JP3377314B2 - Low odor polyphenylene ether 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 polyphenylene ether having a low odor.
The present invention relates to a polyester resin composition. Specifically, the present invention
Composition containing phenylene ether as an essential component (hereinafter, referred to as
"Polyphenylene ether-based resin composition")
Polyphenylene ether as manufactured and processed
Odor caused by conventional polyphenylene ether-based
Low odor polyphenylene ether significantly lower than fat composition
The present invention relates to a polyester resin composition. [0002] 2. Description of the Related Art Polyphenylene ether has mechanical strength,
Thermoplastic resin with excellent heat resistance, dimensional stability, etc.
And other components such as styrene resin and polyamide resin
Compositions with resin components such as are used for various applications
ing. [0003] However, these conventional techniques
The polyphenylene ether-based resin composition is produced by
Due to polyphenylene ether when processing or processing
Indoors where manufacturing and processing take place
Workplace odors must be ventilated to the outside.
In the manufacture and processing of the composition.
It is desired to reduce odor generation. SUMMARY OF THE INVENTION It is an object of the present invention to manufacture or process
When the odor is generated, the conventional polyphenylene ether
Compared with resin composition, it is significantly reduced, and impact strength etc.
Polyolefin that does not decrease its physical properties to a level that is not practical
An object of the present invention is to provide a phenylene ether-based resin composition. [0005] Means for Solving the Problems The present inventors have developed an impact strength
Properties are not reduced to an inconvenient level,
Polyphenylene acrylate with noticeably reduced odor generation during baking
Continuing research on the development of ter-based resin compositions
Was. As a result, polyphenylene
The terrestrial resin composition has an odor during the production and processing of the composition.
The present invention was found to significantly reduce
It led to. That is, the present invention relates to a method for preparing the component (a)
80% by weight of phenylene ether or styrene resin
Polyphenylene ether and styrene resin contained below
100 parts by weight of a composition consisting of
BE with a central particle size of 150μm or less containing Lumina as the main component
T surface area is 10m^Two/ G or more of alumina 0.1-1
Low odor polyphenylene ether resin containing 5 parts by weight
A composition. The low odor polyphenylene ethers of the present invention
Po, which is an essential component in component (a) constituting the resin composition,
Riphenylene ether is a known polymer,
One or more phenolic compounds represented by the general formula
The top is treated with oxygen or oxygen containing
It is a polymer obtained by oxidative polymerization with a gas. [0007] (Where R₁, R_Two, R_Three, R_FourAnd R_FiveIs hydrogen, ha
Selected from a halogen atom, a hydrocarbon group or a substituted hydrocarbon group.
One of which is a hydrogen atom
) [0008] R in the general formula 1₁, R_Two, R_Three, R
_FourAnd R_FiveSpecific examples of hydrogen, chlorine, bromine,
Nitrogen, iodine, methyl, ethyl, n- or iso-
Ropyl, pri-, sec- or t-butyl, chloro
Ethyl, hydroxyethyl, phenylethyl, benzyl
, Hydroxymethyl, carboxyethyl, methoxyca
Rubonylethyl, cyanoethyl, phenyl, chlorophen
Nil, methylphenyl, dimethylphenyl, ethylphen
Nil, allyl. A specific example of the general formula 1 is phenol
, O-, m-, or p-cresol, 2,6-,
2,5-, 2,4- or 3,5-dimethylphenol
, 2-methyl-6-phenylphenol, 2,6-di
Phenylphenol, 2,6-diethylphenol, 2
-Methyl-6-ethylphenol, 2,3,5-, 2
3,6- or 2,4,6-trimethylphenol, 3
-Methyl-6-t-butylphenol, thymol, 2-
Methyl-6-allylphenol is exemplified. Polyphenyl which is an essential component in component (a)
Renether is also a phenolic compound other than general formula 1.
Such as bisphenol-A, tetrabromobisphene
Nord-A, resorcin, hydroquinone, novolak
Polyvalent hydroxy aromatic compound such as resin and general formula 1
And a copolymer of Preferred polyphenylene used in the present invention
2,6-dimethylphenol or
2,6-diphenylphenol homopolymer, a large amount of
2,6-dimethylphenol and a small amount of 3-methyl-6
-T-butylphenol or 2,3,6-trimethyl
Copolymers with phenol are exemplified. Used for oxidative polymerization of phenolic compounds
The oxidation coupling catalyst used is not particularly limited.
Alternatively, any catalyst capable of polymerizing can be used. The preferred components of the above polyphenylene ether
The range of the amount of particles is as follows: chloroform at 25 ° C.
In terms of the intrinsic viscosity value measured by using, 0.30 to
In the range of 0.75 dl / g, preferably 0.35 to 0.5
0 dl / g, more preferably 0.35 to 0.45
dl / g. With intrinsic viscosity smaller than this
When used, the resulting polyphenylene ether-based resin
Low mechanical strength of the composition and higher intrinsic viscosity
If you use the one, the resulting polyphenylene ether
It is not preferable because the processability of the resin composition is reduced. Polyphenyl which is an essential component in component (a)
The renether further comprises the polyphenylene ether described above.
In addition, styrene,
methyls such as α-methylstyrene and p-methylstyrene
Halogenated styrene such as styrene and chlorostyrene
Obtained by grafting a styrenic compound exemplified in
Polymer. Styrene as an optional component in component (a)
As the resin, styrene, α-methylstyrene, p-methyl
One selected from styrene compounds such as
Is a polymer of two or more compounds, a large amount of styrene compounds
Parts and a small amount of compounds such as acrylonitrile and maleic acid
And impact-resistant styrenic resins.
You. Specific examples of styrene resins include polystyrene and polystyrene.
Li-α-methylstyrene, poly-p-methylstyrene,
Styrene-acrylonitrile copolymer, styrene-male
Formic acid copolymer, polybutadiene rubber reinforced polystyrene
Is mentioned. The component (a) is composed of 80% by weight of a styrene resin.
It may be contained in the following ratio. Styrene tree in component (a)
When the mixing ratio of fat exceeds 80% by weight, the obtained resin
The degree of odor of the composition is small enough to cause little problem.
No. The low odor polyphenylene ether of the present invention
Component (b), which is an essential component of the resin composition,
Transition alumina having a constant center particle size and BET surface area
Alumina as the main component, for example, aluminum hydroxide
Transition alumina in the process of changing from aluminum to α-alumina
Alumina as the main component. Alumina to be component (b)
The center particle size of the obtained polyphenylene ether resin
A size that does not adversely affect the mechanical properties of the composition
It is necessary to be 150 μm or less,
Preferably 100 μm or less, more preferably 50 μm or less
Below. The term "center particle size" used herein means a sieving method or
Cumulative weight distribution curve measured by centrifugation.
Is a particle diameter corresponding to a cumulative weight of 50%. Also,
The BET surface area of alumina (b) is 10 m^Two/ G or less
Above, preferably 50m^Two/ G or more, more preferably 80
m^Two/ G or more, particularly preferably 100 m^Two/ G or more
You. Component (b) has a large value of BET surface area of alumina
The odor is generated by blending a smaller amount of component (b).
Polyphenylene ether exhibiting the effect of the present invention of reducing raw material
Thus, a polyester resin composition can be obtained. The mixing ratio of component (a) and component (b) is
Component (b) is 0.1 to 100 parts by weight of component (a)
15 parts by weight, preferably 0.5 to 5 parts by weight. component
When the compounding ratio of (b) is less than 0.1 part by weight, it is obtained.
Reduction of odor generation of polyphenylene ether resin composition
If the effect is not stable and exceeds 15 parts by weight,
Odor generation of polyphenylene ether-based resin composition
Although the effect is reduced, the mechanical properties are unfavorable
Drops to a degree. The low odor polyphenylene ether of the present invention
The resin composition comprises an essential component (a) and a component.
In addition to (b), various optional components may be included. These optional
The components are exemplified below. [0020]Component (c) carbon black The carbon black as the component (c) is, for example, for coloring,
Carbon used for rubber reinforcement, conductivity imparting, etc.
Black. In particular, the amount of carbon black added
To efficiently obtain a conductive resin composition with conductivity
In order to absorb carbon black dibutyl phthalate oil
The amount is preferably 70 ml / 100 g or more. here,
“Dibutyl phthalate oil absorption” (hereinafter “DBP oil absorption”)
"Amount") is defined in ASTM D2414.
Is a value measured by the following method. The preferred DBP oil absorption is
In the range of 100ml / 100g-600ml / 100g
And a more preferred range is 150 ml / 100 g to 55
It is 0 ml / 100 g. To obtain a conductive resin composition
As a particularly preferred carbon black, acetylene brick
Acetylene black and crude oil
As a raw material, it is manufactured by furnace type incomplete combustion.
May be exemplified. These carbon bras
The mixing ratio is small and the resin composition obtained is highly efficient.
High conductivity. When the conductive resin composition is obtained, component (c)
Is from 5 to 35 parts per 100 parts by weight of component (a).
Parts by weight, preferably 5 to 30 parts by weight, particularly preferably 8 parts by weight.
-30 parts by weight. 5 parts by weight of component (c)
If less, the resulting resin composition has conductivity and antistatic properties.
Is not sufficient and exceeds 35 parts by weight, the obtained resin
The impact strength of the composition is not sufficient. [0022]Component (d) rubber-like substance The rubber-like substance as the component (d) is an elastic material at room temperature.
Natural and synthetic polymers, for example, the impact resistance of resin compositions
It is blended when you want to increase the impact strength. Increased impact strength
As particularly preferred component (d) for use, for example, ethyl
-Propylene copolymer rubber, ethylene-propylene-non-
Conjugated diene copolymer rubber, ethylene-butene-1 copolymer rubber
Block, polybutadiene, styrene-butadiene block
Polymerized rubber, styrene-butadiene copolymer rubber, partially hydrogenated
Styrene-butadiene-styrene block copolymer rubber,
Styrene-isoprene block copolymer rubber, partially hydrogenated
Tylene-isoprene block copolymer rubber, polyurethane
Rubber, styrene graft-ethylene-propylene-non-
Role diene copolymer rubber, styrene-graft-ethylene-
Propylene copolymer rubber, styrene / acrylonitrile-
Graft-ethylene-propylene-non-conjugated diene copolymer
Rubber, styrene / acrylonitrile-graft-ethylene
-Propylene copolymer rubber, styrene / methyl methacrylate
Rate-graft-ethylene-propylene-non-conjugated die
Copolymer rubber, styrene / methyl methacrylate-gra
Ft-ethylene-propylene copolymer rubber, or
A mixture may be exemplified. In addition, these rubbers
Functional monomers having an acid group such as luic acid and maleic anhydride;
Functionality with epoxy group such as vinyl glycidyl ether
Modified with a reactive monomer is also used as component (d)
I can do it. The mixing ratio of component (d) is 10
50 parts by weight or less, preferably 2 to 48 parts by weight with respect to 0 parts by weight
It is in the range of parts by weight. 50% by weight of component (d)
Parts, the heat resistance and processability of the resulting resin composition
Becomes insufficient. [0024]Component (e) carboxylic acid amide-based high softening point
Box The component (e) is used for the flow of the obtained resin composition during molding.
To improve workability (generally referred to as "workability")
Used, known carboxylic acid amide-based soft
Wax point waxes may be used. Carboxylic acid as component (e)
Amide-based high-melting wax refers to higher aliphatic monocarboxylic acids.
Acid (hereinafter also referred to as “component (e-1)”) and polybasic acid (hereinafter referred to as “component (e-1)”).
The following “component (e-2)” is also referred to as a diamine (hereinafter referred to as “component (e-2)”).
(Also referred to as "(e-3)").
Carboxylic acid amide-based high melting point wax. As the component (e-1), a conventional wax
Fatty monocarbo used in the production of
Acid can be used, and preferably has 16 or more carbon atoms.
Of saturated aliphatic monocarboxylic acids and hydroxycarboxylic acids
Acid, and specific compounds such as palmitic acid and stearic acid
Phosphoric acid, behenic acid, montanic acid, hydroxystearin
The acid, oleic acid, may be exemplified. Component (e-2) is a carboxylic acid of dibasic acid or more.
Acid, such as malonic acid, succinic acid, adipic acid,
Aliphatic dica such as pimelic acid, azelaic acid and sebacic acid
Aromatic dicarbo such as rubonic acid, phthalic acid and terephthalic acid
Acid, cyclohexanedicarboxylic acid, cyclohexylco
Alicyclic dicarboxylic acids such as succinic acid are exemplified. As the component (e-3), a conventional wax
Diamines used in the production of
Diamine, 1,3-diaminopropane, 1,4-di
Aminopropane, hexamethylenediamine, metaxylene
Diamine, tolylenediamine, paraxylylenediamine
, Phenylenediamine and isophoronediamine
obtain. Component (e) comprises component (e-1), component (e-
2) and component (e-3) by polycondensation reaction.
Obtained. The reaction temperature is generally preferably from 180 to 300 ° C.
And more preferably 200 to 270 ° C. When reacting
The time is 3 to 7 hours, preferably 3 to 5 hours. Obtained
In order to prevent coloring of component (e), phosphorus
It is preferable to add an acid, hypophosphorous acid and the like. The component (e)
-1), use ratio of component (e-2) and component (e-3)
Means that the amine value of the component (e) is 10 or less, preferably 5 or less.
It is better to be below. The amount of component (e-2) used is
The range of 0.18 to 1.0 mol is preferable for 2 mol of 1).
Suitable. The amount of component (e-3) used is
3) The amino group of component (e-1) and component (e-2)
Reacts with carboxyl groups to form acid amide bonds
In an amount of 1.2 to 1.2 mol per 2 mol of the component (e-1).
A range of 2.0 moles is preferred. Component (e) is the polyphenylene ether of the present invention.
-Softens when heating and molding the polyester resin composition
It is. Heats polyphenylene ether resin composition
The temperature at the time of molding is generally 240 to 350 ° C.
Since the temperature is preferably 260 to 330 ° C, the softening of the component (e)
The conversion point is 350 ° C or less, usually 105-350 ° C, preferably
Or 150-330 ° C. Here, the softening point is J
IS-K2531-1960 petroleum asphalt softening point test
It is a value measured by the test method (ring and ball method). The softening point of component (e) is determined by the
It varies depending on the type and amount of component (e-1) to component (e-3).
Become For example, the components (e-1) and (e-2)
The type and amount used, and the type of component (e-3) are the same
However, depending on the amount of component (e-3) used,
The softening point changes. Component (e) includes components (e-1) to
Product obtained by the polycondensation reaction of (e-3)
(Carboxylic acid amide-based high softening point wax)
The cal containing the tetraamide compound represented by (1)
Bonamide amide-based high softening point waxes are preferred, and tetraa
Carboxamide containing 10% by weight or more of a amide compound
A system high softening point wax is more preferred. In general formula (1)
And R¹Is a divalent organic group, R^TwoAnd R^ThreeAre the same or different
A divalent organic group, R^FourAnd R^FiveAre the same or different monovalent
Is an organic group.   R^Four-CONH-R^Two-NHCO-R¹-CONH-R^Three-NHCO-R^Five                                                                 (1) The tetraamide compound represented by the general formula (1)
Examples of the product are given as components (e-1) to (e-
3), that is, component (e-1) -component (e-
2)-Component (e-3) Exemplified by a method described as a polycondensate.
And stearic acid-sebacic acid-ethylenediamine polycondensation
Compound, stearic acid-adipic acid-ethylenediamine
Condensate, and stearic acid-sebacic acid-metaxile
And diamine polycondensates. Component (e-1), component (e-2) and component
Component (e) obtained by the polycondensation reaction of (e-3) is generally
It may contain a diamide compound represented by the formula (2)
No. In the general formula (2), R⁶Is a divalent organic group, R⁷
And R⁸Are the same or different monovalent organic groups.   R⁷-CONH-R⁶-NHCO-R⁸                          (2) The diamide compound represented by the general formula (2)
Examples include ethylene-bis-stearic acid amide, ethyl
Len-bis-palmitic acid amide, and ethylene-bis
-Oleic acid amides. The mixing ratio of the component (e) is as follows.
50 parts by weight or less, preferably 2 to 30 parts by weight with respect to 0 parts by weight
Parts by weight, particularly preferably 2 to 20 parts by weight. Mix ratio
If the amount exceeds 50 parts by weight, the resulting resin composition is processed.
Although heat resistance is improved, it is preferable because heat resistance decreases
Absent. In order to adjust the softening point of component (e),
Carboxylic acids having a softening point not included in the softening point range
An amide wax may be used in combination. [0039]Component (f) polyolefin As the polyolefin as the component (f), for example, low density
Polyethylene, high density polyethylene, linear low density poly
Ethylene, polypropylene, poly-4-methylpentene
-1 may be exemplified. Improves processability of the resulting resin composition
Examples of preferred components (f) that can be used for
Polyethylene or linear low-density polyethylene. Improving the processability of the obtained resin composition
The mixing ratio of component (f) used for the
20 parts by weight or less, preferably 1 to 15 parts by weight with respect to 0 parts by weight
Parts by weight. The proportion of component (f) exceeds 20 parts by weight
In other words, the processability of the obtained resin composition is improved.
Of the delamination near the gate of the processed product (molded product)
It is not preferable because it causes problems. [0041]Component (g) Non-conductive inorganic filler Improvement of rigidity of the obtained resin composition, improvement of heat resistance or
In order to improve dimensional stability, component (g)
Machine filler may be included. As the component (g), for example,
Lath fiber, silica, calcium carbonate, talc, mica,
Clay, kaolin, magnesium sulfate, wollastonie
, Titanium oxide, zinc oxide, antimony oxide
May be exemplified. The mixing ratio of the component (g) is 10
30 parts by weight or less, preferably 1 to 25 parts by weight with respect to 0 parts by weight
It is in the range of parts by weight. 30% by weight of component (g)
If the amount exceeds 100 parts, the impact resistance of the obtained resin composition is preferred.
It falls to the extent that it is not. [0043]Component (h) conductive inorganic filler Improvement of conductivity, antistatic property, rigidity of obtained resin composition
(H) conductive inorganic filler
May be blended. As the component (h), for example, surface-treated titanium
Potassium whisker, carbon fiber, stainless steel fiber
Examples include fibers and aluminum flakes. Component (h) and
Then, one or more fillers may be blended. The orientation ratio of the component (h) is determined based on the component (a) 10
50 parts by weight or less, preferably 2 to 48 parts by weight with respect to 0 parts by weight
It is in the range of parts by weight. 50% by weight of component (h)
If the amount exceeds the limit, the processability of the obtained resin composition is reduced.
It is not preferable. The low odor polyphenylene ether of the present invention
The resin composition further comprises the above components (c) to (h).
In addition, pigments, flame retardants, plasticizers, antioxidants, weathering agents, etc.
Additives may be included. The low odor polyphenylene ether of the present invention
The method for producing the resin composition is not limited. For example, use
After blending the ingredients in a known manner, the blend is kneaded,
Conventional melt kneading equipment such as roll mills and Banbury mixers
By mixing and kneading in a mixer, the low-odor polyolefin of the present invention is obtained.
A phenylene ether-based resin composition can be produced. In particular, low odor and conductive compositions,
Low odor conductive polyphenylene ether resin composition,
Component (a), component (b) and component (c) are essential components
If necessary, components (d) to (h) are also blended and dissolved.
It is obtained by melt-kneading. [0048] EXAMPLES Examples of the present invention will be described below in comparison with comparative examples.
Although shown, the present invention is not limited to these examples.
No. The following components were used.Component (a) As polyphenylene ether, 2,6-dimethylphenyl
At 25 ° C obtained by homopolymerization of
The intrinsic viscosity value measured with loroform is 0.41.
dl / g (hereinafter also referred to as “PPE-1”) and
0.50 dl / g (hereinafter also referred to as “PPE-2”)
U) was used. As a styrene resin, Sumitomo Chemical
Sumibright, a polystyrene manufactured by
E183 (hereinafter also referred to as "GPPS") and Sumitomo
With polybutadiene reinforced polystyrene manufactured by Chemical Industry Co., Ltd.
A certain Sumibright (registered trademark) M584 (hereinafter referred to as "HI
PS "). [0050]Component (b) As the alumina according to the resin composition of the present invention,
Al-1 and Al-2 were used.
The code | symbol 1 of Al-3 and Al-4 was used. Central grain
The diameter was measured by a sieving method. Here, Al-1 is Sumitomo Chemical
Activated Alumina A-11, Al-
2 is the company's hydraulic alumina BK-112, Al-3 is
The company's regular grain alumina A-21 and Al-4 are
Active alumina AC-21 for adsorption purification. [0051]Component (c) As carbon black according to the resin composition of the present invention,
Use code 2 of CB-1, CB-2 and CB-3
For comparison, reference numeral CB-4 in Table 2 was used. [0052]Component (d) Ethylene-propylene-non-conjugate produced as described below
Styrene and methyl methacrylate in diene copolymer rubber
Styrene / methyl
Methacrylate-graft-ethylene-propylene-non
A conjugated diene copolymer rubber was used. [0053]Component (e) Made by Kyoeisha Yushi Kagaku Kogyo Co., Ltd. and sold by Kyoeisha Chemical Co., Ltd.
Trade name of carboxylic acid amide-based high softening point wax
Is a light amide WH-215A (hereinafter referred to as "W
X ") was used. Here, WX stands for Steari.
Acid (2 mol)-sebacic acid (0.33 mol)-ethyl
Diamine (1.30 mol) polycondensate having a softening point
Is at 215 ° C. [0054]Component (f) Sumi, a low-density polyethylene manufactured by Sumitomo Chemical Co., Ltd.
Kasen (registered trademark) F210-6 (hereinafter also referred to as “PO”)
Say) was used. [0055]Ingredient (g) The trade name of talc manufactured by Hayashi Kasei Co., Ltd. is talc 5000.
S (hereinafter simply referred to as "talc"), and
The product name of mica manufactured by Nada Mica is Mica Repc
oMica S-325 (hereinafter simply referred to as “My
”). [0056]Component (h) conductive inorganic filler Product name of carbon fiber manufactured by Rika Hercules Co., Ltd.
Is Magnumite 1800AS (hereinafter referred to as “C
F "), Nippon Seisen's stainless steel with a diameter of 12 µm
Fiber whose product name is NASLON (hereinafter referred to as “S
F ”), and potassium titanate manufactured by Otsuka Chemical Co., Ltd.
The brand name of Umwhisker is DENTOL WK-200
(Hereinafter also referred to as “WK”). [0057]Reference example Component (d), styrene / methyl methacrylate-g
Raft-ethylene-propylene-non-conjugated diene copolymer
(SMEPR) was produced as follows. Equipped with a stirrer
Asahi Denka Kogyo Co., Ltd.
Water of 6g of dispersing agent whose product name is Pluronic F68
2200 ml of liquid and ethylene-manufactured by Sumitomo Chemical Co., Ltd.
Esprene, a propylene-non-conjugated diene copolymer rubber
(Registered trademark) E502 (repeated unit derived from propylene
Content 44% by weight, iodine value 8.5, at 120 ° C
Mooney viscosity 63) cut into 3-6 mm squares 3
And then suspended under stirring. Then, 101 g of styrene, methyl methacrylate
19 g of acrylate, 9 g of t-butyl peroxypivalate
And immediately after adding 0.18 g of p-benzoquinone
Place the autoclave in a 30 ° C oil bath at about 1 ° C per minute.
Temperature to 110 ° C at the rate of and kept at 110 ° C for 30 minutes
Then, a polymerization reaction was performed. Rinse the reaction product granules with water
After cleaning, vacuum dry at 95 ° C.
Acrylate-graft-ethylene-propylene-non-conjugated
Diene copolymer rubber (hereinafter also referred to as "SMEPR")
Obtained. [0059]Examples 1-27, Comparative Examples 1-12 and 14-24 Examples 1-27 and Comparative Examples 1-12 and 14-24 of
Among them, Examples 1 to 14 and Comparative Examples 1 to 12 are components (c)
Or a composition without the corresponding comparative component.
AndExamples 15 to 27 and Comparative Examples 14 to 24
Relates to the composition containing component (c) or a component corresponding thereto.
Is what you do. Mixing ratio of each component shown in Tables 3-12
(Parts by weight), and the mixture is mixed with TE manufactured by Toshiba Machine Co., Ltd.
After extruding with an M50 twin screw extruder and cooling in a water tank,
It was pelletized by a strand cutter. here,Real
Examples 8 to 14 and 27, and Comparative Examples 5 to 12In the case of
Extruder cylinder temperature is 260 ° C, otherwise
Was 300 ° C. The obtained pellets are heated indoors.
Dry for 3 hours with a wind dryer, and from the dried pellets
Test specimens were formed. Here, Examples 8 to 9 and Comparative Example 5
The hot air drying temperature in the case of ~ 7 is 80 ° C, and in other cases
The drying temperature was 130 ° C. Also, the molding of the test piece
Test with Toshiba Machine Co., Ltd. IS220EN injection molding machine
This was performed by using a mold for mold molding (mold temperature was 80 ° C.).
here,Examples 8 to 14 and 27 and Comparative Examples 5-1
2The cylinder temperature of the injection molding machine is 260 ° C
In other cases, the cylinder temperature was 330 ° C. The test method of the test piece is as described below.
The test results are shown in Tables 3 to 12.Odor determination method During hot air drying of the pellets, during drying or drying
When removing the pellets from the dryer,
The degree of odor at which work can be performed without worrying
The degree of odor that can not be worked unless ventilation of the
Was. The results are shown in Tables 3 to 12. [0062]Impact strength ASTM using a 3.2 mm thick notched test piece
Izod impact strength was measured based on D-256. Measurement
The unit of the fixed value is kg · cm / cm. Practical
Izod impact strength of polyphenylene ether resin composition
The degree is usually 2 kg · cm / cm or more. [0063]Surface resistivity (SSR) Using a flat test piece of 54 mm × 75 mm size,
Yuka Denshi Co., Ltd. trade name is Hiresta IP (MCP-
HT260 type). Practical
Of conductive polyphenylene ether-based resin composition
The surface resistivity is usually 1 × 10¹³It is as follows. [0064] According to the present invention, polyphenylene ether
By blending a specific alumina into the
The physical properties such as impact strength of the composition to an inconvenient degree.
Prominent odor generation during production and processing without lowering
Can be reduced. As shown in the comparative example,
Odor of polyphenylene ether-based resin composition containing no na
Q is x (Comparative Examples 1, 2, 6 to 12, 14, 17 to
24). Although alumina is included, the present invention
Satisfies the requirements for polyphenylene ether-based resin composition
No composition (See Comparative Examples 3, 4, 15, and 16) Shock
It is not preferable in terms of strength and SSR. Note that Comparative Example 5
A composition that contains a large amount of styrene resin,
problemWithoutA composition. On the other hand, according to the present invention, the embodiment
As is evident, the addition of specific alumina
Therefore, physical properties such as impact strength are reduced to an inconvenient degree.
Odor generation during manufacturing and processing
To obtain a cured polyphenylene ether-based resin composition.
it can. In particular, specific alumina and carbon black
By using them together, low odor conductive polyphenylene
A polyester resin composition is obtained (Examples 15 to 26).
Polyphenylene containing alumina that meets the requirements of the present invention
The greatest significance of providing an ether-based resin composition is
Workers who manufacture or process the composition indoors
No trouble with odor caused by nylene ether
It has become. [0066] [Table 1] ────────────────────────────────────                           Al-1 Al-2 Al-3 Al-4 ────────────────────────────────────   Chemical composition (% by weight)     Al_TwoO_Three            99.6 99.7 99.6 99.7     Fe_TwoO_Three            0.03 0.05 0.01 0.02     SiO_Two              0.02 0.01 0.01 0.02     Na_TwoO 0.33 0.25 0.25 0.25   Al_TwoO_ThreeCrystal form χ, γ γ α χ, γ   BET surface area (m^Two/ G) 130 280 1.2 120   Central particle size (μm) 40 11 45 200 ──────────────────────────────────── [0067] [Table 2] ────────────────────────────────────                   CB-1 CB-2 CB-3 CB-4 ────────────────────────────────────   Type Ketjen Acetylene Furnace Furnace                   Black Black Black Black   Manufacturer Lion (Electric Chemistry Cabot Mitsubishi Kasei (                   Co., Ltd.)   Grade name 600JD Denkabra Vulcan C Diabra                                 Cook # 45   DBP oil absorption 495 212 100 55 (Ml / 100g) ──────────────────────────────────── [0068] [Table 3] ────────────────────────────────────             Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 ────────────────────────────────────   PPE-1 100 100 100 100 100 100 100   Al-1 20 10   Al-2 10   Al-3 10   Al-4 10   Odor × × ○ ○ ○ ○   Impact strength 9 4 <2 <2 4 5 ──────────────────────────────────── [0069] [Table 4] ───────────────────────────────             Example 3 Example 4 Example 5 Example 5 Example 6 Example 7 ───────────────────────────────   PPE-1 100 100 100 100 100 100   Al-15 0.55   Al-2 0.55   Al-35   Odor ○ ○ ○ ○ ○   Impact strength 4 8 8 6 7 ─────────────────────────────── [0070] [Table 5] ───────────────────────────────             Comparative Example 5 Comparative Example 6 Comparative Example 7 Example 8 Example 9 ───────────────────────────────   PPE-1 10 30 30 30 30   GPPS 90 70 70   HIPS 70 70   Al-12 2   Odor ○ × × ○ ○   Impact strength 4 4 9 3 8 ─────────────────────────────── [0071] [Table 6] ────────────────────────────────────             Comparative Example 8 Comparative Example 9 Comparative Example 10 Example 10 Example 11 Example 12 ────────────────────────────────────   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 10   WX 55 55 55   PO 22   Odor × × × ○ ○ ○   Impact strength 20 17 18 18 16 16 ──────────────────────────────────── [0072] [Table 7] ──────────────────────────             Comparative Example 11 Comparative Example 12 Example 13 Example 14 ──────────────────────────   PPE-2 60 60 60 60   GPPS 40 40 40 40   Al-12 2   SMEPR 10 10 10 10   WX 55 55 55   PO 2 2 2 2   Talc 10 10   Mica 10 10   Odor × × ○ ○   Impact strength 12 10 11 10 ────────────────────────── [0073] [Table 1] ────────────────────────────────────             Example 27    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 32 22 40 18 22   Odor ○ × ○ ○ ○   Impact strength 5 3 <2 3 2   SSR> 1 × 10¹³  3 × 10^Five <1 × 10^Four   9 × 10⁷   3 × 10^Five  ──────────────────────────────────── [0074] [Table 9] ────────────────────────────                 Comparative Example 16 Example 17 Example 18 ────────────────────────────   PPE-1 60 60 60   GPPS 40 40 40   Al-1 2 2 2   CB-18   CB-3 33   CB-4 40   Odor ○ ○ ○   Impact strength <2 32   SSR> 1 × 10¹³    4 × 10^Five    4 × 10⁷ ──────────────────────────── [0075] [Table 10] ──────────────────────────────   Comparative Example 17 Comparative Example 18 Example 19 Example 20   PPE-2 60 60 60 60   GPPS 40 40 40 40   Al-12 2   CB-2 22 22 22 22 22   SMEPR 10 10 10 10   WX 55   Odor × × ○ ○   Impact strength 5 5 4 4   SSR 5 × 10^Five  6 × 10^Five  5 × 10^Five  6 × 10^Five ────────────────────────────── [0076] [Table 11] ────────────────────────────────────             Comparative Example 19 Comparative Example 20 Comparative Example 21 Example 21 Example 22 Example 23 ────────────────────────────────────   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 22   SMEPR 10 10 10 10 10 10 10   WX 55 55 55 55   PO 2 2 2 2 2 2   Talc 10 10   Mica 10 10   Odor × × × ○ ○ ○   Impact strength 5 3 3 4 3 3   SSR 6 × 10^Five1 × 10^Five2 × 10^Five6 × 10^Five1 × 10^Five1 × 10^Five ──────────────────────────────────── [0077] [Table 12] ────────────────────────────────────             Comparative Example 22 Comparative Example 23 Comparative Example 24 Example 24 Example 25 Example 26 ────────────────────────────────────   PPE-2 60 60 60 60 60 60   GPPS 40 40 40 40 40 40   Al-1 2 2 2   CB-2 20 20 20 20 20 20 20   SMEPR 10 10 10 10 10 10 10   WX 55 55 55 55   PO 2 2 2 2 2 2   Talc 10 10 10 10 10 10   CF 55   SF 55   WK 55   Odor × × × ○ ○ ○   Impact strength 4 4 3 4 4 3   SSR <1 × <1 × 2 × <1 × <1 × 2 ×               10^Four    10^Four    10^Five    10^Four    10^Four    10^Five ────────────────────────────────────

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 71/12 C08K 3/22 C08L 25/04-25/14

Claims (1)

(57) Claims 1. Component (a) 100 parts by weight of a composition comprising a polyphenylene ether or a styrene-based resin containing 80% by weight or less of a styrene-based resin and a component (b) A) low-odor polyphenylene ether-based resin composition containing transition alumina as a main component and having a center particle size of 150 μm or less and 0.1 to 15 parts by weight of alumina having a BET surface area of 10 m ² / g or more.