JP3073779B2 - Resin composition for IC heat resistant tray - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant tray for an IC which has conductivity, is excellent in moldability, heat resistance and heat aging, and has no problems such as peeling.

[0002]

2. Description of the Related Art When an IC component absorbs moisture, when it is heated to 100.degree.
During heating, water vapor is generated inside, causing blisters or cracks and causing breakage. Therefore, baking is performed in advance at a temperature of 100 ° C. or more. At this time, to protect the IC, 10
An IC tray made of a conductive material of ⁸ Ω or less is used. Conventionally, this tray was made of polyamide resin, polyester resin, etc. In recent years, for the purpose of improving productivity, baking time has been shortened due to temperature rise, and due to environmental issues, reuse from conventional disposable has been promoted. And a higher temperature type is required.

As a molding material for IC members, Japanese Patent Laid-Open No. 2-17
No. 5754 discloses that the heat distortion temperature is 130 ° C. or higher and the melt flow index is 3 g / 10 min (JIS-K72).
A molding material has been proposed in which the molded article has a surface resistance of 10 ⁷ Ω or less and a polyphenylene ether resin content of at least 50% by weight or more. Specifically, as means for satisfying these physical properties, two methods have been proposed in which an acid imide compound is added to a polyphenylene ether resin / conductive carbon system or a polyphenylene ether resin having a low intrinsic viscosity is used.

Japanese Patent Application Laid-Open No. 2-180958 discloses an IC for an IC molded from a resin composition obtained by adding an ABA ′ type hydrogenated block copolymer elastomer to a polyphenylene ether resin / conductive carbon system. Heat resistant trays have been proposed. However, these materials
The heat aging properties at high temperatures required for high temperature type IC trays and the peeling of molded products have not been sufficiently solved.
Also, the improvement of the fluidity is insufficient.

[0005] Japanese Patent Application Laid-Open No. 2-285302 has a similar proposal. On the other hand, JP-A-63-15262
No. 8 discloses a method of melting and kneading a polyphenylene ether resin in the presence of a compound having a carbon-carbon double bond, in the absence of a radical generator, at a temperature higher than the glass transition temperature of the polyphenylene ether resin. A method for producing an excellent polyphenylene ether resin has been proposed. Japanese Patent Publication No. 57-56941 discloses that impact resistance is improved by adding a hydrogenated styrene-butadiene-styrene block copolymer to a polyphenylene ether resin. The composition shown in the article has insufficient compatibility, has a problem of peeling, and has problems such as a decrease in fluidity.

Japanese Patent Application Laid-Open No. 2-276823 proposes a polyphenylene ether resin having a cyclized terminal group of the present invention, and a resin composition comprising the resin and a polystyrene resin.

[0007]

Under these circumstances, a heat-resistant tray material for ICs having conductivity and excellent moldability, heat resistance, and heat aging resistance has been intensively studied. This has led to the invention.

That is, the present invention comprises: (I) an average of 0.01 or more cyclized terminal groups represented by the following general formula (a) per 100 phenylene ether units constituting a resin; Number average molecular weight is 1,
(II) a block copolymer comprising at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B in the range of 000 to 100,000. And a vinyl aromatic compound polymer block A in the block copolymer.
Is 50% by weight or more and 90% by weight or less, and 90 to 1% by weight of a block copolymer in which the degree of unsaturation of the olefin compound polymer in the olefin compound polymer block B is 20% or less;

(III) a block copolymer comprising at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B, wherein the vinyl aromatic compound polymer in the block copolymer is 0 to 10% by weight of the block copolymer in which the content of the united block A is 20% by weight or more and less than 50% by weight and the degree of unsaturation of the olefin compound polymer in the olefin compound polymer block B is 20% or less. %, (IV) A resin composition comprising 3 to 40 parts by weight of conductive carbon with respect to 100 parts by weight of (I), (II) and (III), and a molded article using the same, particularly a heat-resistant tray. .

[0010]

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(Wherein R _{1 to} R ₅ are each independently hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group, and R _{6 to} R ₉ are each independently a hydrogen atom , An alkyl group, a substituted alkyl group, an alkenyl group,
Substituted alkenyl group, halogen group, aryl group, substituted aryl group, alkoxy group, N-lactam group, carboxylic acid group, carboxylic anhydride group, carboxylic ester group, carboxylic amide group, nitrile group, acyloxy group or acyl group It is. R ₆ and R ₇ , and R ₈ and R ₉ may be independently bonded to each other to form a ring having a spiro ring structure. )

That is, the present inventors have found that a polyphenylene ether resin having a specific structure having improved moldability and thermal stability has a vinyl aromatic compound polymer content in a block copolymer of 50% by weight to 90% by weight. It has been found that a heat-resistant tray material for ICs having conductivity, and excellent in moldability, heat resistance, and heat aging resistance can be obtained by combining a conductive carbon having a composition of not more than% by weight with conductive carbon. It has been reached.

The polyphenylene ether resin used in the present invention needs to contain an average of 0.01 or more of the cyclized terminal group represented by the general formula (a) per 100 phenylene ether units constituting the resin. There is. The average molecular weight (about 10,
000 to 30,000), the number of cyclized terminal groups is preferably 0.15 or more on average per 100 phenylene ether units. More preferably, the average is 0.2 or more. There is no particular upper limit, and the larger the number, the more preferable in terms of thermal oxidation deterioration. Further, a resin in which all of the terminal groups have the structure of the general formula (a) is also an extremely stable resin.

This polyphenylene ether resin generally has a repeating unit excluding its terminal group.

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It is defined as containing a phenylene ether unit represented by the formula, and is not particularly limited. A typical example is the following formula (b):

[0016]

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(Wherein, R _{1 to} R ₅ are each independently selected from hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group and a substituted aryl group). Consists of seeds.

When the basic skeleton of such a polyphenylene ether resin is produced by industrially advantageous oxidative coupling polymerization of phenols, R ₁ is methyl, ethyl,
Propyl, isopropyl, lower alkyl or phenyl, such as n- butyl, naphthyl, and preferably, R ₂ ~
R ₅ is preferably hydrogen or a lower alkyl group. The most preferred combination is where R ₁ is a methyl or phenyl group and R ₂ -R ₅ are hydrogen, R ₁ and R ₂ are methyl groups and R ₃ -R ₅ are hydrogen. In particular,
R ₁ is a methyl group, R _{2 to} R ₅ are hydrogen, and the phenylene ether unit is 9
Preferably it is 0 to 100%.

Most preferably, R ₁ to R ₁ satisfying these conditions.
Examples of the monomer corresponding to the phenylene ether unit having R ₅ include 2,6-dimethylphenol, 2-methyl-6-phenylphenol, 2,3,6-trimethylphenol, and the like. These monopolymers,
A copolymer is preferably used as the polyphenylene ether polymer as the resin basic skeleton of the present invention.

In the polyphenylene ether resin of the present invention, various other phenylenes which have been proposed to be allowed to exist in the polyphenylene ether resin have been proposed so far as they do not contradict the purpose of improving the thermal stability. An ether unit may be included as a partial structure. Examples of those proposed to coexist in a small amount include 2- (dialkylaminomethyl) 6-methylphenylene ether units described in Japanese Patent Application No. 63-12698 and JP-A-63-301222. , 2-
(N-alkyl-N-phenylaminomethyl) 6-methylphenylene ether unit and the like.

The polyphenylene ether resins also include those in which a small amount of diphenoquinone or the like is bonded in the main chain.
The molecular weight of the polyphenylene ether resin used in the present invention is 1,000 to 100,000 in number average molecular weight. The preferred range is about 6,000-60,00.
0. The number average molecular weight in the present invention is a number average molecular weight in terms of polystyrene obtained by gel permeation chromatography using a standard polystyrene calibration curve.

In the cyclized terminal group (a) of the polyphenylene ether resin used in the present invention, R _{1 to} R ₅ are each independently hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group. , R _{6 to} R ₉ each independently represent hydrogen, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a halogen group, an aryl group,
A substituted aryl group, an alkoxy group, an N-lactam group, a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid amide group, a nitrile group, an acyloxy group or an acyl group. Note that R ₆ and R ₇ , R ₈ and R ₉ are
Each may be independently bonded to form a ring having a spiro ring structure.

In the above definition of R _{1 to} R ₅ , the alkyl group is alkyl having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. As the substituent of the substituted alkyl, fluorine,
Halogens such as chlorine and bromine; hydroxyl groups; amino groups; lower alkoxy groups. Aryl is aryl having 6 to 20 carbon atoms. Examples of the substituent of the substituted aryl include halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and a lower alkoxy group.

In the definition of R _{6 to} R ₉ , the alkyl group is alkyl having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably lower alkyl. Examples of the substituent of the substituted alkyl include a halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and a lower alkoxy group. Alkenyl is ethylenyl, 3
Lower alkenyl such as -propenyl is preferred. A representative example of a substituted alkenyl is 1-hydroxy-3-propenyl. Aryl is aryl having 6 to 20 carbon atoms. As the substituent of the substituted aryl, a lower alkyl group;
Lower alkoxy groups; halogens such as fluorine, chlorine and bromine; hydroxyl groups; amino groups; and aminoalkyl groups such as aminomethyl groups.

The aryl group means an aromatic ring group in a broad sense, and includes, in addition to aryl in a narrow sense, a heteroaromatic ring group such as a pyridyl group and a triazyl group. Representative examples of N-lactam include N-2-pyrrolidonyl, N-ε-caprolactamoyl and the like. Representative examples of carboxylic acid amides include carbamoyl, phenylcarbamoyl, seryl, and the like. Preferred examples of the carboxylic anhydride are acetoxycarbonyl and benzoyloxycarbonyl. Representative examples of carboxylic esters include methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, and the like. Representative examples of the acyl group include acetyl and benzoyl, and preferred examples of acyloxy include acetoxy and benzoyloxy.

From the viewpoint of stability, it is preferable that two to three, and particularly three of R _{6 to} R ₉ are hydrogen. At this time, other groups include an aryl group, a substituted aryl group, a carboxylic acid group,
It is preferable to select from a carboxylic anhydride group, a carboxylic ester group, a carboxylic amide group, a nitrile group, and an N-lactam group. In particular, the case where at least one of R ₈ and R ₉ is an aryl group or a substituted aryl group is preferable from the viewpoint of stability against thermal oxidative deterioration and a production method described later. R
Representative examples of aryl or substituted aryl groups in the definitions of _{6 to} R ₉ include phenyl, tolyl, chlorophenyl, naphthyl, 4-pyridyl, 3,5-diamino-
(S) -triazyl group and the like.

The structure and amount of such a cyclized terminal group can be measured using a nuclear magnetic resonance spectrum.
Since the polyphenylene ether resin having the cyclized terminal group (a) has the cyclized terminal group, when melted (molded), the generation of the transition structure represented by the following general formula (e) is smaller than that of the conventional polyphenylene ether resin. It has excellent properties such that the molecular weight is hardly changed and the molecular weight is hardly changed.

[0028]

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(Wherein R _{1 to} R ₅ are each independently hydrogen,
It is an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group. ) This stabilized polyphenylene ether resin can be produced as follows.

That is, the general formula (c):

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(Wherein, R _{1 to} R ₅ are the same as defined in the formula (a), and R ₁₀ and R ₁₁ are each independently hydrogen,
Represents an alkyl group or a substituted alkyl group, but not simultaneously hydrogen. A) a polyphenylene ether polymer having a terminal group represented by the general formula (d):

[0032]

Embedded image (In the formula, R _{6 to} R ₉ are the same as those defined in the formula (a).)

By heating to a temperature above the glass transition temperature of the polyphenylene ether polymer in the absence of a compound having a carbon-carbon double bond (hereinafter referred to as an unsaturated compound) and a radical polymerization initiator Can be manufactured.

The alkyl group and substituted alkyl group in R ₁₀ and R ₁₁ in the formula (c) are preferably (C ₁ -C ₂₀ ) alkyl group, (C ₁ -C ₂₀ ) hydroxyalkyl group, (C ₂
-C ₂₂₎ alkoxyalkyl group, (C ₃ ~C ₂₂₎ acyloxyalkyl group or a (C ₄ ~C ₂₀₎ polyalkylene ether groups. The polyphenylene ether having such a terminal group (c) can be obtained by oxidative coupling polymerization or co-polymerization of a phenol compound having at least one benzylic hydrogen at the ortho position of a hydroxyl group in the presence of a catalyst containing a primary or secondary amine. It is obtained by polymerization (for example, US Pat. No. 4,788,277).

In this case, the polymer obtained has the general formula
(c) is obtained as a mixture of a polyphenylene ether having a terminal group represented by (c) and a polyphenylene ether having a terminal structure in which a primary or secondary amine is not bonded at a benzyl position, which is separated in the present invention. Can be used without doing. The usage ratio of the former and the latter is not particularly limited, but is preferably 0.9 or more if expressed as a ratio of the number of terminal groups of the former / the number of terminal groups of the latter.

In the present invention, the amount of reaction between the polyphenylene ether having a terminal group represented by the general formula (c) and the unsaturated compound represented by the general formula (d) is preferably the amount used in the general formula (c). The unsaturated compound represented by the general formula (d) may be used in an amount of about 2 to 50 equivalents to the polyphenylene ether having a terminal group represented. When producing the stabilized polyphenylene ether resin of the present invention, the unsaturated compound (d) may be formed intermediate radical (f), for example, biradil.
In order to stabilize in the form of (g), R ₈ and / or R ₉
Is preferably an aryl or substituted aryl group.

[0037]

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Preferred specific examples of the unsaturated compound (d) include styrene, α-methylstyrene, chlorostyrene,
Methyl styrene, stilbene, cinnamon alcohol, benzalacetone, ethyl cinnamate, nitrile cinnamate, 4
-Vinylpyridine, 2-vinyl-3,5-diamino-
(S) -triazine and the like.

As the unsaturated compound (d), a compound containing no aromatic ring can be used. Such unsaturated compounds
Specific examples of (d) include acrylic acid; methyl, ethyl, propyl, butyl, isobutyl, t-butyl, 2-ethylhexyl, octyl, isodecyl, lauryl, lauryl-tridecyl, tridecyl, cetyl-stearyl, stearyl , Acrylic acid esters such as cyclohexyl and benzyl ester; acrylamide, acrylonitrile, methacrylic acid; methyl methacrylate;
Ethyl, propyl, butyl, isobutyl, t-butyl,
Methacrylic acid esters such as 2-ethylhexyl, octyl, isodecyl, lauryl, lauryl-tridecyl, tridecyl, cetyl-stearyl, stearyl, cyclohexyl, benzyl ester; methallylamide, methacrylonitrile, itaconic acid; dimethyl itaconate;
Itaconic acid diesters such as diethyl, dibutyl, di-2-ethylhexyl, dinolyl, dioctyl ester;
Itaconic acid monoesters such as monomethyl, monoethyl, monobutyl, mono-2-ethylhexyl, mononolyl, monooctyl ester; itaconic anhydride; N-vinyl compounds such as N-vinylpyrrolidone; vinyl ethers such as butyl vinyl ether And the like.

In the production of the stabilized polyphenylene ether resin of the present invention, the polyphenylene ether polymer is mechanically mixed with the unsaturated compound (d) before being heated to a glass transition temperature of 180 ° C. or higher. It is preferable to keep it. The method of mixing is not particularly limited, but a method of dry blending with a Henschel mixer or the like, a method of drying after melt blending, the unsaturated compound (d) does not dissolve the polyphenylene ether but dissolves the unsaturated compound (d), for example, After dissolving in a solvent such as methanol or pentane, impregnating the polyphenylene ether-based polymer having a terminal group (c) in a powder form, a method of removing the solvent by drying, or the like.

The polyphenylene ether polymer and the unsaturated compound (d) mechanically mixed as described above are then heated and melted to a temperature equal to or higher than the glass transition temperature (about 208 ° C.) of the polyphenylene ether polymer. A preferred temperature range is a glass transition temperature of 20 to 150 ° C or higher, and more preferably 50 to 120 ° C or higher. Although the heating time cannot be unconditionally determined in relation to the temperature, the heating may be carried out for a time sufficient to complete the desired reaction. Generally, it is about 1 minute to 1 hour, and preferably about several minutes. There is no point in making it too long.

Since the reaction for forming the cyclized terminal group (a) is usually sufficiently fast at a temperature higher than the glass transition temperature, it is better not to apply unnecessary heat excessively. Further, as described above, the heating needs to be performed in the absence of the radical polymerization initiator. Oxygen should also be removed as much as possible, and for that purpose, the reaction atmosphere is preferably a nitrogen gas atmosphere or the like.

Next, the block copolymer used in the present invention is a block copolymer comprising at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B. The content of the vinyl aromatic compound polymer block A in the copolymer is 50% by weight or more and 90% by weight or less, and the degree of unsaturation of the olefin compound in the olefin compound polymer block B is 20% or less. is there.

The olefin compound polymer block of the block copolymer is a monoolefin such as ethylene, propylene, 1-butene or isobutylene, or a conjugated diolefin such as butadiene, isoprene or 1,3-pentadiene. A polymer block having a form in which at least one olefin compound selected from non-conjugated diolefins such as hexadiene, norbornene and norbornene derivative is polymerized or copolymerized, and the degree of unsaturation of the block is 20. % Or less. Therefore, when the above-mentioned diolefins are used as the constituent monomers of the olefin compound polymer block, the degree of unsaturation is reduced by a method such as hydrogenation so that the degree of unsaturation of the block does not exceed 20%. Action must be taken. Further, a vinyl aromatic compound may be randomly copolymerized in the olefin compound polymer block as long as its properties are not impaired.

A preferred block copolymer is a block copolymer composed of a vinyl aromatic compound polymer block and a polymer block mainly composed of a conjugated diene compound (hereinafter referred to as a “block copolymer as a precursor”). Polymers ''
Conjugated diene portion) is selectively hydrogenated to such an extent that the degree of unsaturation of the conjugated diene portion does not exceed 20%. As the vinyl aromatic compound constituting the “block copolymer as a precursor”, one or more of styrene, α-methylstyrene, vinyltoluene and the like are selected, and styrene is particularly preferred. The conjugated diene compound is selected from one or more of butadiene, isoprene, 1,3-pentadiene and the like, and among them, butadiene and / or isoprene is particularly preferred.

In the "block copolymer as a precursor", the weight ratio of the content of the vinyl aromatic compound to the content of the conjugated diene compound is preferably in the range of 50/50 to 90/10, and 55/45 to 90/10. A range of 85/15 is more preferred. When the content of the vinyl aromatic compound is less than 50% by weight, a phase separation phenomenon due to poor compatibility occurs during molding of the resin composition, and the fluidity also has an adverse effect. On the other hand, if the content of the vinyl aromatic compound exceeds 90% by weight, the effects of improving the impact resistance, the heat aging property and the like cannot be seen.

The above block copolymer has a number average molecular weight of 2,000 to 500,000, preferably 20,000.
And the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably in the range of 1.05 to 10. The molecular structure of the block copolymer is
Linear, branched, radial or combinations thereof. Among them, those having a linear structure are more preferable.

As a method for producing the “block copolymer as a precursor”, for example, JP-B-36-19286, JP-B-43-14979, and JP-B-49-36
957, JP-B-48-2423, JP-B-4
8-4106, and the like. All of these are methods in which a vinyl aromatic compound and a conjugated diene compound are block-copolymerized using an organic lithium compound or the like as an anionic polymerization initiator in a hydrocarbon solvent and optionally using a vinylating agent, a coupling agent, or the like. It is.

The above-mentioned “block copolymer as a precursor” is hydrogenated by a known method, for example, the method described in JP-B-42-8704, whereby the block copolymer used in the present invention is obtained. can get.

Next, the block copolymer (III) used in the present invention is a block copolymer comprising at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B. The content of the vinyl aromatic compound polymer block A in the block copolymer is 20% by weight or more and less than 50% by weight;
Moreover, the degree of unsaturation of the olefin compound in the olefin compound polymer block B is 20% or less. This block copolymer is the same as the block copolymer (II) except that the content of the vinyl aromatic compound polymer block A in the copolymer is 20% by weight or more and less than 50% by weight. is there.

The polyphenylene ether resin of the present invention / block copolymer (II) / block copolymer (III)
Is suitably 10 to 99% by weight / 90 to 1% by weight / 10 to 0% by weight. Preferably 30 to
97% by weight / 62 to 2% by weight / 8 to 1% by weight, more preferably 50 to 94% by weight / 48 to 4% by weight / 6 to 2% by weight.

The conductive carbon used in the present invention is used for the purpose of dispersing it in the composition to impart conductivity and greatly reducing the surface resistance of the resin molded product. For example, acetylene black and furnace black may be used. it can.
Specific examples of furnace black include Ketchen Black EC, EC600JD (by Akzo), Asahi HS
-500 (made by Asahi Carbon Co., Ltd.), Vulcan XC72 (CA
Commercially available products such as BOT Corporation).

The amount of conductive carbon to be added is a total of 10 of the polyphenylene ether resin of the present invention and the block copolymer.
3 to 40% by weight, preferably 5 to 30% by weight based on 0 part by weight
%, More preferably 5 to 20% by weight. If it is less than 3% by weight, the conductivity is insufficient, and if it exceeds 40% by weight, the fluidity and mechanical strength are reduced, and a good resin molded product cannot be obtained.

Such a composition ratio can be obtained by blending and extruding at the same time or after the production of a stabilized polyphenylene ether resin containing a cyclized terminal group. A vinyl aromatic resin may be added to this composition as long as the characteristics are not impaired.

Examples of the vinyl aromatic resin include a homopolymer of styrene and a copolymer with another ethylenically unsaturated monomer as long as the compatibility of the composition is not impaired. A vinyl aromatic polymer obtained by reinforcing these resins with an elastomer may be used. Examples of specific comonomers include α-methylstyrene, acrylonitrile,
Examples include methacrylonitrile, acrylates, methacrylates, maleic anhydride, N-alkylmaleimides, N-arylmaleimides, and vinyl oxazolines.

To the resin composition of the present invention, an antistatic agent, an inorganic filler, various stabilizers, a plasticizer, a flame retardant, a pigment, etc. are appropriately added according to a known method, as long as the properties are not impaired. be able to. From the resin composition of the present invention,
There is no particular limitation on the method of forming the heat-resistant tray for IC, and a usual method using an injection molding machine or a method using a melt press is used.

[0057]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In addition, each measurement was performed on condition of the following. Viscosity of polymer: 30% 0.5% chloroform solution
Ηsp measured using a Ubbelohde viscosity tube under the condition of
/ C. ¹ H- nuclear magnetic resonance spectrum; a CDCl ₃ Japanese GX-270 manufactured by Electronic Co. measured as solvent, with tetramethylsilane as a reference. Gel permeation chromatography (hereinafter, referred to as
GPC); measured by HL-802RTS manufactured by Toyo Soda Kogyo Co., Ltd. As a calibration curve in GPC, one prepared using standard polystyrene is used.

Free phenolic OH in polymer
Group; methods such as EHUD SHCHORI [Journal
Of Applied Polymers Science; Applied Polymer Symposium, 34, 103-117
Page, (1978)]. Melt flow rate: measured at 280 ° C. under a load of 10 kg. Heat deformation temperature: Measured under a load of 18.6 kg / cm ² according to ASTM D-648. Izod impact strength; measured according to ASTM D-256.

Phase peelability: The vicinity of the gate of an injection-molded 1 / 8-inch thick dumbbell specimen is bent and broken, and the fractured surface is evaluated by visual observation. Conductivity: Surface resistivity is measured according to ASTM D-257. (10) Thermal aging; 1 in a hot air oven at 150 ° C
After aging for a week, a tensile test is performed and the tensile strength before and after aging is expressed.

Examples 1-3 and Comparative Example 1 The raw material polyphenylene ether was prepared according to US Pat.
It is prepared by oxidative coupling polymerization of 2,6-xylenol in the presence of dibutylamine according to the method described in US Pat. No. 8,277. The viscosity of the resulting polyphenylene ether is 0.545 and the glass transition temperature is about 208 ° C. As a result of analysis by ¹ H-nuclear magnetic resonance spectrum, formula (i) was obtained;

[0061]

Embedded image It is confirmed that there are 0.32 terminal groups per 100 main repeating units (h) described below.

[0062]

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The amount of free phenolic hydroxyl groups is
It is confirmed that there are 0.34 per 100 main repeating units (h). After uniformly blending 10 parts by weight of styrene with 100 parts by weight of this polyphenylene ether using a Henschel mixer, a twin-screw extruder having a screw diameter of 30 mmφ (PCM manufactured by Ikegai Iron Works Co., Ltd.)
−30) The mixture is melt-kneaded at 300 ° C. and pelletized through a water tank. The pellet thus obtained was analyzed by ¹ H-nuclear magnetic resonance spectrum.

[0064]

Embedded image The terminal group of the main repeating unit (h) per 100
The presence of 0.25 is confirmed from the area value of the signal at 5.02 ppm.

The amount of free phenolic hydroxyl groups is
It is confirmed that there are 0.45 out of 100 main repeating units (h). The number average molecular weight determined by GPC is 24,500, and the viscosity is 0.547.
80 parts by weight of the pellets, 20 parts by weight of the block copolymer shown in Table 1, and 100 parts by weight thereof were mixed with 7 parts by weight of Ketchen Black EC600JD (conductive carbon manufactured by Akzo Co., Ltd.). 32 in twin screw extruder
The mixture is melt-kneaded at 0 ° C and pelletized. The pellets are processed by an injection molding machine (IS80EPN manufactured by Toshiba Machine Co., Ltd.) to 330
Mold under the condition of ° C. to prepare a test piece and evaluate. Table 1 shows the results.

[0066]

[Table 1]

As is clear from Table 1, the compositions of Examples 1 to 3 are excellent in phase releasability and fluidity, and have excellent properties as a resin composition for IC trays.

Comparative Example 2 A polyphenylene ether having the same terminal group (i) as that used in Example 2 was extruded into pellets under the same conditions except that styrene was not used. The results of analysis of the pellets are as follows. Number average molecular weight 26,000 Solution viscosity (ηsp / c) 0.672 Free phenolic OH group 0.58 Furthermore, this pellet was formed into a composition with a block copolymer and conductive carbon in the same manner as in Example 1 and evaluated. I do.

Comparative Example 3 The pellets obtained in Example 2 were evaluated without adding only the block copolymer. Table 2 shows the results.

[0070]

[Table 2]

Examples 4 to 7 Evaluations were made in exactly the same manner as in Example 2 except that the amounts of the polyphenylene ether resin and the block copolymer were changed as shown in Table 3.

[0072]

[Table 3]

Examples 8 to 10 Evaluations were made in exactly the same manner as in Example 2 except that the compounds shown in Table 4 were used instead of styrene.

[0074]

[Table 4]

Example 11 The conductive carbon in Example 2 was replaced with the type shown in Table 5 below.
Exactly the same evaluation was performed except that the amount was used.

[0076]

[Table 5] * 1) Akzo conductive carbon

Examples 12 to 16 The block copolymer (II) was evaluated in the same manner as in Example 2 except that the following properties were used and the amounts shown in Tables 6 and 7 were used. Styrene content; 60% by weight Number average molecular weight: 8.0 × 10 ⁴ Unsaturation degree: 2%

[0078]

[Table 6]

[0079]

[Table 7] * 2) Use a maleic anhydride-modified product (1% added).

Examples 17 to 20 Evaluations were made in exactly the same manner as in Example 13 except that the amounts of the polyphenylene ether resin and the block copolymer were changed as shown in Table 8.

[0081]

[Table 8]

[0082]

Molding material of the present invention exhibits good moldability, heat resistance, shows the thermal aging resistance, phase separation, and the like without trouble is electrically conductive also with 10 ⁸ or less good, IC tray - material Suitable as.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-305814 (JP, A) JP-A-2-276823 (JP, A) JP-A-3-231962 (JP, A) JP-A-3-231 163154 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (3)

(57) [Claims] (I) The cyclized terminal group represented by the following general formula (a) contains an average of 0.01 or more per 100 phenylene ether units constituting a resin, and has a number average molecular weight of at least 0.01. In the range of 1,000 to 100,000,
10 to 99% by weight of polyphenylene ether resin, (I
I) a block copolymer comprising at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B, wherein the vinyl aromatic compound polymer block A in the block copolymer is 90 to 1% by weight of a block copolymer having a content of 50% by weight or more and 90% by weight or less and an unsaturation degree of the olefinic compound polymer in the olefinic compound polymer block B of 20% or less; A) a block copolymer comprising at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B, and containing the vinyl aromatic compound polymer block A in the block copolymer; The amount of olefin in the olefin compound polymer block B is 20% by weight or more and less than 50% by weight. Degree of unsaturation compound polymer is 20% or less block copolymer is 0-10 wt%, (IV)
(I) A resin composition comprising 3 to 40 parts by weight of conductive carbon based on 100 parts by weight of (II) and (III). Embedded image (Wherein, R _{1 to} R ₅ are each independently a hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group, and R _{6 to} R ₉ are each independently a hydrogen, an alkyl group A substituted alkyl group, alkenyl group, substituted alkenyl group, halogen group, aryl group, substituted aryl group, alkoxy group, N-lactam group, carboxylic acid group, carboxylic anhydride group, carboxylic ester group, carboxylic amide group, A nitrile group, an acyloxy group, or an acyl group; R ₆ and R ₇ , and R ₈ and R ₉ may be independently bonded to each other to form a ring having a spiro cyclic structure.) 2. A resin molded article molded from the resin composition according to claim 1. 3. A heat-resistant tray for IC molded from the resin composition according to claim 1.