GB2295155A - A low odor polyphenylene ether resin composition - Google Patents

Description

2295155 A LOW ODOR POLYPHENYLENE ETHER RESIN COMPOSITION The present

invention relates to a low odor polyphenylene ether resin composition. Particularly, the present invention relates to a polyphenylene ether resin composition where the odor caused by the polyphenylene ether when preparing and processing the composition is, remarkably low, as compared with a conventional polyphenylene ether resin composition.

A polyphenylene ether is a thermoplastic resin having an excellent mechanical strength, heat resistance and dimension stability, and a composition of a polyphenylene ether with other component, for example, a resin component, such as a styrene resin and a polyamide resin, is used for various uses.

However, owing to an odor caused by a polyphenylene ether at preparing and processing these conventional polyphenylene ether resin compositions, there is a 1 problem that an odor generated in an -indoor workshop where preparation and processing are performed must be discharged to outdoors by ventilation, and the reduction of the odor caused by the polyphenylene ether when preparing and processing said composition is desirable.

The purpose of the present invention is to provide a polyphenylene ether resin composition having a remarkably low odor at preparing and processing as compared with a conventional polyphenylene ether resin composition, and maintaining properties such as an impact strength to a level in practical use.

The present inventors have studied extensively the development of a polyphenylene ether resin composition maintaining properties such as an impact strength to a practical use level, and having a remarkably low odor at preparing and processing.

As the result, the present inventors found out that a polyphenylene ether resin composition containing a specified alumina reduced remarkably an odor at preparing and processing, and attained the present invention.

Namely, the present invention provides a low odor polyphenylene ether resin composition comprising (a) loo, 2 parts by weight of a composition comprising from 20 to 1000-. by weight of a polyphenylene ether and from 0 to 8016- by weight of a styrenic resin, and (b) from 0.1 to 15 parts by weight of alumina comprising a transition alumina as a main component and having a medium particle diameter of 150 Am or less and a BET specific surface area of 10 M2/g or more.

The present invention also provides a low odor polyphenylene ether resin composition according to the above-mentioned, wherein said low order composition further comprises (c) from 5 to 35 parts by weight of carbon black having an oil absorption by dibutylphthalate of 70 ml/100g or more, per 100 parts by weight of component (a).

The polyphenylene ether which is an essential component in the component (a) constituting the low odor polyphenylene ether resin composition of the present invention is a known polymer and a polymer obtainable by oxidative polymerization of one or more phenol compounds represented by the following formula with oxygen or oxygen-containing gas using oxidative-coupling catalysts; 3 OH R5 R, R4R2 R3 (, wherein R1, R2, R3, R4 and Rs were selected from a hydrogen, a halogen atom, a hydrocarbon or hydrocarbonoxy group or a substituted hydrocarbon or hydrocarbonoxy group and at least one of them is a hydrogen atom).

The examples of R,, R2, R3, R4 and Rs in the f ormula include hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and allyl.

The examples of the above-mentioned formula includ phenol, o-, m- or pcresol, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2, 3,6- or 2,4,6-trimethylphenol, 3-methyl-6-t-butylphenol, thym 4 e and 2-methyl-6-allylphenol.

The polyphenylene ether which is an essential component in the component (a) may also be the copolymer of any of the phenol compounds of the abovementioned formula with other phenol compounds, for example, polyhydroxy aromatic compounds such as bisphenol A, tetrabromobisphenol-A, resorcin, hydroquinone and novolak resin.

Examples of the preferable polyphenylene ether used in the present invention are homopolymers of 2,6-dimethylphenol or 2,6-diphenylphenol and copolymers. of large part of 2,6-dimethylphenol with small part of 3methyl-6-t-butylphenol or 2,3,6-trimethylphenol.

oxidative coupling catalysts employed for oxidative polymerization of phenol compound are not restricted particularly, and any catalyst may be used as long as it has a polymerization ability.

The preferable molecular weight range of the aforementioned polyphenylene ether wherein said molecular weight is represented by an intrinsic viscosity measured at 25 IC in chloroform, is within the range of 0.30 to 0.75 dl/g, preferably 0.35 to 0.50 dl/g, and more preferably 0.35 to 0.45 dl/g.

When the polyphenylene ether having an intrinsic 1 D viscosity of less than 0.30 dl/g is used, the mechanical strength of the polyphenylene ether resin composition obtained is low, and when the polyphenylene ether having an intrinsic viscosity of more than 0.75 dl/g is used, i is not preferred because the processability of the polyphenylene ether resin composition obtained decreases.

Furthermore, as well as the afore-mentioned polyphenylene ether, the polyphenylene ether which is an essential component in the component (a) may include a polymer obtained by grafting a styrenic compound, such as styrene, a-methyl styrene, p-methylstyrene and halogenated styrene such as chlorostyrene, onto these polyphenylene ethers.

Examples of the styrenic resin which is an arbitrary component in the component (a) include polymers of one or more compounds selected from a styrenic compound such as styrene, a-methylstyrene and p-methylstyrene, copolymers of large part of a styrenic compound with small part of a compound such as acrylonitrile, maleic anhydride and maleic acid, and an impact resistant styrenic resin.

Examples of the styrenic resin include polystyrene, poly- a -methyl styrene, poly-p-methy 1 styrene, styreneacrylonitrile copolymer, styrenemaleic anhydride copolymer, styrene-maleic acid copolymer and polystyrene 6 reinforced with polybutadiene rubber.

The component (a) may contain the styrenic resin at a ratio of 80% by weight or less. When the blending ratio of the styrenic resin in the component (a) exceeds 80% by weight, the odor of the resin composition obtained becomes negligibly small. Therefore, there is no problem about an odor.

The component (b) constituting an essential component of the low odor polyphenylene ether resin composition of the present invention is alumina containing a transition alumina as a main component and having a specified medium particle diameter and BET specific surface area, for example, an alumina containing, as the main component, a transition alumina in a process where aluminium hydroxide changes to ualumina, i.e. having a crystal structure intermediate between that of aluminium hydroxide and that of a-alumina.

The alumina preferably comprises greater than 501i by weight, more preferably greater than 7001 by weight, of transition alumina.

Said transition alumina has a density of preferably 2.50 to 3.90 g/CM3, more preferably 2.90 to 3.90 g/CM3, and most preferably 3.40 to 3.90 g/CM3.

A medium particle diameter of the alumina of the component (b) is 150 Am or less, preferably 100 Am or less, and more preferably 50 Am or less, as the diameter is necessary for maintaining the mechanical property of the polyphenylene ether resin composition obtained.

The term "medium particle diameter" used in this specification, including the claims, means the particle diameter corresponding to 50-. of cumulative weight in a cumulative weight distribution curve measured by a sieving method or a centrifugal sedimentation 7 method.

Besides, BET (Brunauer-Emmett-Teller) specific surface area of the alumina of the component (b) is 10 ml/g or more, preferably 50 m2/g or more, more preferably 80 m2/g or more, and most preferably 100 m 2/g or more. When the numerical value of BET specific surface area of the alumina of the component (b) is the greater, the smaller blending amount of the component (b) may reduce an odor caused by the polyphenylene ether resin composition.

The blending ratio of the component (b) is 0.1 to 15 parts by weight, and preferably 0.5 to 5 parts by weight, per 100 parts by weight of the component (a). When the blending ratio of the component (b) is less than 0.1 parts by weight, an effect of reducing an odor caused by the polyphenylene ether resin comoposition obtained is unstable, and when the blending ratio of the component (b) is more than 15 parts by weight, an effect of an odor caused by the polyphenylene ether resin comoposition obtained appears but a mechanical strength decreases to an undesirable level.

The low odor polyphenylene ether resin composition of the present invention may contain many arbitrary components in addition to the components (a) and (b) of the essential components. Examples of these arbitrary 8 components are illustrated as follows Component (c) a carbon black The carbon black of the component (c) is a carbon black used for, for example, coloring, reinforcing a rubber, and giving an electroconductivity. Particularly, in order to obtain a low order resin composition having effectively an electroconductivity, the oil absorption by dibutylphthalate of the carbon black is preferably more than 70 ml/100g.

Here, " the oil absorption by dibutylphthalate hereinafter, may be represented as " DBP oil-absorption tt) is a numerical value measured by a method prescribed in ASTM D2414. The DBP oil-absorption is preferably within the range of 100ml/100g to 600ml/100g, and more preferably 150ml/lOOg to 550ml/100g.

As the particularly preferable carbon black in order to obtain a low order resin composition having an electroconductivity, an acetylene black obtained by the thermal decomposition of acetylene and a Ketjen Black prepared by an insufficient combustion of crude oil as a raw material with a furnace are exemplified.

These carbon blacks can give effectively an electroconductivity to the resin composition obtained, 9 with a small blending ratio.

When the low order resin composition having an electroconductivity is obtained, the blending ratio of the component (c) is 5 to 35 parts by weight, preferably 5 to 30 parts by weight, and more preferably 8 to 30 parts by weight, per 100 parts by weight of the component (a). If the blending ratio of the component (c) is less than 5 parts by weight, an electroconductivity and an antistatic property of the resin composition obtained are insufficient, and if it is more than 35 parts by weight, an impact strength of the resin composition obtained is insufficient.

Component (d); a rubber A rubber of a component (d) means a natural or synthetic polymer material which is elastic at room temperature, and is blended, for example. in order to enhance an impact strength of the resin composition of the present invention. The especially preferred rubber of the component (d) to enhance an impact strength includes, for example, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, ethylene-butene-1 copolymer rubber, polybutadiene, styrene-butadiene block copolymer rubber, styrene-butadiene copolymer rubber, partially hydrogenated styrene- butadiene-styrene block copolymer rubber, styrene-isoprene-block copolymer rubber, partially hydrogenated styrene-isoprene block copolymer rubber, polyurethane rubber, styrene-grafted-ethylenepropylene-non- conjugated rubber, styrene-graftedethylene-propylene copolymer rubber, styrene/acrylonitrile-grafted-ethylene-propylene-nonconjugated diene copolymer rubber, styrene/acrylonitrilegrafted-ethylene-propylene copolymer rubber, styrene/methylmethacrylate-grafted-ethylenepropylenenon-conjugated diene copolymer rubber, and styrene/methylmethacrylate-grafted-ethylene-propylene copolymer rubber or a mixture therof.

Furthermore, the rubber, which is modified with a functional monomer having acid group such as acrylic acid and maleic anhydride, or a functional monomer having epoxy group such as vinylglycidyl ether, may be used.

The blending ratio of the component (d) is 50 parts by weight or less, and preferably 2 to 48 parts by weight, per 100 parts by weight of the component (a). If the blending ratio of the component (d) exceeds 50 parts by weight, the thermal resistance and processability of the resin composition become insufficient.

11 Component (e): a carboxylic acid ami-de wax having a high softening point A component (e) is used generally for improving a 46 rocessability flowability ( usually, called as a pA at the processing of the resin composition of the present invention, and a carboxylic acid amide wax having a high softening point can be used. The carboxylic acid amide wax having a high softening point of the component (e) is obtained by reacting a higher aliphatic monocarboxylic acid ( hereinafter,, named as " the component (e-1) and a polybasic acid ( hereinafter, named as " the component (e-2) ") with a diamine ( hereinafter, named as " the component (e-3)) by polycondensation.

As the component (e-1), an aliphatic monocarboxylic acid used in preparing a wax hitherto can be used, and a saturated aliphatic monocarboxylic acid and a hydroxy carboxylic acid having 16 or more carbon atoms are preferred. An example of the component (e-1) includes a palmitic acid, a stearic acid, a behenic acid, a montan acid and a hydroxy stearic acid.

The component (e-2) is a carboxylic acid comprising a dibasic acid or more, and includes, for example, an aliphatic dicarboxylic acid such as malonic acid, 12 succinic acid, adipic acid, pimelic acid, azelaic acid and sebacic acid, an aromatic dicarboxylic acid such as phthalic acid and terephthalic acid, and an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid and cyclohexyl succinic acid.

The component (e-3) includes a diamine used in preparing a wax hitherto, for example, ethylenediamine, 1,3-diamino propane, 1,4-diaminopropane, hexamethylenediamine, m-xylyienediamine, tolylenediamine, pxylylenediamine, phenylenediamine and isophoronediamine.

The component (e) is obtained by polycondensation of the components (e-1). (e-2) and (e-3). The reaction temperature is preferably 180 to 300 C, and more preferably 200 to 270 'C. The reaction time is preferably 3 to 7 hours, and more preferably 3 to 5 hours. Phosphorous acid or hypophosphorous acid is preferably added to the reaction system in order to prevent the coloring of the component (e) obtained.

Besides, the using ratio of the components (e-1), (e2) and (e-3) is preferred to be adjusted so that an amine value of the component (e) is 10 or less, and more preferably 5 or less.

The using amount of the component (e-2) is preferably 13 within the range of 0.18 to 1.0 mole per 2 moles of the component (e-1).

The using amount of the component (e-3) is the amount wherein amino groups of the component (e-3) react with carboxyl groups of the components (e-1) and (e-2) to form acid amide groups, and is preferably within the range of 1.2 to 2.0 moles per 2 mole of the component (e-1).

The component (e) is softened when the polyphenylene ether resin composition of the present invention is heated and molded. The molding temperature of heating and molding the polyphenylene ether resin composition is generally 240 to 350 C and preferably 260 to 330 C.

Therefore, the softening point of the component (e) is generally 3500C or less, preferably 105 to 350'C, and more preferably 150 to 330 'C. Hereby, the softening point is a numerical value measured by the softening point test method of petroleum asphalt ( a circular ball method according to JIS-K2531-1960.

The softening point of the component (e) is varied according to the kind and the using amounts of the components (e-1), (e-2) and (e-3). For example, even if the kind and using amounts of the components (e-1) and (e-2), and the kind of the component (e-3) are not changed, the softening point of the component (e) is 14 varied according to the using amount of the component (e- 3).

As the component (e). the carboxylic acid amide wax having a high softening point containing tetramide compound shown in the follow.&-ng formula (1) is preferred, and the carboxylic acid amide wax having a high softening point containing at least 10 parts by weight of tetramide compound is more preferred. In the formula (1), R' is a divalent organic group, R2 and R3 are each same or different divalent organic groups, and R4 and R5 are each same or different monovalent organic groups.

R 4-C ONH-R2-NHCO-Rl-CONH-R3-NHCO-R5(1) The example of the tetramide compound represented by the formula (1) is illustrated by the combination of the components (e-1), (e-2) and (e-3), that is, as the component (e-1)-component (e-2)-component (e-3) polycondensation product.

It includes, for example, stearic acid-sebacic acidethylenediamine polycondensation product, stearic acid-adipic acid-ethylenediamine polycondensation product and stearic acid-sebacic acid-m-xylylened-Jamine polycondensation product.

The component (e) obtained by polycondensation reaction of the components ( e-1), (e-2) and (e-3) may contain a diamide compound represented by the formula (2).

In the formula (2), R6 is a divalent organic group, and R 7and R8 are each same or different monovalent organic groups.

R 7-CONH-R6 -NHCO-Rll (2) The diamide compound represented by the formula (2) includes, for example, ethylene-bis-stearic amide, ethylene-bis-palmitic amide and ethylene-bis- oleic amide.

The blending ratio of the component (e) is 50 parts by weight or less. preferably 2 to 30 parts by weight, and more preferably 2 to 20 parts by weight. per 100 parts by weight of the component (a). If the blending ratio exceeds 50 parts by weight, a thermal resistance decreases although the processability of the resin composition obtained is improved.

In order to adjust the softening point of the component (e), a carboxyl amide wax having a softening point other than the component (e) may be used together with.

16 Component (f); a polyolefin A,polyolefin of a component (f) includes, for example, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene and poly-4-methylpentene-1.

The preferable component (f) used for enhancing the processability of the resin composition obtained is for example, low-density polyethylene and linear low-density polyethylene.

The blending ratio of the component (f) used for enhancing the processability of the resin composition obtained is 20 parts by weight or less, and preferably 1 to 15 parts by weight, per 100 parts by weight of the component (a). If the blending ratio of the component (e) exeeds 20 parts by weight, the processability of the resin composition obtained is enhanced, but it is not preferred because the problem of delamination occurs near the gate of a injection molded article.

Component (9) a non-electroconductive inorganic filler A non-electroconductive inorganic filler of the component (g) can be blended in order to enhance a stiffness of the resin composition obtained, improve the thermal resistance or enhance a dimensional stability.

17 The component (g) includes for example, an inorganic filler such as glass fiber, silica, calcium carbonater talc, mica, clay, kaolinite, magnesium sulfate, wollastonite, ZnO, Ti02 and Sb203- The blending ratio of the component (g) is 30 parts by weight or less, preferably 1 to 25 parts by weight, per 100 parts by weight of the component (a). If the blending ratio of the component (g) exeeds 30 parts by weight, the impact strength of the resin composition obtained decreases to an undesirable level.

Component (h); an electroconductive inorganic filler An electroconductive inorganic filler of the component (h) can be blended for enhancing an electroconductivity and improving an antistatic property and a stiffness of the resin composition obtained.

The component (h) includes for example, potassium titanate whisker treated with surface treatment, carbon fiber, stainless fiber and aluminium flake. One kind or more of fillers may be blended as the component (h).

The blending ratio of the component (h) is 50 parts by weight or less, and preferably 2 to 48 parts by weight, per 100 parts by weight of the component (a). If the blending ratio of the component (h) exceeds 50 parts by 18 weight, it is not preferred because the processability of the resin composition obtained decreases.

The low odor polyphenylene ether resin composition of the present invention may contain, furthermore. customarily used additives, for example, such as a pigment, a flame retardant, a plasticizer, an antioxidant and a weather proof agent, in addition to the abovementioned components (c) to (h).

The preparing method of the low odor polyphenylene ether resin composition of the present invention is not restricted. The low odor polyphenylene ether resin composition of the present invention may be prepared, for example, by blending the components with a conventional method, and successively, melt-kneading the blended components with a customary melt-kneading machine such as a kneader. an extruder, a roll mill and a Banbury mixer.

Particularly, the low odor polyphenylene ether resin composition of the present invention can be obtained by blending and melt-kneading the components (a) and (b) as indispensable components and optionally the components (c) to (h).

EXAMPLE

19 The following Examples illustrate the present invention.

The following materials were used as the components. Component (a) The polyphenylene ethers obtained by homopolymerization of 2.6- dimethylphenol and having the intrinsic viscosity measured in chloroform at 25 'C of 0.41 dl/g ( hereinafter named as " PPE-1 ") and 0.50 dl/g ( hereinafter named as " PPE-2) were used.

As the styrenic resin, Sumibrite Registered Trade Mark) E183 (hereinafter named as 11GPPS"), which is a polystyrene resin manufactured by Sumitomo Chemical Company Ltd.; and Sumibrite (Registered Trade Mark) M584 (hereinafter named as "HIPS"), which is a polystyrene resin reinforced with polybutadiene manufactured by Sumitomo Chemical Company Ltd., were used. Component (b) As the alumina for Examples of the present invention, Al-1 and Al-2 shown in Table 1 were used, and Al-3 and Al-4 shown in Table 1 were used as comparisons.

The medium particle diameter was measured by the method of using the model 5000-ET of SEDIGRAPH manufactured by Shimazu-Micromeritics Company Ltd.

The BET (Brunauer-Emmett-Teller) specific surface area was measured by using MULTI SORB-12 manufactured by Yuasa Ionics Company Ltd.

Here, Al-l is an activated alumina A-11 for purification by adsorption, Al-2 is a hydraulic alumina BK-112, Al-3 is a regular particle alumina A21, and Al-4 is an activated alumina AC-21 for purification by adsorption, that are manufactured by Sumitomo Chemical Company Ltd. Component (c) As the carbon black for Examples of the present invention, CB-1, CB-2 and CB-3 shown in Table 2 were used, and CB-4 shown in Table 2 was used as a comparison. Component (d) The polymer obtained by graft-polymerizing styrene and methylmethacrylate onto the ethylene-propylene-nonconjugated diene copolymer rubber, prepared as described afterward, that is, the styrene/methylmethacrylategrafted ethylene-propylene-non-conjugated diene copolymer rubber, was used.

Componen (e) The trade name of Lightamide WH-215A ( hereinafter named as " WX ") which is a carboxylic acid amide wax 21 having a high softening point manufactured by Kyoeisya Oil & Fats Chemical Company Ltd., and sold by Kyoeisya Chemical Company Ltd., was used. Here, WX is the stearic acid (2 moles)-sebacic acid (0.33 moles)- ethylenediamine (1.30 moles) polycondensation product and has the sof tening point of 215 C. Component (f) Sumikathene ( Registered Trade Mark) F210-6 hereinafter named as " PO ") which is a low density polyethylene manufactured by Sumitomo Chemical Company Ltd., was used. Component (g) The trade name of Talc 5000S ( hereinafter named as " Talc) which is a talc manufactured by Hayashi Chemical Ltd., and the trade name of RepcoMica S-325 ( hereinafter named as " mica ") which is a mica manuf actured by Canada Mica Company Ltd., were used. Component (h) The trade name of Magnamite 1800 AS ( hereinafter named as " CF ") which is a carbon f iber manufactured by Rika Hercules Company Ltd., the trade name of Naslone ( hereinafter named as " SF ") which is a stainless steel fiber having a diameter of 12 um manufactured by Nippon Seisen Company Ltd., and the trade name of Dentol 22 WK-200 ( hereinafter named as ', WK ") which is a potassium titanate whisker manufactured by Otsuka Chemical Company Ltd., were used.

Reference ExamDle The styrene/methylmethacrylate-grafted-ethylenepropylene-non-conjugated diene copolymer rubber of the component (d) was prepared as follows.

The 2200 ml of pure water dissolving 6 g of PLURONIC F68 ( Trade name) manufactured by Asahi Denka Kogyo K.K., as a dispersing agent, and 300g of Esprene ( Registered Trade Mark) E502 (44 parts by weight of a repeating unit derived from propylene, an iodine value of 8.5 and Mooney viscosity at 120 C of 63) cut in 3 to 6mm cubes were fed in 5 1 autoclave with a stirrer and dispersed in suspension uder stirring.

Then, 101 g of styrene,-19 g of methylmethacrylate, 9 g of t-butylperoxy pivalate and 0.18 g of p-benzoquinone were added, and immediately, the autoclave was immmersed in a oil bath heated at 30. C. It was heated until 110 'C at a rate of about 1 - C/min., and the graftpolymerization was performed by maintaining the temperature at 110 'C for 30 minutes. Thus obtained granulated materials were dried under vacuum at 95. C 23 after washed by water, and the styrene/methylmethacrylate-graftedethylene-propylenenon-conjugated diene copolymer rubber ( hereinafter named as " SMEPR ") was obtained.

ExamDles I to 26 and Comparative Examples 1 to 24 Examples 1 to 14 and Comparative Examples 1 to 12 relate to the compositions not containing the component (c), and Examples 15 to 26 and Comparative Examples 13 to 24 relate to the compositions containing the component (c) or the component corresponding to that.

Each component was blended as the blending ratio parts by weight) shown in Tables 3 to 12.

The blended materials were extruded with a model TEM 50 of a twin-screw extruder manufactured by Toshiba Machine Company Ltd., and pelletized by a strand cutter after cooled in water tank.

Here, the cylinder temperatures of the extruder in cases of Examples 8 to 14 and Comparative Examples 5 to 13 were 260. C, and the cylinder temperatures in other cases were 300 C.

Thus obtained pellets were dried for 3 hours by a hot air drier, and the pellets dried were molded to each test piece.

24 Here, the hot-air dryng temperatures in cases of Examples 8 to 9 and Comparative Examples 5 to 7 were 80 IC and the drying temperatures in other cases were 130 t - Besides, the molding of a test piece was performed by using a model IS220EN of injection molding machine manufactured by Toshiba Machine Company Ltd., and a mold for molding the test piece( a mold temperature of 80. C Here, the cylinder temperatures of the injection molding machine in cases of Examples 8 to 14 and Comparative Examples 5 to 13 were 260. C and the cylinder temperatures in other cases were 330. C.

The evaluation method of the test pieces is as follows and the tested results were shown in Tables 3 to 12.

The evaluation method of an odor At the hot-air drying of the afore-mentioned pellets, when the pellets in drying or dried was taken out from the drier, a level of odor wherein a work could be done withoutindoor ventilation was estimated as 0, and a level of odor wherein a work could not be done without indoor ventilation was estimated as X. The results were shown in Tables 3 to 12.

Impact strength An Izod impact strength was measured in accordance with ASTM D-256 by using a notched test piece of 3.2 mm in thickness. The unit of the measured value is kg. cm/cm.

The Izod impact strength of the polyphenylene ether resin composition available practically is usually 2 kg cm/cm or more. Surface specific resistivity ( SSR A test piece plate of 54 mm X 75 mm was subjected to the measurement of surface specific resistivity by the trade name of HIRESTA IP ( model MCP- HT 260) which is a high resistance resistometer manufactured by Yuka Denshi Company Ltd.

The surface specific resistivity of the polyphenylene ether resin composition having an electroconductivity available practically is usually less than 1013.

According to the present invention, by blending the specified alumina to the polyphenylene ether resin composition, the odor generated during preparation and processing can be reduced remarkably, while maintaining the properties of the said composition such as the impact 26 strength. As illustrated in Comparative Examples, an odor of the polyphenylene ether resin composition not containing the alumina is X ( ref er to Comparative Examples 1, 2, 6 to 12, 14, 17 to 24).

Besides, although alumina is contained, the composition not satisfying the requisites for the polyphenylene ether resin composition of the present invention ( refer to Comparative Examples 3, 4, 13, 15, 16) is not preferred from the point of the impact strength and SSR.

Besides, Comparative Example 5 wherein the composition contains a lot of styrenic resin is a composition having originally no problem of an ordor.

Over against this, by the present invention, it is clear fr6m Examples that the polyphenylene ether resin composition having remarkably low odor at preparing and processing, without decreasing properties such as an impact strength to an inconvenient level, can be obtained by blending the specified alumina.

Particularly, by using the specified alumina and the carbon black together with, the low odor and electroconductive polyphenylene ether resin composition is obtained (Examples 15 to 26).

The significance of providing a resin composition 27 satisfying the requisites of the present invention is that a worker preparing and pr. ocessing the said resin composition indoors does not suffer from odor caused by polyphenylene ether.

28 [ Table

Al-1 Al-2 A1-3 Al-4 Chemical composition (weight %) A1203 99.6 99.7 99.6 99.7 Fe203 0.03 0.05 0.01 0.02 Si02 0.02 0.01 0.01 0.02 Na20 0.33 0.25 0.25 0.25 Crystal type of A1203 X 1 r r a X F r BET specific surface area (M2/g) 130 280 1.2 120 Medium particle diameter ( lum) 40 11 45 200 29 [Table 21

CB- 1 CB-2 CB-3 CB-4 Kind Ketjen Acetylene Furnace Furnace black black black black Maker Lion Denki Kagaku Kyabot Mitsubishi Co., Ltd. Kogyo Co., Ltd.

Grade name 600JD Denka Black Vulcan C Chemical Industry Co., Ltd. Dia BlackZ45 DBP oil-absorption (M1/100g) 495 212 100 55 (Table 3] xample 2 Comparative Comparative Compararative Comparative Example 1 E Example 1 Example 2 Example 3 Example 4 PPE-1 100 100 100 100 100 100 Al-1 20 10 Al-2 Al-3 10 Al-4 10 Odor X X 0 0 0 0 Impact strength 9 4 < 2 < 2 4 5 (Table 41

Example 3 1 Example 4 Example 5 Example 6 Example 7 PPE-1 100 100 100 100 100 Al-1 5 0.5 5 Al-2 0.5 5 Al-3 5 Odor 0 0 0 0 0 Li Impact strength 4 8 8 6 7 M [Table 5]

Comparative Comparative comparative Example 8 Example 9 Example 5 Example 6 Example 7 PPE-1 10 30 30 30 30 GPPS 90 70 70 HIPS 70 70 Al-1 2 2 odor 0 X X 0 0 w 8 w Impact strength 4 4 9 3 1 (Table 6]

Comparative Comparative Comparative Example 10 Example 11 Example 12 Example 8 Example 9 Example 10 PPE-2 60 60 60 60 60 60 GPPS 40 40 40 40 40 40 Al-1 2 2 2 SMEPR 10 10 10 10 10 10 WX 5 5 5 5 PO 2 2 odor 10 X X X 0 0 0 Impact strength 20 17 18 18 16 16 [Table 71

Comparative Comp arative Example 13 Example 14 Example 11 Example 12 PPE-2 60 60 60 60 GPPS 40 40 40 40 Al-l 2 2 SMEPR 10 10 10 10 WX 5 5 5 5 PO 2 2 2 2 Talc 10 10 Mica 10 10 odor X X 0 0 Impact strength 12 10 11 10 [Table 8]

Comparative Example 13 Comparative Example 14

Comparative Example 15

Example 15

Example 16

PPE-1 60 60 60 60 60 GPPS 40 40 40 40 40 Al-1 2 2 2 2 CB-2 3 22 40 18 22 Odor 0 X 0 0 0 impact strength 5 3 < 2 3 2 SSR >1X101, 3X10' <lXl0, qX10I 3X10' (Table 9] i Comparative Example 16

Example 17

Example 18

PPE-1 60 60 60 GPPS 40 40 40 Al-l 2 2 2 CB-1 8 CB-3 33 CB-4 40 odor 0 0 0 Impact strength <2 3 2 SSR >1XIO" 4X10' 4X107 [Table 10]

Comparative Example 17 Comparative 1 Example 18

Example 19

Example 20

PPE-2 60 60 60 60 GPPS 40 40 40 40 Al-1 2 2 CB-2 22 22 22 22 SMEPR 10 10 10 10 WX 5 5 Odor X X 0 0 Impact strength 5 5 4 4 SSR 5X10' 6X10' 5X10' 6X10' [Table 11]

Comparative Comparative Comparative Example 21 Example 22 Example 23 1 Example 19 Example 20 Example 21 PPE-2 60 60 60 60 60 60 GPPS 40 40 40 40 40 40 Al-1 2 2 2 CB-2 22 22 22 22 22 22 uj SMEPR 10 10 10 10 10 10 WX 5 5 5 5 5 5 PO 2 2 2 2. 2 2 Talc 10 10 mica 10 10 Odor X X X 0 0 0 Impact strength 5 3 3 4 3 3 SSR 6X10' 1X105 2X101 6X101 1X10, 1X10, [Table 121

Comparative Comparative Comparative Example 24 Example 25 Example 26 Example 22 Exdmple 23 Example 24 PPE-2 60 60 60 60 60 60 GPPS 40 40 40 40 40 40 Al-1 2 2 2 CB2 20 20 20 20 20 20 SMEPR 10 10 10 10 10 10 wx 5 5 5 5 5 5 PO 2 2 2 2 2 2 Talc 10 10 10 10 10 CF 5 5 SF 5. 5 WK 5 5 Odor X X X 0 0 0 Impact strength 4 4 3 4 4 3 SSR <1X101 <1X101 2X10' <1X101 <1X101 2 X 10'

Claims (1)

1. A low odor polyphenylene ether resin composition comprising:

(a) 100 parts by weight of a composition comprising from 20 to 100% by weight of a polyphenylene ether and from 0 to 80% by weight of a styrenic resin, and (b) from 0.1 to 15 parts by weight of alumina comprising a transition alumina as a main component and having a medium particle diameter, as hereinbefore defined, of 150 gm or less and a BET specific surface area of 10 m 2 /g or more.

2. A low odor polyphenylene ether resin composition according to claim 1, which further comprises (c) from 5 to 35 parts by weight of carbon black having an oil absorption by dibutylphthalate of 70 ml/100g or more, per 100 parts by weight of component (a).

3. A low odor polyphenylene ether resin composition according to claim 1 or 2, wherein the polyphenylene ether of component (a) has an intrinsic viscosity of 0.30 to 0.75 dl/g.

-- 4. A low odor polyphenylene ether resin composition according to claim 3, wherein the polyphenylene ether of component (a) has an intrinsic viscosity of 0.35 to 0.50 dl/g.

S. A low odor polyphenylene ether resin composition according to claim 3, wherein the polyphenylene ether of component (a) has an intrinsic viscosity of 0.35 to 0.45 dl/g.

41 6. A low odor polyphenylene ether resin composition according to any one of the preceding claims, wherein the alumina has a medium particle diameter of 100 Am or less.

7. A low odor polyphenylene ether resin composition according to claim 6, wherein the alumina has a medium particle diameter of 50 Am or less.

8. A low odor polyphenylene ether resin composition according to any one of the preceding claims, wherein the alumina has a BET specific surface area of 50 m 2 /g or more.

9. A low odor polyphenylene ether resin composition according to claim 8, wherein the alumina has a BET specific surface area of 80 M2/g or more.

10. A low odor polyphenylene ether resin composition according to claim 8, wherein the alumina has a BET specific surface area of 100 M2/g or more.

11. A low odor polyphenylene ether resin composition according to any one of claims 2 to 10, which comprises carbon black having an oil absorption by dibutylphthalate of 100 to 600 ml/100g.

12. A low odor polyphenylene ether resin composition according to claim 11, wherein the carbon black has an oil absorption by dibutylphthalate of 150 to 550 m1/100g.

13. A low odor polyphenylene ether resin composition according to any one of the preceding claims, which further comprises (d) up to 50 parts by weight of a 42 rubber which is elastic at room temperature, per 100 parts by weight of the component (a).

14. A low odor polyphenylene ether resin composition according to any one of the preceding claims which further comprises (e) up to 50 parts by weight of carboxylic acid amide wax having a high softening point, per 100 parts by weight of the component (a).

is. A low odor polyphenylene ether resin composition according to claim 14, wherein the carboxylic acid amide wax has a softening point of 150 to 330'C.

16. A low odor polyphenylene ether resin composition according to any one of the preceding claims, which further comprises (f) up to 20 parts by weight of a polyolefin, per 100 parts by weight of the component (a).

17. A low odor polyphenylene ether resin composition according to any one of the preceding claims, wherein the transition alumina has a density of 2.50 to 3.90 g/CM3.

18. A low odor polyphenylene ether resin composition according to any one of the preceding claims in shaped form.

19. A low odor polyphenylene ether resin composition according to claim 1 substantially as hereinbefore described.

43