JPH09279013A - Conductive polyphenylene ether resin composition reduced in emission of odor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a conductive polyphenylene ether resin composition which emits less odor when it is melt-processed or its molding is heated to high temperatures by mixing a mixture of a polyphetylene ether resin with a styrene resin with carbon black and an aromatic carboxylic acid anhydride. SOLUTION: One hundred (100) pts.wt. resin mixture (A) comprising 95-50wt.% polyphenylene ether resin [e.g. poly(2,6-dimethyl-1,4-phenylene)ether] and 5-50wt.% styrene resin is mixed with 3-40 pts.wt. carbon black (B) and 1×10<-3> to 1×10<-3> h equivalent of the acid anhydride groups, per kg of the total of components A and B, of an aromatic carboxylic acid anhydride. Although a resin composition comprising components A and B can give a molding which does not deform even when it is used at 120 deg.C or higher for a long time, it has a drawback that a foreign odor is emitted when it is subjected to melt processing such as granulation or injection molding or its molding is heated to high temperatures. By adding components C to the mixture of components A and B, a resin composition freed from the above drawback and having unimpaired properties can be obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a conductive polyphenylene ether resin composition having improved odor.

[0002]

2. Description of the Related Art Polyphenylene ether resins are widely used as extremely useful engineering plastics because they have excellent electrical and mechanical properties, high heat distortion temperature and self-extinguishing property. For example, in the electric and electronic fields, a surface resistance of an IC tray or a TAB carrier is in the range of 10 ³ to 10 ¹⁰ Ω, and a molded product which is not deformed even when used at a high temperature of 120 ° C. or higher for a long time is required. This can be achieved by a resin composition composed of a polyphenylene ether resin and a styrene resin and carbon black as disclosed in JP-A-2-180958. However, this resin composition has a drawback that it emits an offensive odor during melt processing such as granulation and injection molding, and at the time of heating a molded product at a high temperature, which significantly deteriorates the working environment. There is no method to improve this odor effectively,
For example, a method for improving the odor during melt processing of the polyphenylene ether resin itself is disclosed in JP-A-2-265960, but this method is problematic in the case of a polyphenylene ether resin composition containing carbon black. The odor is not sufficiently improved.

[0003]

SUMMARY OF THE INVENTION With respect to the above problems, the present invention improves the odor at the time of melt processing such as granulation / injection molding and at the time of heating a molded article at a high temperature even when it contains carbon black, and has physical properties. It is an object of the present invention to provide a polyphenylene ether resin composition which does not deteriorate

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be achieved by adding an acid anhydride having a specific structure even when carbon black is used. They have found the present invention and completed the present invention.

That is, according to the present invention, 100 parts by weight of a resin mixture comprising (A) 95 to 50% by weight of polyphenylene ether resin and 5 to 50% by weight of styrene resin, (B) 3 to 40 parts by weight of carbon black and (C). Aromatic carboxylic anhydride 1 is 1 × 10 ⁻³ to 1 × 1 per 1 kg of (A + B).
0 ^-1 consisting anhydride group equivalent, odor is improved, and it relates not impaired physical properties resin composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene ether resin used in the present invention is obtained by a known method of oxidatively polymerizing a phenol compound represented by Formula 1 (Formula 1) with oxygen or an oxygen-containing gas using an oxidative coupling catalyst. Is a polymer.

[0007]

Embedded image (In the formula, R1, R2, R3, R4 and R5 are each independently hydrogen, halogen, alkyl, alkyl halide,
It is selected from the group consisting of aryl and aryl halide, and at least one is hydrogen. ) Specific examples of the phenol compound include phenol,
o-, m-, or p-cresol, 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, thymol, 2-methyl-
6-allylphenol and the like can be mentioned. Two or more kinds of the above phenol compounds may be copolymerized to form a copolymer, and two or more kinds of homopolymers or copolymers obtained may be mixed and used. Of the above phenolic compounds, 2,6-dimethylphenol is particularly suitable, and therefore poly (2,6-dimethyl-1,4-phenylene) ether obtained by polymerizing the same gives good results in the present invention. .

The preferred molecular weight of the polyphenylene ether resin in the present invention is such that its intrinsic viscosity is 0.3.
~ 0.7 dl / g, more preferably 0.35 to 0.5 d
It is in the range of 1 / g (25 ° C, in chloroform). If it is less than 0.3 dl / g, the mechanical strength of the resulting composition may be poor, and if it exceeds 0.7 dl / g, the processability of the composition may be poor.

The styrene resin used in the present invention is composed of an aromatic vinyl compound represented by the formula 2 (formula 2), and known methods such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization. It is obtained by polymerizing with.

[0010]

Embedded image (In the formula, R1 and R2, R3, R4, R5, and R6 are each independently selected from the group consisting of hydrogen, halogen, alkyl, and alkyl halide.) Specific examples of the aromatic vinyl compound include ,styrene,
α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, chlorostyrene, dichlorostyrene,
Examples include bromostyrene, dibromostyrene, p-ethylstyrene, p-tert-butylstyrene and the like.
Of these, styrene and α-methylstyrene are particularly preferable. Further, as the styrene resin used in the present invention, a modified product obtained by polymerizing the above aromatic vinyl compound in the presence of a rubber-like polymer and / or other copolymerizable monomer may be used if necessary.

Examples of the rubber-like polymer include diene rubber-like polymers represented by polybutadiene, butadiene-styrene copolymer, polyisoprene, etc., ethylene-propylene copolymer and ethylene-propylene-diene copolymer. Ethylene-α-olefin rubbery copolymer represented by, for example, acrylic rubber mainly composed of acrylic acid ester, isobutylene-isoprene copolymer, polyurethane rubber and the like can be used, but among them, polybutadiene A diene rubber-like polymer such as or butadiene-styrene copolymer is preferably used.

Other copolymerizable monomers include vinyl cyanide monomers, maleic acid and maleic anhydride, their derivatives, and acrylic acid-based esters. Specifically, the vinyl cyanide monomer may be acrylonitrile, methacrylonitrile, or the like, the maleic acid derivative may be maleic acid ester such as dibutyl maleate, and the maleic anhydride derivative may be N-phenylmaleimide or the like. Substituted maleimides and methyl acrylate, methyl methacrylate, etc. are preferable as acrylic acid-based esters. The above-mentioned aromatic vinyl compounds, rubber-like polymers and other copolymerizable monomers can be used alone or in combination of two or more. Further, two or more kinds of the obtained polymers may be mixed and used.

In the present invention, the content of the rubbery polymer in the styrene resin is preferably 80% by weight or less, more preferably 5 to 70% by weight. In order to increase the impact strength of the composition, it is preferable that the rubber-like polymer is contained in an amount of 5% by weight or more, but if it exceeds 80% by weight, the processability of the composition may not be improved. It is also preferable that 50% by weight or more, more preferably 70% by weight or more, of the matrix component excluding the rubbery polymer is the aromatic vinyl compound represented by the formula (Formula 2). When the amount of the aromatic vinyl compound is less than 50% by weight, the compatibility with the polyphenylene ether resin may be poor and mechanical strength and surface appearance may be impaired, which is not preferable. In the present invention, so-called high-impact polystyrene obtained by grafting styrene onto polybutadiene is particularly preferably used.

In the present invention, the ratio of the polyphenylene ether resin to the styrene resin is 95 to 50% by weight,
The latter is preferably in the range of 5 to 50% by weight. If the styrene-based resin exceeds 50% by weight, a heat distortion temperature of 120 ° C. or higher may not be obtained, which is not preferable.

The carbon black used in the present invention is added mainly for the purpose of imparting conductivity to the resin. A so-called high structure carbon black is preferable in order to develop good conductivity with a small amount of addition, and a dibutyl phthalate oil supply amount (ASTM D24 which is an index of the structure).
14) is preferably in the range of 100 to 600 ml / 100 g. If it is less than 100 ml / 100 g, the conductivity-imparting effect may be inferior, and if it exceeds 600 ml / 100 g, the viscosity of the composition may be high, resulting in poor processability. Specific examples thereof include acetylene black obtained by thermally decomposing acetylene gas, and Ketjen black produced by furnace type incomplete combustion using crude oil as a raw material. In the present invention, these may be used alone or in combination of two or more.

The preferred amount of carbon black added in the present invention is in the range of 3 to 40 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the resin mixture comprising the polyphenylene ether resin and the styrene resin. 3
If it is less than 10 parts by weight, the surface resistance of the molded product of the resin composition is 10
^It may be ¹⁰ Ω or more, and if it exceeds 40 parts by weight, the mechanical strength may be poor, which is not preferable.

The carboxylic acid anhydride used in the present invention is aromatic and refers to a compound having an acid anhydride group formed by dehydration of a plurality of carboxyl groups in a single ring or a condensed ring. For example, phthalic anhydride, pyromellitic dianhydride, -1,2-naphthalic anhydride, -2,3-naphthalic anhydride, -1,8-naphthalic anhydride, naphthalene-1,
Examples include 4,5,8-tetracarboxylic dianhydride. The hydrogen of these aromatic rings may be substituted with various alkyl, aryl, halogen and other substituents. The range of the addition concentration of the aromatic carboxylic acid anhydride suitable in the present invention is determined by the “acid anhydride group equivalent” of the aromatic carboxylic acid anhydride per 1 Kg of the total amount of the component (A) and the component (B). . The acid anhydride group equivalent here is a value obtained by dividing the number of moles of an aromatic carboxylic acid anhydride by the number of acid anhydride groups that one molecule has, and specifically 1 ×
10 ⁻³ to 1 × 10 ⁻¹ acid anhydride group equivalent / kg, more preferably 5 × 10 ^{−3 to} 5 × 10 ⁻² acid anhydride group equivalent / k
The range of g is preferred. When the addition concentration of the aromatic carboxylic acid anhydride is less than 1 × 10 ⁻³ acid anhydride group equivalent / kg, the odor improving effect of the composition, which is a feature of the present invention, may be poor, and 1 × 10 ^{− If} it exceeds ¹ acid anhydride group equivalent / kg, the mechanical strength and heat resistance of the composition may be deteriorated, which is not preferable. These aromatic acid anhydrides can be used alone or in combination of two or more. In this case, the total number of acid anhydride group equivalents corresponding to the combination ratio needs to be included in the above range.

The above-mentioned resin composition contains other thermoplastic resins and elastomers within the range not impairing the characteristics of the present invention.
Alternatively, plasticizers, pigments, stabilizers, flame retardants and other additives, metal powders, glass fibers, carbon fibers and other fillers can be appropriately used according to the purpose and application. Further, the method for producing the resin composition of the present invention is not particularly limited, and a generally known method can be adopted. That is, after the components (A), (B), (C) and other necessary components are uniformly mixed, they are melted with a uniaxial or multiaxial extruder, a mixing roll, a kneader, a brabender, etc., having a sufficient kneading ability. It can be manufactured by a method such as kneading.

[0019]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 3 polyphenylene ether resin (GEM Polymer Co., Ltd.)
Manufactured, 25 ° C, the intrinsic viscosity measured in chloroform is 0.
47 dl / g), high impact polystyrene as styrene resin (Mitsui Toatsu Chemicals, Inc., trade name Topolex 873-01, hereinafter "styrene resin"), carbon black (Colombian Carbon Co., Ltd., product Name: CONDUCTEX975, hereinafter "carbon black 1"), and phthalic anhydride (reagent, hereinafter "aromatic carboxylic acid anhydride 1") as an aromatic carboxylic acid anhydride in the proportions shown in Table 1 and then thoroughly mixed with a tumbler mixer. After mixing, they were melt-mixed with a twin-screw extruder having a screw diameter of 37 mm and L / D = 32 at 300 ° C. and a screw rotation speed of 80 rpm, and extruded into pellets. Evaluation was performed using the pellets and test pieces obtained by injection molding from the pellets. The results are shown in Table 1.

Example 4 The same evaluation was performed using the aromatic carboxylic acid anhydride 1 of Example 2 as tetrabromophthalic anhydride (reagent, hereinafter "aromatic carboxylic acid anhydride 2"). Table 2 shows the results.

Example 5 The same evaluation was carried out using the aromatic carboxylic acid anhydride 1 of Example 2 as pyromellitic dianhydride (reagent, hereinafter "aromatic carboxylic acid anhydride 3"). Table 2 shows the results.

Example 6 The aromatic carboxylic acid anhydride 1 of Example 2 was converted into anhydrous-1,8-
The same evaluation was performed for naphthalic acid (reagent, hereinafter “aromatic carboxylic acid anhydride 4”). Table 2 shows the results.

Example 7 Carbon black 1 of Example 2 was replaced with carbon black 2
The same evaluation was performed (trade name: 3050B, manufactured by Mitsubishi Chemical Corporation). Table 2 shows the results.

Examples 8 to 9 The same evaluation was performed by changing the ratio of the polyphenylene ether resin and the styrene resin of Example 2. The results are shown in Table 3.

Examples 10 to 11 The same evaluation was performed by changing the addition amount of carbon black 1 of Example 2. The results are shown in Table 3.

Comparative Examples 1 and 2 Similar evaluations were carried out using the aromatic carboxylic acid anhydride 1 of Examples 1 to 3 as an unsuitable addition amount. The results are shown in Table 4.

Comparative Example 3 The same evaluation was carried out by setting the ratio of the styrene resin to the polyphenylene ether resin of Example 2 in an unsuitable range. The results are shown in Table 4.

Comparative Examples 4 to 5 Similar evaluations were conducted using carbon black 1 of Example 2 as an unsuitable addition amount. The results are shown in Table 4.

Comparative Example 6 The same evaluation was performed using the aromatic carboxylic acid anhydride 1 of Example 2 as maleic anhydride (reagent, "aliphatic carboxylic acid anhydride 1"). Table 5 shows the results.

Comparative Example 7 The same evaluation was performed using the aromatic carboxylic acid anhydride 1 of Example 2 as succinic anhydride (reagent, "aliphatic carboxylic acid anhydride 2"). Table 5 shows the results.

Comparative Example 8 The products containing no aromatic carboxylic acid anhydride 1 of Examples 1 to 3 were evaluated in the same manner. Table 5 shows the results.

The above evaluations are based on the following methods. (1) Odor evaluation Under the conditions shown in the odor evaluations A to C, the odor of the resin composition was 1
0 evaluators judged according to the following criteria, and the total score of all was used as the evaluation score. 1 point: Weak 2 points: Weak to medium 3 points: Medium 4 points: Medium to strong 5 points: Strong Since the evaluation score is the sum of the points judged by each individual, it is 10-5.
The range is 0 points, and the lower this value is, the higher the deodorizing effect is. Here, odor evaluation A: 50c from the die exit of the extruder during extrusion processing
The odor at the m position. Odor evaluation B: 50 g of pellets were put in a 300 ml capacity stoppered Erlenmeyer flask and heated in an oven at 150 ° C. for 3 hours to give an odor. Odor evaluation C: Odor after 10 pieces of molded products having a size of 63 × 12 × 3 mm were placed in an Erlenmeyer flask with a stopper of 300 ml and heated in an oven at 150 ° C. for 3 hours.

(2) Izod impact strength: Based on JIS K-7110. Thickness of test piece: 3.
2 mm. (3) Heat distortion temperature It was based on JIS K-7207. Bending stress: 18.6
kgf / cm ² . (4) Surface Resistance of Molded Product The surface resistance of the molded product (80 × 40 × 2 mm) of the present resin composition was measured with a surface high resistance meter (Mitsubishi Yuka Co., Ltd., trade name Hiresta) at 23 ° C. It was measured under the condition of relative humidity of 50%. Applied voltage: 500 V, distance between terminals: 20 mm.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

[0039]

EFFECTS OF THE INVENTION The polyphenylene ether resin composition of the present invention has an improved odor during melt processing such as granulation and injection molding, and during high temperature heating of molded articles, and does not deteriorate the working environment. Further, the composition of the present invention does not impair the original physical properties of the polyphenylene ether resin. Because of this, electricity
The application to the electronic field, especially IC trays, etc. becomes easier.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyasu Daichi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A polyphenylene ether resin (A) 95.
100 parts by weight of a resin mixture consisting of -50% by weight and styrene resin 5-50% by weight, (B) carbon black 3
40 parts by weight and (C) aromatic carboxylic acid anhydride (A)
+ B) A conductive resin composition having an odor-improved composition comprising 1 × 10 ⁻³ to 1 × 10 ⁻¹ acid anhydride group equivalent per 1 kg. 2. The resin composition according to claim 1, wherein the polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene) ether. 3. The resin composition according to claim 1, wherein the amount of carbon black added is 5 to 30 parts by weight. 4. The resin composition according to claim 1, wherein the addition concentration of the aromatic carboxylic acid anhydride is 5 × 10 ^{−3 to} 5 × 10 ⁻² acid anhydride group equivalent per 1 kg of (A + B).