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.

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

(V Notch, 1/8 inch Test Specimen) (7) Vicat Softening Temperature Measured by a method in accordance with ASTM-D1525 and used as a measure of heat resistance.

(8) 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.

(9) 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) (Nippon Zeon ( Co., Ltd., brand name Nipol 122 OSL)｝
Was dissolved in the following mixture to give a uniform solution.

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

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

HIPS-1: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 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.

Non-Rubber Modified Styrene Resin (GPPS) Polystyrene having a weight average molecular weight of 200,000 (produced by Asahi Kasei Corporation) 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.

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

(C) Liquid additive: phosphorus-based flame retardant triphenyl phosphate (TPP) Commercially available aromatic phosphate ester monomer [trade name TPP (trade name: TPP) manufactured by Daihachi Chemical Industry Co., Ltd.] Was.
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, the above aromatic phosphate ester monomer mixture (FR-1) was distilled and further fractionated by liquid chromatography to obtain BNPP.

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

Examples 1 to 4 Comparative Examples 1 to 8 A resin composition consisting of HIPS / FR-1 = 100/7 (weight ratio) was prepared by using a twin-screw extruder having a vent connected to a vacuum device. Melt extrusion was performed under the conditions described. The discharge rate was 60 kg / hour, and the extruder rotation speed was 295 rpm. The results are shown in Table 1.

[0164]

[Table 1]

According to Table 1, the average degree of pressure reduction at the vent port was 1
~ 300 Torr and average vent port temperature is 150
When the temperature is 300 ° C., it is understood that the amount of the low-volatile components having a weight loss temperature of 200 ° C. or less, which are low volatile components, is extremely small while retaining the phosphorus atom as the active component in the component (B).

Examples 5 to 11 The resin compositions shown in Table 2 were mixed mechanically, and a twin-screw extruder (cylinder inner diameter D) capable of side feeding in the same manner as in Example 1
= 40 mmΦ) and melt extrusion was performed. That is,
HIPS / PP at the front end of the extruder (from the main feed opening to the first feed opening [side feeder])
After feeding E-1 from the main feeder and melting at a barrel temperature of 300 ° C, FR-1 was fed from a side feeder and melting at a barrel temperature of 230 ° C. Also,
The average degree of pressure reduction at the vent was 40 Torr, and the average temperature at the vent was 250 ° C. The pellets thus obtained are injected into an injection molding machine (Model IS manufactured by Toshiba Machine Co., Ltd.)
At 80A), test pieces were prepared under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and various physical properties were evaluated. The results are shown in Table 2.

[0167]

[Table 2]

Table 2 shows that the addition of PPE has higher heat resistance. Also, the reduced viscosity ηs of the resin part
It can be seen that when a styrene resin having a p / C of 0.4 to 0.6 is used, the balance characteristics of flame retardancy, fluidity and impact strength are excellent.

Examples 12 to 19 Melt extrusion, molding and evaluation were carried out in the same manner as in Example 5, except that the resin composition was changed to the components and weight ratios shown in Table 3. The results are shown in Table 3.

[0170]

[Table 3]

According to Table 3, the reduced viscosity ηsp / C was 0.1.
With a polyphenylene ether that is 3-0.6,
It can be seen that the flame retardancy, fluidity and impact strength balance characteristics are excellent.

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

[0173]

[Table 4]

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

Examples 20 to 30 In Example 5, the resin composition was changed to HIPS / GPPS.
/ PPE-1 / Aromatic phosphate ester described in Table 5 = 70
Except for changing to / 30/3/7 (weight ratio), melt extrusion, molding and flame retardancy evaluation were performed in the same manner as in Example 5. Further, the temperature of the aromatic phosphate was raised at a rate of 40 ° C./min under a nitrogen stream by a thermogravimetric balance test method, and the relationship between the temperature and the weight loss was determined. Table 5 shows the results.

[0176]

[Table 5]

[0177]

Industrial Applicability The present invention relates to a method for producing a styrene resin composition which can be made less volatile by a special melt extrusion method of a styrene resin containing a liquid additive.

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

Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 55/02 LMC C08L 55/02 LMC // B29K 25:00

Claims (4)

[Claims] When melt-extruding a resin composition comprising (A) 100 parts by weight of a styrene resin and (B) 1 to 100 parts by weight of a liquid additive having a viscosity at 25 ° C. of 100,000 centistokes or less, The extruder is provided with a vent connected to a vacuum device, and the average degree of decompression at the vent port is 1 to 300T.
orr and the average temperature of the vent is 150-300 ° C
A method for producing a low-volatile styrenic resin composition, characterized in that: 2. The method for producing a low-volatile styrenic resin composition according to claim 1, wherein (B) is a flame retardant. 3. The method for producing a low-volatile styrenic resin composition according to claim 1, wherein (B) is a flame retardant represented by the following formula (1). Embedded image (Where a, b, and c are 1 to 3, R ¹ , R ² , and R ³ are hydrogen or an alkyl group having 1 to 30 carbon atoms, and the substituents R ¹ , R ² , R The total number of carbon atoms of ³ is an average of 12 to 30. Here, when a plurality of aromatic phosphates having different substituents are used, the substituents R ¹ , R ² , R The total number of carbon atoms of ³ is represented by a number average and is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituents of each component.) 4. A resin composition comprising (A) 100 parts by weight of a rubber-modified styrene resin having a reduced viscosity ηsp / C of 0.4 to 0.6 in the resin portion, and (B) a flame retardant 1 as a liquid additive. ~
100 parts by weight, and (C) reduced viscosity ηsp / C is 0.3
The method for producing a low-volatile styrenic resin composition according to claim 1, comprising 1 to 100 parts by weight of polyphenylene ether having a molecular weight of 0.6 to 0.6.