JPH06220332A - Thermoplastic resin composition excellent in both molding processability and heat resistance - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition having high-level molding processability (fluidity), heat resistance and impact resistance. CONSTITUTION:This resin composition comprises (A) a thermoplastic resin, (B) an organophosphorus compound represented by hydroxyl group-contg. aromatic phosphoric ester and (C) a processing auxiliary selected from aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher aliphatic alcohols and metallic soaps, and having specific absolute values of the differences for the solubility parameters (SP values) between the components A, B and C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent moldability. More specifically, it relates to a thermoplastic resin composition having excellent moldability (fluidity), heat resistance and impact resistance.

[0002]

2. Description of the Related Art Thermoplastic resins are superior in moldability as compared with inorganic materials such as glass, and are also excellent in impact resistance, so that they can be used in a wide variety of fields including automobile parts, home electric appliance parts, and OA equipment parts. Has been used in the field of. recent years,
With respect to thermoplastic resins used in such fields, production of large-sized thin-walled molded products and shortening of molding cycle are required, and demands for improvement of fluidity are increasing.

In order to improve the flowability of thermoplastic resins,
Techniques for blending various additives are disclosed. With the addition of mineral oil that has been industrially practiced since ancient times,
Although the fluidity is improved, the heat resistance is significantly reduced. Furthermore, esters of polyhydric alcohols and fatty acids (JP-A-61-223045 and JP-A-61-275).
341), higher fatty acids and their metal salts (JP-A-62-62).
-132951), metal salts of higher fatty acids and specific phosphites (JP-A-62-190242), fatty acid amides and aliphatic alcohols and ethylenebisstearylamide (JP-A-62-257951). Gazette), esters of higher fatty acids such as stearyl stearate and higher alcohols (JP-A-2-135219), isocyanuric acid ester compounds (JP-A-2-19).
Japanese Patent No. 4047) and the like are disclosed.
Even with these techniques, a satisfactory resin composition has not been obtained because the improvement of the fluidity is insufficient or the heat resistance is remarkably lowered at a high addition amount.

Further, JP-A-1-223158 discloses a combination of a hydroxyl group-containing aromatic phosphate ester and a phenol resin. However, it has not been disclosed that the combination of a thermoplastic resin and the above phosphoric ester improves the fluidity while maintaining the heat resistance.

[0005]

In view of the above situation, the present invention provides a thermoplastic resin composition which does not have the above-mentioned problems, that is, has high moldability, heat resistance and impact resistance. It is intended to be provided.

[0006]

Means for Solving the Problems The inventors of the present invention have made earnest studies on improvement of molding processability of a thermoplastic resin, and as a result, compared with the conventional (A) thermoplastic resin, (B) containing a special hydroxyl group. By combining an organic phosphorus compound having an aromatic phosphate and (C) a special processing aid, surprisingly, it becomes possible to dramatically improve molding processability while maintaining heat resistance. The inventors have found that and reached the present invention.

That is, the present invention provides (A) a thermoplastic resin,
From (B) an organic phosphorus compound having a hydroxyl group-containing aromatic phosphate ester, and (C) an organic compound of an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic alcohol, or a metal soap. A resin composition containing a selected processing aid, wherein the hydroxyl group-containing aromatic phosphate ester in the component (A) and the component (B), and the hydroxyl group-containing aromatic phosphate ester in the component (B). And (C) component, and the absolute value of the difference in solubility parameter (SP value) between the (C) component and the (A) component are represented by ΔS1, ΔS2, and ΔS3, respectively, 1.0 ≦ ΔS
1 ≤ 2.0, 0 ≤ ΔS2 ≤ 2.5, 0.5 ≤ ΔS3 ≤
A thermoplastic resin composition excellent in molding processability and heat resistance, characterized by satisfying the relationship of 4.5 [unit: [cal / cm ³ ] ^0.5 ].

The present invention will be described in detail below. The thermoplastic resin composition of the present invention comprises (A) a thermoplastic resin, (B) an organic phosphorus compound having a special hydroxyl group-containing aromatic phosphate ester, and (C) a special processing aid.
The component (A) constitutes the main component of the molding resin composition and plays a role of maintaining the strength of the molded product, while the component (B) retains heat resistance and impact resistance with respect to the component (A). The component (C) is a component for imparting fluidity, and the component (C) is a component for promoting the above effects of the component (B).

In the resin composition of the present invention, (A),
Between the hydroxyl group-containing aromatic phosphate ester in the component (B) and the component (C), a specific compatibility, that is, a specific S
It is important to have a P value difference. Here, by containing a hydroxyl group in the component (B), the polarity of the aromatic phosphoric acid ester is increased, and partial compatibility with the thermoplastic resin such as a styrene resin is exhibited. We have
It has been found that this partial compatibility is the principle of greatly improving fluidity while maintaining heat resistance and impact resistance. Next, the component (C) maintains a specific compatibility with the hydroxyl group-containing aromatic phosphate ester in the component (A) and the component (B), thereby further enhancing the partial compatibility of the component (B), The inventors have found that the above effects are promoted and have completed the present invention.

The thermoplastic resin as the component (A) of the present invention is a polystyrene type, a polyolefin type, a polyvinyl chloride type, a polyphenylene ether type, a polyamide type, a polyester type, a polyphenylene sulfide type, or a polycarbonate type. , A polymethacrylate type thermoplastic resin, and includes a single type or a mixture of two or more types. Here, a polystyrene-based thermoplastic resin is particularly preferable as the thermoplastic resin. The polystyrene-based resin is a rubber-modified styrene-based resin or a rubber-unmodified styrene-based resin.

The most preferable combination as the thermoplastic resin of the present invention is a polymer blend of a rubber-modified styrene resin and a polyphenylene ether resin, wherein the rubber-modified styrene resin is 50% or more in the component (A). It is preferable to contain The rubber-modified styrenic resin as the component (A) of the present invention is a polymer in which a rubber-like polymer is dispersed in particles in a matrix composed of a vinyl aromatic polymer, and the presence of the rubber-like polymer. An aromatic vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith are added to the monomer mixture to perform known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization. can get.

Examples of such resins include high impact polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer) and the like. Here, the rubbery polymer needs to have a glass transition temperature (Tg) of -30 ° C or lower, and if it exceeds -30 ° C, the impact resistance is lowered.

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

The aromatic vinyl monomer which is 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-chlorostyrene, p-
Bromostyrene, 2,4,5-tribromostyrene and the like are preferable, and styrene is the most preferable, but styrene may be the main component and other aromatic vinyl monomers may be copolymerized.

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component of the rubber-modified styrene resin. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to reduce the melt viscosity during blending, an acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used. Furthermore, when it is necessary to further increase the heat resistance of the resin composition, a monomer such as α-methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, or N-substituted maleimide may be copolymerized. The vinyl monomer copolymerizable with the vinyl aromatic monomer is preferably in the range of 0 to 40% by weight in the monomer mixture.

The rubber-like polymer in the rubber-modified styrenic resin of the present invention is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 20%. %, More preferably 90 to 50% by weight. Within this range, the desired resin composition is particularly excellent in the balance between impact resistance and rigidity. Furthermore, the rubber particle size of the styrene-based polymer is
0.1 to 5.0 μm is preferable, especially 0.2 to 3.0 μm
m is preferred. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / 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 is preferably in the range of 0.40 to 0.60
More preferably, it is in the range of dl / g. As means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the rubber-modified styrene resin, the amount of the polymerization initiator, the polymerization temperature,
And the adjustment of the amount of chain transfer agent. That is, in order to increase the molecular weight, the above factors are decreased, while in order to decrease the molecular weight, the above factors are increased.

The polyphenylene ether as the component (A) of the present invention
Tell (hereinafter abbreviated as PPE) is a homopolymer and / or copolymer composed of a bonding unit represented by the following formula.

[0019]

[Chemical 1]

However, R1, R2, R3, and R4 are each selected from the group consisting of hydrogen, hydrocarbons, and substituted hydrocarbon groups, and may be the same or different. As a specific example of this PPE, poly (2,
6-dimethyl-1,4-phenylene ether, 2,6-
Dimethylphenol and 2,3,6-trimethylphenol
Copolymers with poly (2,6-
Dimethyl-1,4-phenylene ether) is preferred.
The method for producing such PPE is not particularly limited, and, for example, using a complex of a cuprous salt and an amine according to the method described in US Pat. No. 3,306,874 as a catalyst, for example, 2,6 xyleno It can be easily produced by oxidative polymerization of silane, and it is also possible to obtain it in addition to US Pat. No. 3,306,875 and US Pat.
No. 7,357, U.S. Pat. No. 3,257,358, and Japanese Examined Patent Publication No. 52-17880.
It can be easily manufactured by the method described in 0-51197. The reduced viscosity of the PPE used in the present invention (0.5
g / dl, chloroform solution, measured at 30 ° C) was 0.
It is preferably in the range of 20 to 0.70 dl / g,
It is more preferably in the range of 0.30 to 0.60 dl / g. Examples of means for satisfying the above requirements regarding the reduced viscosity of PPE include adjustment of the amount of catalyst during production of the PPE.

The component (B) of the present invention is an organic phosphorus compound having a hydroxyl group-containing aromatic phosphoric acid ester, and can also contain an organic phosphorus compound having no hydroxyl group. Here, in particular, the hydroxyl group-containing aromatic phosphate ester is preferably contained in the component (B) in an amount of 20% or more. The hydroxyl group-containing aromatic phosphoric acid ester contains one or more phenolic hydroxyl groups in tricresyl phosphate, triphenyl phosphate, condensed phosphoric acid ester thereof and the like. It is a phosphoric acid ester, for example, the following compound.

[0022]

[Chemical 2]

[0023]

[Chemical 3]

(However, Ar1, Ar2, Ar3, Ar4
, Ar5 and Ar6 are aromatic groups selected from a phenyl group, a xylenyl group, an ethylphenyl group, an isopropylphenyl group and a butylphenyl group, and at least one hydroxyl group is substituted with the above aromatic group in the phosphoric acid ester. ing. Further, n represents an integer of 0 to 3, and m represents 1
Represents the above integers. ) Among the hydroxyl group-containing aromatic phosphates of the present invention, diphenylresorcinyl phosphate (formula 4 below) or diphenylhydroquinonyl phosphate (formula 5 below) is particularly preferable. The manufacturing method is described in, for example, JP-A 1-223158.
It is disclosed in Japanese Patent Application Publication No. JP-A No. 1993-242, and is obtained by the reaction of phenol, hydroxyphenol, aluminum chloride and phosphorus oxychloride.

[0025]

[Chemical 4]

[0026]

[Chemical 5]

The organophosphorus compound containing no hydroxyl group in the component (B) is a phosphine, a phosphine oxide, a biphosphine, a phosphonium salt, a phosphinate, a phosphoric acid ester containing no hydroxyl group, or a phosphorous acid Ester and the like, specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite,
Methylneopentylphosphonate, phenylneopentylphosphate, pentaerythritol diphenyldiphosphate, dicyclopentylhypophosphite, dineopentylhyphophosphite, phenylpyrocatecholphosphite, ethylpyrocatecholphosphate, dipyrocatecholhypophosphosphate Such as fate.

The special processing aid (C) of the present invention is a processing aid selected from aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher aliphatic alcohols and organic compounds of metal soaps. And preferably a compound having at least one hydroxyl group in one molecule. The above-mentioned aliphatic hydrocarbons are liquid paraffins, natural paraffins, microwaxes, polyolefin waxes, synthetic paraffins, and partial oxides thereof, or aliphatic hydrocarbons containing a hydroxyl group in fluoride, chloride or the like. Specific examples thereof include 1-hydroxypentacontane and oxyethylene / oxypropylene block polymer.

The higher fatty acids include those partially substituted with aromatic groups, and include α-oxycaproic acid, 14-oxyhexadecanoic acid, ω-oxypalmitic acid, 12-hydroxystearic acid and 12-hydroxyphenylstearin. Examples thereof include a hydroxyl group-containing saturated fatty acid such as acid and ferronic acid, and a hydroxyl group-containing unsaturated fatty acid such as ricinoleic acid, lysine belaidic acid and 9-oxy12 octadecenoic acid.

The above-mentioned higher fatty acid esters include those partially substituted with aromatic groups, and are monovalent alcohol esters of hydroxyl group-containing fatty acids such as methyl 12-hydroxyphenylstearate and butyl 12-hydroxyphenylstearate. And a monovalent alcohol ester of a hydroxyl group-containing polybasic acid such as phthalic acid diester of phthalic acid di (12-hydroxyphenyl) stearyl,
Further, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate. -, Sorbitan esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate, fatty acid esters of glycerin monomers such as stearic acid monoglyceride, oleic acid monoglyceride, capric acid monoglyceride and behenic acid monoglyceride Polyglycerin stearic acid ester, polyglycerin oleic acid ester, polyglycerin lauric acid ester and other fatty acid esters of polyglycerin, polyoxyethylene monolaurate, polyoxy ester Ethylene monostearate - DOO, polyoxyethylene monooleate - such bets Poriarukiren'e - hydroxyl group-containing fatty acid ester having an ether unit,
And neopentylpolyol fatty acid ester such as neopentylpolyol distearic acid ester. Also included are higher fatty acid esters containing no hydroxyl group, such as polyoxyethylene distearate.

The above-mentioned higher fatty acid amides include those partially substituted with aromatic groups, and include hydroxyl group-containing saturated fatty acids such as 12-hydroxyphenylstearic acid amide, methylol stearic acid amide, and methylol behenic acid amide. Monoamide, coconut oil fatty acid dietanol,
Lauric acid diethanolamide, coconut oil fatty acid dietanolamide, oleic acid dietanolamide, and other hydroxyl group-containing N, N'-2 substituted monoamides, and methylenebis (12-hydroxyphenyl) stearic acid amide, ethylene Hydroxyl group-containing saturated fatty acid bisamides such as bis (12-hydroxyphenyl) stearic acid amide and hexamethylenebis (12-hydroxyphenyl) stearic acid amide, and m-
It is a hydroxyl group-containing aromatic bisamide such as xylylenebis (12-hydroxyphenyl) stearic acid amide.

The above-mentioned higher aliphatic alcohols include those partially substituted with aromatic groups, such as monovalent alcohols such as stearyl alcohol and cetyl alcohol, sorbitol and mannitol. Polyoxyethylene dodecylamine, polyoxyethylene voctadecylamine, and the like, and polyallyl ether having a polyalkylene ether unit such as polyoxyethylene allyl ether. Ter, and polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether Such as polyoxyethylene alkylphenyl ether, polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A ether, poly It is a divalent alcohol having a polyalkylene ether unit such as oxyethylene polyoxypropylene glycol ether.

The metal soap is a metal salt of higher fatty acid such as 12-hydroxyphenylstearic acid such as barium, calcium, zinc, aluminum or magnesium. The resin composition of the present invention comprises the above (A) and (B).
A hydroxyl group-containing aromatic phosphoric acid ester in the component (A) and the component (B), which has a specific compatibility with the hydroxyl group-containing aromatic phosphoric acid ester in the component and the component (C). The absolute value of the difference in the solubility parameter (SP value) between the ester, the hydroxyl group-containing aromatic phosphate ester in the component (B) and the component (C), and between the component (C) and the component (A) is shown. , ΔS1, ΔS2, ΔS3 respectively, 1.0 ≦ ΔS1 ≦ 2.0, 0 ≦ ΔS2 ≦ 2.5,
The relationship of 0.5≤ΔS3≤4.5 is satisfied.

Here, the SP value is the SP value (Solubility Para) calculated by the Fedors equation.
meter: solubility parameter). The calculation method is as follows: Polymer Engineering a
nd Science, 14, (2), 147 (197)
It is shown by the following formula by the calculation method of the SP value (δ) described in 4).

[0035]

[Equation 1]

(Here, Δel: cohesive energy per unit functional group, Δv1: molecular volume per unit functional group.) Hydroxyl group-containing aromatic phosphorus in the above components (A) and (B) It is essential that the absolute value .DELTA.S1 of the difference in SP value from the acid ester is in the range of 1.0 to 2.0. When .DELTA.S1 is less than 1.0, the thermoplastic resin and the above aromatic phosphate ester are completely compatible with each other and the fluidity is improved, but the heat resistance is significantly lowered. On the other hand, ΔS1 is 2.0
If it exceeds, the compatibility of the both decreases and phase separation occurs.
Further, the absolute value Δ of the difference in SP value between the hydroxyl group-containing aromatic phosphate ester in the component (B) and the component (C).
It is essential that S2 is in the range of 0 to 2.5. Δ
When S2 exceeds 2.5, the compatibility between the above-mentioned aromatic phosphate and the processing aid decreases and phase separation occurs.

It is essential that the absolute value ΔS3 of the difference in SP value between the component (C) and the component (A) is in the range of 0.5 to 4.5. When ΔS3 is less than 0.5, the thermoplastic resin and the processing aid are completely compatible and the fluidity is improved, but the heat resistance is significantly lowered. On the other hand, ΔS3 is 4.
When it exceeds 5, the compatibility of the both decreases and phase separation occurs.

Here, the component (A), the hydroxyl group-containing aromatic phosphate in the component (B), and the component (C) are related to each other, and as described in FIG. 1, ΔS1 and ΔS2.
.., .DELTA.S3 is naturally determined as follows. ΔS1 ≦ 2.0 ── ΔS2 ≦ 2.5 ─── + ΔS3 ≦ ΔS1 + ΔS2 ≦ 4.5 When it is necessary to impart flame retardancy to the resin composition of the present invention, (D) A flame retardant and (E) flame retardant aid can be blended.

The flame retardant of the component (D) of the present invention is a halogen-based, phosphorus-based or inorganic flame-retardant. The halogen-based flame retardant is an aromatic halogen compound, a halogenated epoxy resin, a halogenated polycarbonate, a halogenated aromatic vinyl polymer, a halogenated cyanurate resin, a halogenated polyphenylene ether or the like. . Of these, particularly preferred halogen-based flame retardants are decabromodiphenyl oxide, tetrabromobisphenol A, tetrabromobisphenol A oligomers and brominated bisphenols.
Epoxy resin, brominated bisphenol type phenoxy resin, brominated bisphenol type polycarbonate,
Examples thereof include brominated polystyrene, brominated crosslinked polystyrene, brominated polyphenylene ether, polydibromophenylene ether, decabromodiphenyl oxide bisphenol condensate and halogen-containing phosphate ester.

The phosphorus-based flame retardant is red phosphorus, inorganic phosphate, or the like. Red phosphorus of the phosphorus-based flame retardant of the present invention, in addition to general red phosphorus, its surface in advance, aluminum hydroxide, magnesium hydroxide, zinc hydroxide,
A coating made of a metal hydroxide selected from titanium hydroxide, a coating made of aluminum hydroxide, magnesium hydroxide, zinc hydroxide, a metal hydroxide selected from titanium hydroxide and a thermosetting resin. Those that have been coated, those that have been double coated with a thermosetting resin coating on a metal hydroxide coating selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide, etc. is there.

The inorganic phosphate of the phosphorus-based flame retardant of the present invention is typically ammonium polyphosphate. And
Inorganic flame retardants include water of inorganic metal compounds such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, and tin oxide hydrate. Metal oxides such as hydrate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide, iron oxide, copper oxide, titanium oxide, aluminum oxide, manganese oxide, zinc oxide, and zinc borate, zinc metaborate, Examples thereof include barium metaborate, zinc carbonate, magnesium carbonate, mu-calcium, calcium carbonate and barium carbonate. These may be used alone or in combination of two or more.

The flame retardant aid (E) of the present invention is a triazine skeleton-containing compound, a silicone resin, a polyphosphazene, a fluorine resin or the like. Here, the above-mentioned triazine skeleton-containing compound is particularly preferable as the flame retardant aid for the phosphorus-based flame retardant. Specific examples thereof include melamine, melam, melon,
Examples thereof include melamine cyanurate, succinoguanamine, adipoguanamine, methylglutaloganamin, melamine phosphate, melamine resin and BT resin, with melamine cyanurate being particularly preferred.

The above-mentioned fluororesin is a resin containing fluorine atoms in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination so long as the drip resistance is not impaired.

Methods for producing these fluororesins are described in US Pat. No. 2,393,697 and US Pat.
534,058, for example, tetrafluoroethylene in an aqueous medium using a radical initiator such as ammonium persulfate, potassium persulfate, 7-70 kg
Polymerization at a temperature of 0 to 200 ° C. under a pressure of / cm ² and then polytetrafluoroethylene powder is obtained from the suspension, dispersion or emulsion by coagulation or by precipitation.

The resin composition of the present invention comprises (A) 100 parts by weight of a thermoplastic resin, (B) 5 to 40 parts by weight of an organic phosphorus compound having a hydroxyl group-containing phosphate ester, and (C) a special compound. It is preferable that the processing aid is in the range of 1 to 20 parts by weight, the (D) flame retardant is in the range of 0 to 40 parts by weight, and the (E) flame retardant aid is in the range of 0 to 30 parts by weight. Here, in the above range, the balance characteristics of molding processability (flowability), flame retardancy, 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 in a commercially available single-screw extruder, a twin-screw extruder or the like. Inhibitor, benzotriazole and hinder
UV absorbers such as doamine, 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, coloring agents such as dyes and pigments Etc. can be added as needed.

By molding the composition of the present invention thus obtained, for example, by injection molding or extrusion molding, molding excellent in molding processability (fluidity), flame retardancy, heat resistance and impact resistance is performed. Goods are obtained.

[0048]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. The measurements in Examples and Comparative Examples were performed using the following methods or measuring machines.

(1) Weight average particle diameter of rubber The weight average particle diameter of the rubber-modified styrenic resin is obtained by determining the particle diameter of the butadiene-based polymer in the transmission electron microscope photograph taken by the ultrathin section method of the resin composition, It is calculated by the following formula. Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Ni is the number of butadiene-based polymer particles whose particles are Di.) (2) Reduced viscosity ηSP / C 1 g of rubber-modified styrene-based resin Methyl ethyl ketone 18
Add a mixed solvent of 2 ml of methanol and 2 ml of methanol, and add 2 ml at 25 ° C.
Shake for time and centrifuge at 18000 rpm for 30 minutes at 5 ° C. The supernatant was taken out, the resin component was precipitated with methanol, and then dried.

0.1 g of the resin thus obtained was dissolved in toluene to give a solution having a concentration of 0.5 g / dl, and 10 ml of this solution was placed in a Canon-Fenske type viscometer.
At 30 ° C., the number of seconds t1 during which the solution flows was measured. On the other hand, the flowing seconds t0 of pure toluene was separately measured with the same viscometer and calculated by the following mathematical formula.

[0051]

[Equation 2]

On the other hand, the reduced viscosity ηSP of the component (A) PPE
For / c, 0.1 g was dissolved in chloroform to prepare a solution having a concentration of 0.5 g / dl, and the same measurement as above was performed. (3) Solubility parameter of each component (Solubili
ty Parameter: SP value (δ) Polymer Engineering and S
Science, 14, (2), 147 (1974).

[0053]

[Equation 3]

[Here, Δe1 is the cohesive energy per unit functional group, and Δv1 is the molecular volume per unit functional group. δ [unit: (cal / cm ³ ) ^0.5 ]] The SP value of the copolymer or the blend is assumed to satisfy the addition rule, and the weight of the SP value of each component of the monomer unit or the blend. Calculated by proportional distribution of the ratio.

(4) Izod impact strength Measured at 23 ° C. by a method according to ASTM-D256. (V notch, 1/8 inch test piece) (5) Vicat softening temperature Measured by a method according to ASTM-D1525 and used as a scale of heat resistance.

(6) Melt flow rate (MFR) The melt flow rate was measured by a method according to ASTM-D1238. 10 at a load of 5 kg and a melting temperature of 200 ° C
It was determined from the extrusion rate per minute (g / 10 minutes).
(7) Flame retardance VB (Vertical Bur) compliant with UL-94
Ning) method. (1/8 inch test piece) The following components were used as the components used in Examples and Comparative Examples.

(A) Thermoplastic resin Production of rubber-modified styrene resin (HIPS) Polybutadiene [(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond = 95/2/3 (weight ratio)) (Product name Nipol 1220S, manufactured by Nippon Zeon Co., Ltd.)
L)] was dissolved in the following mixed solution to form 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) -3,3,3 5-Trimethylcyclohexane 0.03% by weight Then, the above mixture was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage was stirred at 190 rpm,
26 ° C, 50 rpm for second stage, 133 ° C for second stage, 20 for third stage
Polymerization was carried out at rpm of 140 ° C. and the fourth stage at 20 rpm of 155 ° C. Subsequently, the polymerization liquid having a solid content of 73% was introduced into a degassing apparatus to remove unreacted monomers and solvent to obtain a rubber-modified styrene resin. The rubber-modified styrene resin thus obtained was analyzed, and as a result, the rubber content was 12.3% by weight and the weight average particle diameter of the rubber was 2.2 μm.
m, and the reduced viscosity ηSP / C was 0.52 dl / g. Also, the SP value of HIPS is 10.3, and the SP values of polystyrene and polybutadiene are 10.5 each.
2 and 8.64 are used, and the weight ratio of the above components is 87.7 / 1.
It was calculated by proportional distribution at the ratio of 2.3.

Production of Polyphenylene Ether (PPE) After fully replacing the inside of a stainless steel reactor having an oxygen blowing port at the bottom of the reactor with a cooling coil and stirring blades with nitrogen, Cupric bromide 54.8 g, di-n
Then, 8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 1110 g of -butylamine, 20 liters of toluene, 16 liters of n-butanol and 4 liters of methanol and charged into a reactor. Continue to blow oxygen into the reactor while stirring and control the internal temperature to 30 ° C.
Polymerization was carried out for 0 minutes. Polymer which is deposited after the completion of polymerization
I separated it. Add a methanol / hydrochloric acid mixture to this,
The residual catalyst in the polymer was decomposed, further thoroughly washed with methanol and dried to obtain powdery polyphenylene ether. (Referred to as PPE) Reduced viscosity ηsp / C
Was 0.55 dl / g. The SP value is 8.67.
Is.

Next, the above PPE and polystyrene (Asahi Kasei Polystyrene 685, trade name, manufactured by Asahi Kasei Corp.)
Were mixed at a weight ratio of 70/30, and were mixed in a twin screw extruder at 350 °
Melt extrusion was performed at C. PPE-
It is called MB. The SP value of PPE-MB is 9.2.
The SP values of PPE and polystyrene are 8.67 and 10.52, respectively, and the weight ratio of the above components is 70.
It was determined by proportional distribution at a ratio of / 30.

ABS resin Commercially available ABS resin [acrylonitrile / butadiene / styrene = 26/14/60 (weight ratio) [Asahi Kasei Kogyo's trade name Stylak ABS120B] (A
This is referred to as BS)] was used. Also, the SP value of ABS is
11.2, and the SP values of polyacrylonitrile, polybutadiene and polystyrene were 14.3 respectively.
Using 9, 8.64, 10.52, the weight ratio of the above components is 2
It was determined by proportional distribution at a ratio of 6/14/60.

Polypropylene Commercially available polypropylene [Asa Polymer K.K. Co., Ltd. trade name Es Polymer E7100 (referred to as PP)] was used.
The SP value is 8.0. (B) Organophosphorus compound Hydroxyl group-containing aromatic phosphate ester (FR-
Preparation of 1) 122.7 parts by weight of phenol (molar ratio 2.0) and 0.87 parts by weight of aluminum chloride (0.01 molar ratio) were placed in a flask and 100 parts by weight of phosphorus oxychloride (molar ratio) at 90 ° C. Ratio 1.0) was added dropwise over 1 hour. 71.7 parts by weight (molar ratio 1.0) of resorcin was added to the produced 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. Then, the reaction product is cooled and washed with water to remove the catalyst and the chlorine content, and a phosphoric acid ester mixture (hereinafter, referred to as FR-1
Called). When this mixture was analyzed by GPC (gel permeation chromatography),
Diphenyl resorcinyl phosphate (hereinafter TPP-
OH) (formula 6 below), triphenyl phosphate (hereinafter referred to as TPP), and condensed aromatic phosphate ester (hereinafter referred to as TPP dimer) (formula 7 below) And the weight ratio is 54.2 / 18.3, respectively.
It was /27.5. The SP values of TPP-OH, TPP and TPP dimer are 11.8, 10.
7, 10.8.

[0063]

[Chemical 6]

[0064]

[Chemical 7]

Production of Hydroxyl Group-Containing Aromatic Phosphate Ester (FR-2) In the production of FR-1, the composition ratio of the raw materials was changed. That is, 61.4 parts by weight of phenol (molar ratio 1.0) and 0.87 parts by weight of aluminum chloride (0.01 molar ratio) were placed in a flask and 100 parts by weight of phosphorus oxychloride (molar ratio 1. 0) was added dropwise over 1 hour. 14.3 parts by weight of resorcin (molar ratio 2.0) was added to the produced 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. Then, the reaction product is cooled and washed with water to remove the catalyst and the chlorine content, and a phosphoric acid ester mixture (hereinafter, referred to as FR-2
Called). When this mixture was analyzed by GPC, the following formula TPP- (OH) ₂ , TPP dimer,
It is composed of TPP oligomers and has a weight ratio of 44.1.
It was /35.3/20.6. In addition, TPP- (O
The SP values of H) ₂ , TPP dimer and TPP oligomer are 12.7, 10.8 and 10.8, respectively.

[0066]

[Chemical 8]

Aromatic Phosphate Ester Not Containing Hydroxyl Group [Triphenyl Phosphate (TPP)] Commercially available aromatic phosphate ester [manufactured by Daihachi Chemical Industry Co., Ltd.,
Trade name TPP (referred to as TPP)] was used. Also,
The SP value of TPP is 10.7. Hydroxyl group-free aromatic phosphate ester (FR
-3) Commercially available aromatic condensed phosphoric acid ester [Dahachi Chemical Industry Co., Ltd.
Manufactured by the company, CR733S (referred to as FR-3)] was used.

The aromatic condensed phosphoric acid ester is
According to GPC analysis, the TPP dimer represented by the following formula
And TPP oligomers, each with a weight ratio of 65 /
It was 35. The SP value of the above component is as described above.

[0069]

[Chemical 9]

(However, n = 1 TPP dimer-n≥2 TPP oligomer.) Hydroxyl group-free aromatic phosphate ester (FR)
-4) Commercially available aromatic condensed phosphoric acid ester derived from bisphenol A [manufactured by Daihachi Chemical Industry Co., Ltd., trade name CR741C
(Referred to as FR-4)] was used.

The aromatic condensed phosphoric acid ester is
According to the GPC analysis, it is composed of TCP-A-dimer represented by the following formula, TCP-A-oligomer and tricresyl phosphate (TCP), and the weight ratio is 80.
It was 4 / 14.1 / 5.5. The SP values of TCP-A-dimer, TCP-A-oligomer and TCP are 9.3, 9.4 and 8.8, respectively.

[0072]

[Chemical 10]

(However, n = 1 TCP-A-dimer n ≧ 2 TCP-A-oligomer.) (C) Processing aid hydroxyl group-containing processing aid a) Ethylenebis (12-hydroxy) stearin Acid amide (EBS-OH) Slippercus H manufactured by Nippon Kasei Co., Ltd. was used. (Hereinafter, referred to as EBS-OH.) The SP value is 10.9.

[C ₁₇ H ₃₄ (OH) CONH] ₂ (CH ₂ ) ₂ b) 12- (p-hydroxyphenyl) stearic acid (SA-OH) Nova Acid P manufactured by NOF CORPORATION was used. (Hereinafter, referred to as SA-OH.) The SP value is
10.3.

[0075]

[Chemical 11]

C) Polyglycerin stearic acid ester (PGS) Unigris GS-106 manufactured by NOF CORPORATION was used. (Hereinafter, referred to as PGS.) The SP value is
It is 12.9.

[0077]

[Chemical 12]

D) Polyoxyethylene nonylphenyl ether (POE-NP) Nonionic NS-270 manufactured by NOF CORPORATION is used. (Hereinafter referred to as POE-NP.) Also, SP
The value is 9.4. _{C 9 H 19 -Ph-O- (} CH 2 -CH 2 -O) 70 -H e) polyoxyethylene bis phenol - Le A et - ether (P
OE-A) NOF DA-350F, trade name, manufactured by NOF CORPORATION
Was used. (Hereinafter, referred to as POE-A.) Also, S
The P value is 11.6.

[0079]

[Chemical 13]

F) Bisphenol A (BPA) A reagent manufactured by Tokyo Kasei Co., Ltd. was used. (Hereinafter, referred to as BPA.) Also, the SP value is 12.3.

[0081]

[Chemical 14]

G) Mannitol (MANN) Mannitol Kao manufactured by Kao Corporation was used.
(Hereinafter, referred to as MANN.) The SP value is 14.
It is 1.

[0083]

[Chemical 15]

Hydroxyl group-free processing aid a) Ethylenebisstearic acid amide (EBS) Kao Wax EB-FF manufactured by Kao Corporation was used. (Hereafter referred to as EBS.) Also, the SP value is
It is 9.8. [C ₁₇ H ₃₅ CONH] ₂ (CH ₂ ) ₂ b) Ethylenebisoleic acid amide (EBO) Alfro-AD-281 manufactured by NOF CORPORATION
Was used. (Hereinafter referred to as EBO.) The SP value is 7.3.

[C ₁₇ H ₃₃ CONH] ₂ (CH ₂ ) c) p-phenylenebisstearic acid amide (PBS) Alfro-AD-618 manufactured by NOF CORPORATION
Was used. (Hereinafter, referred to as PBS.) The SP value is 10.1. [C ₁₇ H ₃₅ CONH] ₂ (C ₆ H ₄ ) d) Methylenebisstearic acid amide (MBS) Bisamide LA, trade name, manufactured by Nippon Kasei Co., Ltd. was used. (Hereinafter, referred to as MBS.) The SP value is
It is 6.8.

[C ₁₇ H ₃₅ CONH] ₂ (CH ₂ ) e) Ethylenebiscapric acid amide (EBC) Slipax C, trade name, manufactured by Nippon Kasei Co., Ltd. was used. (Hereinafter, referred to as EBC.) The SP value is 7.
It is 5. [C ₉ H ₁₉ CONH] ₂ (CH ₂ ) ₂ f) Ethylenebislauric acid amide (EBL) Sripax L manufactured by Nippon Kasei Co., Ltd. was used. (Hereinafter, referred to as EBL.) The SP value is 7.
It is 2.

[C ₁₁ H ₂₃ CONH] ₂ (CH ₂ ) ₂ g) N, N'-distearyl adipic acid amide (DS
A) Nippon Kasei Co., Ltd. trade name Sripax ZSA was used. (Hereafter referred to as DSA.) Also, the SP value is
It is 7.0. Using emissions _{SX - [C 18 H 37 NHCO} ] 2 (CH 2) 4 h) xylylene bisstearyl urea (XBSU) manufactured by Nippon Kasei Chemical Co., trade name peel. (Hereafter referred to as XBSU.) Also, the SP value is
It is 9.8.

(C ₁₈ H ₃₇ NHCONHCH ₂ ) ₂ (CH
₂ ) i) Toluylene bisstearyl urea (TBSU) Hakurin ST manufactured by Nippon Kasei Co., Ltd. was used. (Hereinafter, referred to as TBSU.) The SP value is 1
It is 0.1. _{(C 18 H 37 NHCONH) 2} (CH 3) (C 6 H 3) j) hexamethylene bisstearyl urea (HBSU) manufactured by Nippon Kasei Chemical Co., trade name peel - with emissions SH. (Hereinafter referred to as HBSU.) Also, the SP value is
It is 9.7.

(C ₁₈ H ₃₇ NHCONH) ₂ (CH _2- ) ₆ k) Diphenylmethanebisstearylurea (DBSU) Hakurin SM manufactured by Nippon Kasei Co., Ltd. was used. (Hereinafter referred to as DBSU.) The SP value is 1
It is 0.2. Using _{(C 18 H 37 NHCONHC 6 H} 4) 2 (CH 2) l) stearate (SA) manufactured by NOF Corporation stearic acid powder. (Hereinafter referred to as SA) Further, the SP value is 9.1.

C ₁₇ H ₃₅ COOH m) Polyoxyethylene distearate (POE-D
S) Nippon Oil & Fats Co., Ltd. brand name Nonion DS-60HN was used. (Hereafter referred to as POE-DS.) Also, SP
The value is 9.3. C ₁₇ H ₃₅ COO (CH ₂ —CH ₂ —O) ₁₃₆ OCC ₁₇ H
₃₅ n) Behenyl behenate (BHB), manufactured by NOF CORPORATION, trade name Unistar M-2222S
L was used. (Hereafter referred to as BHB.) Also, SP
The value is 8.6.

CH ₃ (CH ₂ ) ₂₀ COO (CH ₂ ) ₂₁ C
H ₃ o) tris (methyl stearate) isocyanurate - using preparative (ISC) manufactured by NOF Corp. trade name Yunisuta -I76K. (Hereinafter referred to as ISC.) The SP value is 1
It is 0.1.

[0092]

[Chemical 16]

P) Neopentylpolyol stearic acid ester (NPS) Unistar H-476 manufactured by NOF CORPORATION was used. (Hereinafter, referred to as NPS.) Also, the SP value is
It is 6.3. _{[CH 3 (CH 2) 16 COOCH} 2 ] ₄ C q) mineral oil (liquid paraffin) (MO) Matsumura Oil Research Co., Ltd., trade name Sumoiru PS-260
Was used. (Hereinafter, referred to as MO.) The SP value is 8.6.

(D) Flame Retardant Red Phosphorus A commercially available resin-coated red phosphorus powder [Nova Excel 140 (hereinafter referred to as RP), manufactured by Rin Kagaku Kogyo Co., Ltd.] was used. (E) Flame retardant aid Triazine skeleton-containing compound Commercially available melamine cyanurate [manufactured by Nissan Kagaku KK, trade name MC610 (hereinafter referred to as MC)] was used.

Fluorine-based resin (PTFE) A commercially available polytetrafluoroethylene (trade name: Teflon 6J (referred to as PTFE) manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was used as an inhibitor for dropping fire flakes. P
For the method of adding TFE, see PPE-MB / PTFE.
A master batch of / EBS [98/1/1 (weight ratio)] was prepared at 330 ° C., and the master batch was blended with the thermoplastic resin composition to a specified amount.

[0096]

Examples 1 to 2 Comparative Examples 1 to 12 With respect to 100 parts by weight of the thermoplastic resin shown in Table 1, 12 and 2.4 parts by weight of each of the organic phosphorus compound and the processing aid shown in Table 1 were mechanically added. Mix and use Labo Plastomill manufactured by Toyo Seiki Seisakusho,
For compositions containing PPE-MB, a melt temperature of 250
The composition was melted for 7 minutes at a rotation speed of 50 rpm and at a rotation speed of 50 rpm for a composition containing no PPE-MB. A 1/8 inch thick test piece was prepared from the resin composition thus obtained by hot pressing, and the Vicat softening temperature, Izod impact strength and MFR were evaluated. The results are shown in Table 1 and FIG.

According to Table 1 and FIG. 2, when the absolute value ΔS1 of the difference in SP value between the thermoplastic resin and the hydroxyl group-containing aromatic phosphoric acid ester in the organic phosphorus compound is less than 1.0, the system becomes a completely compatible system and the flow It can be seen that although the properties are excellent, the heat resistance is remarkably reduced, while when it exceeds 2.0, it becomes incompatible and phase separation occurs. Therefore, only when .DELTA.S1 is between 1.0 and 2.0, is partial compatibility,
It can be seen that the balance characteristics of fluidity, heat resistance and impact resistance are improved.

[0098]

Examples 3 to 9 Comparative Examples 13 to 16 In Example 1, the composition was treated with HIPS / PPE-MB / FR-1 / processing aid shown in Table 2 = 71/29/12 / 2.4 (weight). The same experiment as in Example 1 was repeated except that the ratio was changed. The results are shown in Table 2 and FIG. Table 2 and FIG.
According to this, when the absolute value ΔS3 of the SP value difference between the thermoplastic resin and the processing aid is less than 0.5, the system becomes a completely compatible system and the balance characteristic of fluidity and heat resistance deteriorates, while ΔS3 is 0.5.
It can be seen that only when it is between 4.5 and 4.5, partial compatibility is achieved, and the balance characteristics of fluidity, heat resistance and impact resistance are improved. Further, if the absolute value ΔS2 of the SP value difference between the hydroxyl group-containing aromatic phosphoric acid ester in the organic phosphorus compound and the processing aid exceeds 2.5, it becomes incompatible and the above balance characteristics may be deteriorated. I understand.

[0099]

Comparative Examples 17 to 23 In Example 1, the composition was changed to H
IPS / PPE-MB / processing aid shown in Table 3 = 71/2
The same experiment as in Example 1 was repeated except that the ratio was changed to 9 / 2.4 (weight ratio). The results are shown in Table 3 and FIG. According to Table 3 and FIG. 4, it can be seen that the composition having no hydroxyl group-containing aromatic phosphoric acid ester does not have the dependency of ΔS3 as shown in FIG. 3 and is inferior in the balance property of fluidity and heat resistance.

[0100]

Comparative Examples 24 to 30 In Example 1, the composition was changed to H
IPS / processing aid shown in Table 4 = 100/3 (weight ratio), and the melting temperature and melting time are each 230
The same experiment as in Example 1 was repeated except that the temperature was changed to 5 ° C for 5 minutes. The results are shown in Table 4 and FIG.

From Table 4 and FIG. 5, it can be seen that the composition without the hydroxyl group-containing aromatic phosphoric acid ester does not have the dependence of ΔS 3 as shown in FIG. 3 and is inferior in the balance property of fluidity and heat resistance. .

[0102]

Examples 10 to 16 Comparative Examples 31 to 35 In Example 1, the composition was changed to HIPS / PPE-MB / organic phosphorus compound described in Table 5 / processing aid described in Table 5 / RP / PTFE.
= 71/29 / X / Y / 2.4 / 0.04 (weight ratio), the same experiment as in Example 1 was repeated, including the evaluation of flame retardancy. The results are shown in Tables 5 and 6 and FIG.

According to Table 5 and FIG. 6, when the absolute value ΔS3 of the difference in SP value between the thermoplastic resin and the processing aid is less than 0.5, the system becomes a completely compatible system and the balance characteristics of fluidity and heat resistance deteriorate, On the other hand, only when ΔS3 is between 0.5 and 4.5,
It can be seen that partial compatibility is achieved and the balance characteristics of fluidity, heat resistance and impact resistance are improved. Further, it is found that the combined use of the flame retardant and the flame retardant aid has an excellent balance of flame retardancy, fluidity, heat resistance and impact resistance.

[0104]

Example 17 Comparative Examples 36 to 52 In Example 1,
The composition is treated with HIPS / PPE-MB / FR-1 / FR-
3 / processing aid shown in Table 7 / RP / MC / PTFE = 71
The same experiment as in Example 1 was repeated, including the evaluation of flame retardancy, except that the weight ratio was changed to /29/12/8/2.4/2.4/8/8/0.04. The results are shown in Tables 7, 8 and 7.

From Table 6 and FIG. 7, it can be seen that only the composition satisfying the requirement of SP value of the present invention has excellent balance characteristics of flame retardancy, fluidity, heat resistance and impact resistance. In addition, between A component and B component in the table, between A component and hydroxyl group-containing aromatic phosphate ester in the organic phosphorus compound, respectively, hydroxyl group-containing aromatic phosphate ester in the organic phosphorus compound -Means between C components.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

[Table 7]

[0113]

[Table 8]

[0114]

The composition of the present invention is a thermoplastic resin composition having excellent moldability (fluidity), heat resistance and impact resistance. Further, the composition in which a flame retardant and a flame retardant auxiliary are blended as required is a thermoplastic resin composition having flame retardancy and the above-mentioned characteristics and excellent balance characteristics.

This composition is suitable for home electric appliances, OA equipment parts and the like. Especially, due to its excellent fluidity, not only can large-sized thin-walled molded products be molded reasonably, but also the molding temperature can be set to a low value, so that the molding cycle can be improved. Can be expected to be shortened,
The role played by these industries is significant.

[Brief description of drawings]

FIG. 1 is a triangular diagram of SP values showing a relationship between a thermoplastic resin, a hydroxyl group-containing aromatic phosphate ester in an organic phosphorus compound, and a processing aid.

FIG. 2 is a diagram showing a relationship between SP values of the thermoplastic resin, the organic phosphorus compound and the processing aid shown in Table 1.

FIG. 3 is a diagrammatic representation of Table 2. It is a figure explaining how the absolute value ΔS3 of the difference in SP value between the thermoplastic resin and the processing aid in the presence of the hydroxyl group-containing aromatic phosphate ester affects the fluidity and the heat resistance. (HIPS / PPE-MB is used as the thermoplastic resin.)

FIG. 4 is a diagrammatic representation of Table 3. When the hydroxyl group-containing aromatic phosphate is not present, the absolute value ΔS3 of the difference in SP value between the thermoplastic resin and the processing aid does not affect the fluidity and heat resistance. is there. (HIPS / PPE-MB is used as the thermoplastic resin.)

FIG. 5 is a diagrammatic representation of Table 4. When the hydroxyl group-containing aromatic phosphate is not present, the absolute value ΔS3 of the difference in SP value between the thermoplastic resin and the processing aid does not affect the fluidity and heat resistance. is there. (HIPS is used as the thermoplastic resin.)

FIG. 6 is a diagrammatic representation of Table 5. It is a figure explaining how the absolute value ΔS3 of the difference in SP value between the thermoplastic resin and the processing aid in the presence of the hydroxyl group-containing aromatic phosphate ester affects the fluidity and the heat resistance. (HIPS / PPE as flame retardant, flame retardant aid and thermoplastic resin)
-Use MB. )

FIG. 7 is a schematic diagram of Table 6. FIG. 3 is a diagram showing balance characteristics of fluidity and heat resistance of a composition satisfying the SP value of the present invention (◯ mark) and a composition not satisfying the above (x mark). (HIPS / PPE-MB is used as a flame retardant, a flame retardant auxiliary, and a thermoplastic resin.)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08K 5/20 KBA 7242-4J 5/521 7242-4J

Claims (1)

[Claims] 1. A thermoplastic resin (A), an organic phosphorus compound (B) having a hydroxyl group-containing aromatic phosphate ester,
And (C) a resin composition containing a processing aid selected from an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic alcohol, and an organic compound of a metal soap. A) component and hydroxyl group-containing aromatic phosphate ester in component (B), hydroxyl group-containing aromatic phosphate ester in component (B) and component (C), and component (C) and component (A) The absolute value of the difference between the solubility parameters (SP value) of ΔS1 and ΔS2, respectively.
, ΔS3, 1.0 ≦ ΔS1 ≦ 2.0, 0
≤ΔS2 ≤2.5, 0.5≤ΔS3 ≤4.5 [Unit:
A thermoplastic resin composition having excellent moldability and heat resistance, which satisfies the relationship [cal / cm ³ ] ^0.5 ].