JP3073475B2 - Flame retardant heat resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition which is free from dripping of fire during combustion, that is, has excellent drip resistance. More specifically, the present invention relates to a flame-retardant resin composition having excellent drip resistance, flame retardancy, fluidity, heat resistance and impact resistance.

[0002]

2. Description of the Related Art Thermoplastic resins are excellent in moldability and superior in impact resistance as compared with inorganic substances such as glass, so that they are widely used in automobile parts, home electric parts, OA equipment parts and the like. However, its use is limited due to the flammability of the thermoplastic resin.

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, in recent years, the demand for fire safety has been intensely highlighted, and home appliances, O
The regulations of the UL (Underwriters Laboratories) vertical combustion test for A equipment, etc. have become stricter over the years, and the thickness of products and parts has been reduced in order to reduce weight and improve economical efficiency. Thus, the fire drops drastically during combustion, which may cause damage to other products and parts. Therefore, there is a strong demand for the development of a technique for preventing the fall of the fire, that is, a so-called drip prevention technique. As a drip prevention technique, a method of increasing the amount of flame retardant is known, but the use of a large amount of expensive flame retardant is not only economical but also promotes generation of toxic gas and deterioration of mechanical properties. Not preferred.

As a conventional technique for preventing drip, Jour
nal of Fire Retardant Che
mystry, Vol. 7 (May 1980), p6
No. 9 discloses a resin composition comprising polystyrene, a novolak resin and red phosphorus. The resin composition of this publication contains not less than 20% by weight of a novolak resin, so that not only is the impact strength and heat resistance inferior, but also the phosphorus content is about 10%.
Due to the content by weight, the molded article turns red, and there remains a problem in appearance.

Also, US Pat. No. 4,632,946 discloses AB
A non-halogen flame-retardant resin composition comprising a thermoplastic resin such as S resin, a phenol / aldehyde resin, a nitrogen-containing organic compound, and an organic phosphorus compound is disclosed. However, although the resin composition of this publication has excellent flame retardancy, it does not contain a hydroxyl group-containing aromatic phosphate, and therefore has poor fluidity, heat resistance, and impact strength,
Industrial use is reduced. According to the publication, not only the drip resistance but also the fluidity and the heat resistance are simultaneously improved by the interaction between a novolak resin which is a kind of phenol / aldehyde resin and a hydroxyl group-containing aromatic phosphate. No effect is disclosed or implied.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention does not have the above-mentioned problems. It is an object of the present invention to provide a thermoplastic resin composition having excellent flame retardancy, impact resistance, heat resistance and fluidity.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on a technique for preventing drip during combustion of a thermoplastic resin composition. As a result, (A) a rubber-modified styrene resin of 50% by weight or more and polyphenylene ether were used. Polymer blend 100
The combination relative parts by weight, and an organic phosphorus compound 5-40 parts by weight <br/> with (B) an aromatic phosphoric acid ester of a hydroxyl group-free, and 0.5 to 20 parts by weight (C) novolac resin Surprisingly, by blending (D) 0 to 30 parts by weight of a triazine skeleton-containing compound and / or (E) 0 to 30 parts by weight of a fluidity improver, the impact strength can be maintained. In addition, they have found that dripping resistance, flame retardancy, fluidity, and heat resistance can be dramatically improved, and have reached the present invention.

That is, the present invention provides (A) 100 parts by weight of a polymer blend of 50% by weight or more of rubber-modified styrene resin and polyphenylene ether, (B) 5 to 40 parts by weight of a hydroxyl group-free organic phosphorus compound , And (C)
A flame-retardant heat-resistant resin composition containing 0.5 to 20 parts by weight of a novolak resin and having excellent drip resistance and fluidity, and / or the above resin composition, and (D) a triazine skeleton-containing compound
0 to 30 parts by weight , and / or (E) a copolymer resin comprising an aromatic vinyl unit and an acrylate unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester,
An object of the present invention is to provide a flame-retardant heat-resistant resin composition containing 0 to 30 parts by weight of one or more fluidity improvers selected from higher fatty acid amides, higher aliphatic alcohols and metal soaps.

Hereinafter, the present invention will be described in detail.

The resin composition of the present invention comprises (A) 100 parts by weight of a polymer blend of at least 50% by weight of a rubber-modified styrene resin and polyphenylene ether, and (B) 5 to 40 parts by weight of a hydroxyl group-free organic phosphorus compound. And (C)
0.5 to 20 parts by weight of a novolak resin, and if necessary, (D) 0 to 30 parts by weight of a compound having a triazine skeleton
And / or (E) 0 to 30 parts by weight of a fluidity improver.

The component (A) constitutes the main component of the resin composition for molding and plays a role in maintaining the strength of the molded product. The component (B) imparts flame retardancy to the component (A). Component (C) prevents component (A) from dripping at the time of flame retardation,
The component (D) acts as a flame retardant aid for the component (B), and the component (E) is a component for imparting fluidity to the component (A).

Here, the novolak resin of the component (C) is
The cross-linking reaction proceeds due to the elimination of active methylene group hydrogen during combustion. As a result, the inventors have found that the suppression of thermal decomposition, the promotion of char formation, and the effect of thickening at the time of combustion by the crosslinked material prevent the molten resin from dripping during combustion of the thermoplastic resin, and have completed the present invention.

The thermoplastic resin of the component (A) of the present invention is not particularly limited as long as it is compatible with or homogeneously dispersed with the components (B) to (E). Polystyrene and PO
What mixed the phenylene ether system can be used. The polystyrene resin is a rubber-modified styrene resin or a non-rubber-modified styrene resin.

The most preferred combination according to the present invention is a polymer blend of a rubber-modified styrene resin and polyphenylene ether.
It is a thermoplastic resin containing not less than weight%.

The rubber-modified styrenic resin used as the component (A) in the present invention is a polymer obtained by dispersing a rubbery polymer in a matrix of a vinyl aromatic polymer in the form of particles. A known bulk polymerization, bulk suspension polymerization, solution polymerization, or a monomer mixture by adding an aromatic vinyl monomer and, if necessary, a copolymerizable vinyl monomer in the presence of the polymer, It is obtained by emulsion polymerization.

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

The rubbery polymer must have a glass transition temperature (Tg) of -30 ° C. or less.
If the temperature exceeds 30 ° C., the impact resistance is reduced.

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, p-methylstyrene, Examples thereof include chlorostyrene, p-bromostyrene, and 2,4,5-tribromostyrene, with styrene being most preferred. Alternatively, the above-mentioned other aromatic vinyl monomer 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.

When it is necessary to lower the melt viscosity during blending, an acrylate comprising an alkyl group having 1 to 8 carbon atoms can be used. When it is necessary to further increase the heat resistance of the resin composition,
Monomers such as α-methylstyrene, acrylic acid, methacrylic acid, 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 0 to 40% by weight.

The rubbery polymer in the rubber-modified styrenic resin of the present invention is preferably from 5 to 80% by weight, particularly preferably from 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably from 95 to 20% by weight. %, More preferably in the range of 90 to 50% by weight. Outside this range, the balance between the impact resistance and the rigidity of the desired polymer composition cannot be achieved. Further, the rubber particle diameter of the styrene polymer is 0.1.
It is preferably from 1 to 5.0 μm, and particularly preferably from 0.2 to 3.0 μm. Within the above range, impact resistance is particularly improved.

The reduced viscosity η _{SP / C} (0.5 g / dl, toluene solution, measured at 30 ° C.), which is a measure of the molecular weight of the rubber-modified styrenic resin of the present invention, is 0.30 to 0.80 dl / g.
Preferably in the range of 0.40 to 0.60 dl
/ G is more preferable. Means for satisfying the above requirements regarding the reduced viscosity η _{SP / C} of the rubber-modified styrenic resin include adjustment of the polymerization initiator amount, the polymerization temperature, the chain transfer agent amount, and the like.

The polyphenylene ether (hereinafter abbreviated as PPE) used as the component (A) in the present invention comprises:
It is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula.

[0025]

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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 PPE include poly (2,6-dimethyl-1,4-phenylene ether,
Copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferred. The method for producing such PPE is not particularly limited. For example, a complex of a cuprous salt and an amine according to the method described in U.S. Pat. No. 3,306,874 is used as a catalyst, and for example, 2,6-xylenol Can be easily produced by oxidative polymerization of the compound. In addition, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, and U.S. Pat.
358, JP-B-52-17880, and JP-A-50-51197. Reduced viscosity η of the PPE used in the present invention
_{SP / C} (0.5 g / dl, chloroform solution, measured at 30 ° C.) is preferably in the range of 0.20 to 0.70 dl / g, and preferably in the range of 0.30 to 0.60 dl / g. Is more preferred. Means for satisfying the above-mentioned requirement regarding the reduced viscosity of PPE include adjustment of the amount of catalyst in the production of PPE.

The hydroxyl group-free organic phosphorus compound (B) of the present invention is, for example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate ester, phosphite ester, etc.
More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate, Dinopentyl hypophosphite, phenyl pyrocatechol phosphate, ethyl pyrocatechol phosphate, dipyrocatechol hypophosphate, and the like. Particularly preferred are hydroxyl group-free aromatic phosphates represented by the following formulas (1) and (2).

[0029]

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(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₅ , A
r ₆ is a phenyl group, a xyenyl group, an ethylphenyl group,
Ar ₄ is an aromatic group selected from an isopropylphenyl group and a butylphenyl group, Ar ₄ is a divalent aromatic group or a bisphephenol residue, and n is 0 to 3
And m represents an integer of 1 or more. In the present invention, a more preferred organic phosphorus compound having a hydroxyl group-free aromatic phosphate is
Triphenyl phosphate, a dimer of triphenyl phosphate and / or an oligomer thereof, tricresyl phosphate, a dimer and / or oligomer thereof, and a condensed phosphate ester product of bisphenol A and triphenyl phosphate.

The novolak resin of the component (C) of the present invention comprises:
It is a thermoplastic resin obtained by condensing phenols and aldehydes in the presence of an acid catalyst such as sulfuric acid or hydrochloric acid. The production method thereof is described in “Polymer Experiment 5,“ Polycondensation and Polyaddition ”, p. 455 (Kyoritsu Shuppan Co., Ltd.).

An example of the production of a novolak resin is shown below.

[0033]

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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 above aldehydes include formaldehyde,
Acetaldehyde, n-propanal, n-butanal, isopropanal, isobutyraldehyde, 3-methyl-n-butanal, benzaldehyde, p-tolylaldehyde, 2-phenylacetaldehyde and the like.

The (D) triazine skeleton-containing compound of the present invention is a component for further improving the flame retardancy as a flame retardant auxiliary of the hydroxyl group-free organic phosphorus compound of the component (B). Specific examples thereof include melamine, melam (formula (3) below), melem (formula (4) below), melon (600 ° C.).
As described above, a product of deammonation of three molecules of melem, melamine cyanurate (following formula (5)), melamine phosphate (following formula (6)), succinoguanamine (following formula)
(7)), adipoguanamine, methylglutaloganamin, melamine resin (formula (8) below), BT resin (formula below)
(9)) and the like, and melamine cyanurate is particularly preferable from the viewpoint of volatility resistance.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The fluidity improver of the present invention is a copolymer resin comprising an aromatic vinyl unit and an acrylate unit,
It is an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty alcohol, or a metal soap, and one or more of them can be combined.

The aromatic vinyl unit of the copolymer resin is
(A) The aromatic vinyl unit described in the description of the component, and the acrylate unit is an acrylate ester having an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate and butyl acrylate. Here, the content of the acrylate unit in the copolymer resin is preferably from 3 to 40% by weight, and more preferably from 5 to 20% by weight. The solution viscosity (MEK solution of 10% by weight of the resin at a measurement temperature of 25 ° C.) as an index of the molecular weight of the copolymer resin is 2 to 2.
It is preferably 10 cP (centipoise). If the solution viscosity is less than 2 cP, the impact strength is significantly reduced, while if it exceeds 10 cP, the effect of improving the fluidity is reduced.

The above-mentioned aliphatic hydrocarbon-based processing aids include liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides, fluorides and chlorides thereof.

The above-mentioned higher fatty acids include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid, and feronic acid, and unsaturated fatty acids such as ricinoleic acid, ricinbereidic acid, and 9-oxy-12-octadecenoic acid. Fatty acids and the like.

The higher fatty acid esters are monohydric alcohol esters of fatty acids such as methyl phenylstearate and butyl phenylstearate, and monohydric alcohol esters of polybasic acids such as diester phthalic acid of diphenylstearyl phthalate. , 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, monoglyceride oleate, monoglyceride caprate,
Fatty acid esters of glycerin monomers such as behenic acid monoglyceride, polyglycerin stearate,
Polyglycerin oleate, fatty acid ester of polyglycerin such as polyglycerin laurate, polyoxyethylene monolaurate, polyoxyethylene monostearate, fatty acid ester having a polyalkylene ether unit such as polyoxyethylene monooleate, and And neopentyl polyol fatty acid esters such as neopentyl polyol distearate.

The higher fatty acid amides 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, oleic acid. N, N'-2-substituted monoamides such as diethanolamide; and further, methylenebis (12-hydroxyphenyl) stearic acid amide, ethylenebis (stearic acid amide), ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-
A saturated fatty acid bisamide such as (hydroxyphenyl) stearic acid amide; and an aromatic bisamide such as m-xylylenebis (12-hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohols include monohydric alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols such as sorbitol and mannitol,
And polyoxyethylene dodecylamine, polyoxyethylene boctadecylamine, etc., and further, an allylated ether having a polyalkylene ether unit such as polyoxyethylene allylated ether, and polyoxyethylene lauryl ether, polyoxyethylene tridodecyl. Ether, polyoxyethylene cetyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyepichlorohydrin ether; polyoxyethylene bisphenol A It is a dihydric alcohol having a polyalkylene ether unit such as ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A ether, and polyoxyethylene polyoxypropylene glycol ether.

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

The resin composition of the present invention may contain a flame retardant other than the component (B) and a flame retardant auxiliary other than the component (D).

The flame retardants other than the component (B) of the present invention are halogen-based, phosphorus-based and inorganic flame retardants.

Examples of the halogen-based flame retardants include aromatic halogen compounds, halogenated epoxy resins, halogenated polycarbonates, halogenated aromatic vinyl polymers, halogenated cyanurate resins, and halogenated polyphenylene ethers. Decabromodiphenyl oxide, tetrabromobisphenol A, oligomer of tetrabromobisphenol A, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated crosslinked polystyrene, brominated polyphenylene oxide , Polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, halogen-containing phosphoric acid ester, fluororesin, etc. A.

The phosphorus-based flame retardants include red phosphorus, inorganic phosphates and the like.

The red phosphorus used in the present invention means, in addition to general red phosphorus, the surface of the red phosphorus in advance.
Coated with a metal hydroxide film selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide, a metal selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide One coated with a film composed of a hydroxide and a thermosetting resin, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, a film of a metal hydroxide selected from titanium hydroxide, a thermosetting resin Those coated twice with a film can also be suitably used.

The inorganic phosphate used in the present invention is typically ammonium polyphosphate.

Further, examples of inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, and hydrates of tin oxide. Hydrate of inorganic metal compounds, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide , Red phosphorus and the like. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite have particularly good flame retardant effects and are economically advantageous.

Examples of the flame retardant aid other than the component (D) include antimony trioxide, copper oxide, magnesium oxide,
Metal oxides such as zinc oxide, molybdenum oxide, iron oxide, manganese oxide, aluminum oxide, tin oxide, and titanium oxide; and silicone resins such as polydiorganosiloxane.

The resin composition of the present invention comprises: (A) 50 parts by weight or more of a rubber-modified styrene resin and 100 parts by weight of a polymer blend of polyphenylene ether and (B)
It is preferable that 5 to 40 parts by weight of the organic phosphorus compound and 0.5 to 20 parts by weight of the (C) novolak resin are blended, and further, if necessary, (D) the triazine skeleton-containing compound 0 to 3
It is preferable to mix 0 part by weight and 0 to 30 parts by weight of the fluidity improver (E). Here, within the above range, the balance characteristics of flame retardancy, moldability (flowability), impact resistance and heat resistance are excellent.

The resin composition of the present invention can be obtained by, for example, melt-kneading the above-mentioned components with a commercially available single-screw extruder or twin-screw extruder, 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 of the present invention thus obtained is molded by, for example, an injection molding machine or extrusion molding to obtain excellent molding processability (fluidity), flame retardancy, heat resistance and impact resistance. Goods are obtained.

[0063]

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

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

(1) Rubber weight average particle diameter: The weight average particle diameter of the rubber-modified aromatic vinyl resin is determined by measuring the butadiene polymer particle diameter in a transmission electron micrograph taken by an ultra-thin section method of the resin composition. It is calculated by the following equation. Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Ni is the number of butadiene-based polymer particles having a particle diameter of Di.) (2) Reduced viscosity ηsp / c Rubber-modified styrene resin 1 g of methyl ethyl ketone 18
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 a resin component was precipitated with methanol, and then dried. The thus obtained resin 0.1
g was dissolved in toluene to obtain a solution having a concentration of 0.5 g / dl. 10 ml of this solution was placed in a Cannon-Fenske viscometer, and the number of seconds t ₁ flowing at 30 ° C. was measured. On the other hand, the flow time t ₀ of pure toluene was measured separately using the same viscometer, and calculated by the following formula.

[0066]

(Equation 1)

On the other hand, the reduced viscosity ηs of the PPE of the component (A)
For p / c, 0.1 g was dissolved in chloroform,
A solution having a concentration of 0.5 g / dl was prepared, and the measurement was performed in the same manner as described above.

(3) Izod impact strength: ASTM-D
It was measured at 23 ° C. by a method according to 256 (V notch,
1/8 inch specimen).

(4) Vicat softening temperature: ASTM-D1
525 was used as a measure of heat resistance.

(5) Melt flow rate (MFR): Measured by a method based on ASTM-D-1238 as an index of fluidity. It was determined from the extruded amount per minute (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
ing) method (evaluation on 1/8 inch test piece).

(7) Solubility parameter of each component (So
Lubricity Parameter: SP value (δ) Polymer Engineering and S
science, 14, (2), 147 (1974).

[0073]

(Equation 2)

(Where, Δel: aggregation energy per unit functional group, Δvl: molecular volume per unit functional group, δ [unit: (cal / cm ³ ) ^1/2 ] The SP value of the polymer or the blend was calculated by proportional distribution of the weight ratio of the SP value of each component of the monomer unit or the blend, assuming that the addition rule was satisfied.

The following components were used in Examples and Comparative Examples.

(A) Thermoplastic resin (component A) Rubber-modified aromatic vinyl resin (HIPS) Polybutadiene {(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2 / 3) (Nipol 122 OSL, manufactured by Zeon Corporation)
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 1,1-bis (t-butylperoxy) -3,3 5-Trimethylcyclohexane 0.03% by weight Next, the mixture was continuously fed to a serial 4-stage reactor equipped with a stirrer, and the first stage was stirred at 190 rpm and 126 rpm.
° C, the second stage is 50 rpm, 133 ° C, the third stage is 20 rpm
m, 140 ° C., and polymerization was performed at 20 rpm and 155 ° C. in the fourth stage. Subsequently, the polymerization solution having a solid content of 73% was led to a devolatilizer to remove unreacted monomers and a solvent to obtain a rubber-modified styrene resin (referred to as HIPS). As a result of analyzing the obtained rubber-modified styrene resin, the rubber content was 12.3% by weight, the weight average particle diameter of the rubber was 2.2 μm, and the reduced viscosity η was η.
sp / c was 0.52 dl / g.

Rubber-unmodified aromatic vinyl resin (polystyrene (GPPS)) Commercially available polystyrene (weight average molecular weight: 270,000, number average molecular weight: 120,000) (manufactured by Asahi Kasei Corporation)
称 す る) was used.

Production of polyphenylene ether (PPE) A) Production of high molecular weight PPE 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. Thereafter, 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 carried out for 180 minutes while controlling the internal temperature to 30 ° C. After completion of the polymerization, the precipitated polymer was separated by filtration. A mixed solution of methanol / hydrochloric acid was added thereto to decompose the remaining catalyst in the polymer, further sufficiently washed with methanol, and dried to obtain a powdery polyphenylene ether (referred to as PPE-1). Reduced viscosity η _SP is 0.55
dl / g. The SP value is 8.67.

B) Production of Low Molecular Weight PPE In the production of the above high molecular weight PPE-1, the polymerization time was 9
The same experiment as PPE-1 was repeated, except shortening to 0 minutes. The obtained polyphenylene ether was converted to PPE-
No. 2. The reduced viscosity ηsp / C was 0.41 dl / g. The SP value is 8.67.

(B) Hydroxyl-free Organic Phosphorus Compound Hydroxyl-free aromatic phosphate (f)
r-1) Commercially available aromatic condensed phosphate ester derived from bisphenol A [manufactured by Daihachi Chemical Industry Co., Ltd., trade name: CR741C
(Referred to as fr-1)].

The above-mentioned aromatic condensed phosphoric acid ester is
According to GPC analysis, TC represented by the following equation (10)
It was composed of PA-dimer, TCP-A-oligomer and tricresyl phosphate (TCP), and the weight ratio was 80.4 / 14.1 / 5.5, respectively.

[0083]

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(However, n = 1: TCP-A-dimer n ≧ 2: referred to as TCP-A-oligomer.) Aromatic phosphate ester containing no hydroxyl group [triphenyl phosphate (TPP)] Commercially available fragrance Aromatic phosphate [Daichi Chemical Co., Ltd.
Trade name TPP (referred to as TPP)] was used.

Aromatic phosphate ester containing no hydroxyl group (fr-2) Commercially available condensed aromatic phosphate ester [Dahachi Chemical Industry Co., Ltd.
And product name CR733S (referred to as fr-2)].

The above-mentioned aromatic condensed phosphoric acid ester is
According to GPC analysis, TP represented by the following formula (11)
It consisted of a P dimer and a TPP oligomer, and each had a weight ratio of 65/35.

[0087]

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(However, n = 1: TPP dimer n ≧ 2: referred to as TPP oligomer) Aromatic phosphate ester containing no hydroxyl group (f
r-3) Commercially available aromatic condensed phosphoric acid ester derived from bisphenol A (trade name: CR741 (f, manufactured by Daihachi Chemical Industry Co., Ltd.)
r-3))).

The above-mentioned aromatic condensed phosphate ester is represented by G
According to the PC analysis, the TPP-
A-dimer, TPP-A-oligomer and triphenyl phosphate (TPP), each having a weight ratio of 8
4.7 / 13.0 / 2.3.

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(However, n = 1: TPP-A-dimer n ≧ 2: referred to as TPP-A-oligomer.) (C) Novolak resin The following novolak resin was used.

Product name Retop PSM-4326 manufactured by Gunei Chemical Industry Co., Ltd. Softening point 118-122 ° C (NK-
Product name AV light RM10 manufactured by Asahi Organic Materials Industry Co., Ltd.
06N Melting point 98 ° C Softening point 122 ° C Number average molecular weight 5
10 Weight average molecular weight 5190 (referred to as NK-RM) (d) Triazine skeleton-containing compound A commercially available melamine cyanurate [manufactured by Nissan Chemical Industries, Ltd., trade name MC610 (hereinafter referred to as MC)] was used.

(E) Flowability improver (EBS) Commercially available ethylene bisstearic acid amide [formula (1)
3) Kao Corporation product name Kaowax EB-F
F (referred to as EBS)].

[C ₁₇ H ₃₅ CONH] ₂ (CH ₂ ) ₂ (13) Examples 1 to 5 Comparative Example 1 The components described in Tables 1 and 2 were mechanically mixed, and a Labo Plast Mill manufactured by Toyo Seiki Seisaku-Sho, Ltd. After melting at a melting temperature of 250 ° C. and a rotation speed of 50 rpm for 8 minutes, the remaining components were melted under the above conditions under the above conditions.

From the resin composition thus obtained, a test piece having a thickness of 1/8 inch was prepared by a hot press, and the Vicat softening temperature, Izod impact strength, MFR, and flame retardancy were evaluated. Table 1 shows the results.

According to Table 1, it can be seen that the resin composition containing the novolak resin has no dripping of fire, and the fluidity, heat resistance and impact strength are remarkably improved.

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

As described above, the resin composition of the present invention is excellent in non-dropping flame retardancy, and has sufficient fluidity, heat resistance and impact strength for practical use.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 55/02 C08L 55/02 71/12 71/12 // (C08L 51/04 71:12 61:04) (C08L 55/02 71: (12 61:04) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (4)

(57) [Claims] 1. A rubber-modified styrenic resin ( 50% by weight)
% Or more and the polymer blend 100 parts by weight of polyphenylene ether, (B) an organic phosphorus compound 5-40 parts by weight of a hydroxyl group-free, and (C) a novolak resin
A flame-retardant heat-resistant resin composition containing 0.5 to 20 parts by weight . 2. A copolymer resin comprising the resin composition according to claim 1 and (D) 0 to 30 parts by weight of a compound having a triazine skeleton, and / or (E) a copolymer resin comprising an aromatic vinyl unit and an acrylate ester unit, and a fat. Aromatic hydrocarbons, higher fatty acids,
A flame-retardant heat-resistant resin composition containing 0 to 30 parts by weight of one or more fluidity improvers selected from higher fatty acid esters, higher fatty acid amides, higher fatty alcohols and metal soaps. 3. The flame-retardant heat-resistant resin composition according to claim 1, wherein (B) the hydroxyl group-free organic phosphorus compound is an organic phosphorus compound having a hydroxyl group-free aromatic phosphate. 4. The organic phosphorus compound (B) having an aromatic phosphate ester containing no hydroxyl group is triphenyl phosphate, a dimer of triphenyl phosphate and / or an oligomer thereof, tricresyl phosphate, a dimer thereof and / or Oligomers,
The flame-retardant heat-resistant resin composition according to claim 3, which is at least one selected from the group consisting of a condensed phosphoric ester product of bisphenol A and triphenyl phosphate.