JPH02265960A - Malodor-free polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether resin composition freed from malodor and made useful for a packaging material or the like by mixing a mixture of a polyphenylene ether resin with optionally a styrene resin with a specified inorganic additive. CONSTITUTION:A mixture (A) is obtained by mixing at least 10wt.% polyphenylene ether resin (a) [e.g. poly(2,6-dimethyl-1,4-phenylene) ether] with optionally a styrene resin (b) desirably a (polybutadiene-modified high-impact) PS. 100 pts. wt. component A is mixed with 0.1-10 pts. wt. at least one member (B) selected from between an alumina-silica inorganic additive (c) having a specific surface area (BET method) of 200-900m<2>/g, a mean particle diameter <=10mum and an Al2O3/SiO2 weight ratio of 0.1-0.8, and a magnesa-silica inorganic additive (d) of a specific surface area of 500-900m<2>/g, a mean particle diameter <=10mum and an MgO/SiO2 weight ratio of 0.3-0.7.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel odor-free polyphenylene ether resin composition. In more detail,
The present invention relates to a polyphenylene ether resin composition that does not pollute the environment due to unpleasant odors during granulation or molding, and is suitable for use in packaging materials and the like.

BACKGROUND OF THE INVENTION Polyphenylene ether resins have been widely used as engineering resins in many fields due to their excellent heat resistance, rigidity, and electrical properties.

However, this polyphenylene ether resin emits a strange odor during granulation or injection molding that involves melting operations, which has a significant negative impact on the working environment.It also gradually emits a strange odor even at room temperature, making it unpleasant when used in packaging materials, etc. The drawback is that it traps odors and contaminates the contents.

A method has been proposed in which a specific amine is used as a catalyst component to improve the off-odor in polyphenylene ether resins (Japanese Unexamined Patent Publication No. 131022/1982), but this method also does not completely remove the off-odor. It is not possible.

Problems to be Solved by the Invention Under these circumstances, the present invention provides a polyphenylene ether which has no malodor and is suitably used as a packaging material which does not generate unpleasant odors during granulation or molding processing. This was made for the purpose of providing a resin composition based on the above.

Means for Solving the Problems As a result of extensive research to develop a polyphenylene ether resin composition that does not have a bad odor, the present inventor has found that polyphenylene ether resin or a mixture of the same and a styrene resin contains a specific alumina. It was discovered that the objective could be achieved by blending a silica-based inorganic compounding agent or a magnesia-silica-based inorganic compounding agent in a predetermined ratio, and based on this knowledge, the present invention was completed.

That is, in the present invention, (B) (a)^(1
! O3/Sin, weight ratio 1 to 0.8, specific surface area measured by BET method 200 to 90011"/g, an alumina-silica based inorganic compound with an average particle diameter of 10μ or less, and (b) MgO/SiO, weight Ratio 0.3-0.7, BET
Specific surface area 500-900 m"/g, measured by method
The present invention provides a polyphenylene ether resin composition free from bad odor, which contains 0.1 to 10 parts by weight of at least one selected from magnesia-silica inorganic compounding agents having an average particle diameter of 1011 m or less.

The present invention will be explained in detail below.

In the composition of the present invention, a polyphenylene ether resin or a mixture of a poly7-L nylene ether resin and a styrene resin is used as component (A). The polyphenylene ether resin has the general formula (in which R- and R2 are hydrogen atoms, halogen atoms, or monovalent residues such as alkyl groups having 1 to 4 carbon atoms excluding L-butyl groups, aryl groups, etc.). A homopolymer consisting of repeating units represented by Number of carbon atoms excluded: 1-4
is a monovalent residue such as an alkyl group or an aryl group, and p
(i and R' cannot both be hydrogen atoms at the same time).

Typical examples of polyphenylene ether homopolymers include poly(2,6-dimethyl-1,4-phenylene)ether, poly(2-methyl-6-nityl-4-phenylene) ether, and poly(2,6-dimethyl-1,4-phenylene)ether. Danicyl-1,4-phenylene) ether, poly(2-ethyl-6-〇-propyl-1,4-phenylene) ether, HoIJ (2,
6-';-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-7dinilene) ether, poly(2-ethyl-6-inpropyl- 1,4-phenylene) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether, Bo'J
Examples include C2-)thyl-6-hydroxyethyl-1,4-phenylene) ether and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether.

Polyphenylene ether copolymers include alkyl substituted 2,3.6-L-limethylphenol represented by the general formula (R3, R', R' and R' in the formula have the same meanings as above). Examples include polyphenylene-chill type copolymers mainly composed of a polyphenylene ether structure obtained by copolymerizing phenol and, for example, O-cresol.

These polyphenylene ether resins may be used alone or in combination of two or more, but among these, poly(2,6-dimethyl-14-phenylene) ether is particularly preferred.

On the other hand, the styrene resin has the general formula (in the formula, R7 is a hydrogen atom, a halogen atom, or a lower alkyl group, Ra is a hydrogen atom,) \ \rogen atom, a vinyl group, or a lower alkyl group, and n is an integer of 1 to 5. (where n is 2 or more, R1 may be of a different number) A compound containing at least 25% by weight of monomer units formed from an aromatic vinyl compound is used.

Examples of such styrene type 1 sealants include styrene homopolymers such as polystyrene, polymethylstyrene, and polychlorostyrene, modified polystyrenes such as rubber modified polystyrene, styrene-acrylonitrile copolymers (AS), and styrene-acrylonitrile copolymers (AS). Butadiene copolymer (SB)
, styrene-7-crylonitrile-butadiene copolymer (
ABS), styrenic copolymers such as ethylvinylbenzene-divinylbenzene copolymer.

These styrene resins may be used alone or in combination of two or more types, and among these, polystyrene, polybutadiene-modified high-impact polystyrene, and mixtures thereof are particularly preferred.

In the composition of the present invention, the polyphenylene ether resin may be used alone as the component (A,), or
This polyphenylene ether resin and the styrene resin may be used as a mixture, but in this case, it is desirable that the polyphenylene ether resin is contained in the resin a in an amount of 10% by weight or more. If this amount is less than 10% by weight, the desirable properties of the polyphenylene ether resin will not be fully exhibited.

In the composition of the present invention, at least one selected from alumina-silica-based inorganic blending agents and magnesia-silica-based inorganic blending agents is used as the inorganic blending agent of component (B). As the alumina-silica inorganic compounding agent,
AQ201/5i02 weight ratio is in the range of 0.1 to 0.8, and the specific surface area measured by the BET method is 200
~90011', /1? with an average particle diameter of 10 μm
The following are used: Examples of such alumina-silica-based inorganic compounding agents include activated clay and synthetic zeolites, with X-type and Y-type synthetic zeolites being particularly preferred.

These alumina-silica-based inorganic compounding agents are easily available on the market.

On the other hand, as for the magnesia-silica-based inorganic compound, Mg
The O/SiO2 weight ratio is in the range of 3 to 0.7, and the specific surface area measured by the BET method is 500 to 900 m
”/g and an average particle diameter of 10 μm or less. Such magnesia-silica-based inorganic compounding agents are easily available in the market, for example, Mizuki Ui 7P-1c as a commercial product. Manufactured by Mizusawa Chemical Industry Co., Ltd., product name]
There is.

In the present invention, i may use one kind of the above-mentioned alumina-silica-based inorganic compounding agent, or may use two or more kinds in combination, or may use one kind of the above-mentioned magneno-silica-based inorganic compounding agent. However, two or more types may be used in combination. Furthermore, one or more types of alumina-silica type inorganic compounding agents and one or more types of magnesia-based inorganic compounding agents may be used in combination. This inorganic compounding agent of component CB) is
It is necessary to mix it in a ratio of 0.1 to 10 parts by weight, preferably 0-5 to 5 parts by weight, per 100 parts by weight of component (A). If the amount is less than 0.1 parts by weight, the deodorizing effect will be insufficient, and if it exceeds 10 parts by weight, impact resistance will tend to decrease.

The composition of the present invention may optionally include elastomers known as impact modifiers, such as polybutadiene elastomers, styrene compound-conjugated diene compound copolymers, and their In addition to hydrides, known resin additives such as colorants, flame retardants, fillers, plasticizers, stabilizers, ultraviolet absorbers, and blowing agents can also be added.

There are no particular limitations on the method for preparing the composition of the present invention, and any commonly used method may be used, such as the above-mentioned (A) component, (B)
A desired composition can be prepared by mixing the components and various additive components used as necessary, and melt-kneading the mixture using a roll mill, Banbury mixer-1 extruder, or the like.

Effects of the Invention In the production of polyphenylene ether, a combination of a metal salt and various amines is used as a catalyst.The removed amine is incorporated into the polyphenylene ether, and the amine component is removed by melt processing or heat at room temperature. This release is thought to be the cause of the off-odor of the polyphenylene ether resin.

In the present invention, the alumina-silica-based inorganic compound and the magnesia-silica-based inorganic compound used as component (B) have a large specific surface area and excellent adsorption performance.
It is believed that when these are melt-kneaded with a polyphenylene ether resin, the inorganic compounding agent effectively adsorbs the amine component, prevents the amine component from being released into the surroundings, and prevents the generation of off-flavors.

Therefore, since no unpleasant odor is generated, environmental pollution during granulation and molding processing is improved, and furthermore, when the resin composition of the present invention is used as a packaging material, there is no trapping of unpleasant odor and the contents are unpleasant. No odor contamination.

Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples.

In addition, the off-flavor was evaluated by the method shown below.

(1) Evaluation method for off-odor (A) During extrusion processing, at a position 50 cm from the die exit of the extruder,
Five testers rated the intensity of the off-odor according to the following criteria and made sensory judgments.

1 point: Strong sense of strange odor.

2 points: The strange odor is felt somewhat strongly.

3 points: I feel a strange odor.

4 points: A slight strange odor is felt.

5 points: No strange odor detected.

The evaluation scores of the five people were totaled, and the value indicates the degree of off-odor generation of the resin composition.

(2) Off-odor evaluation method (B) Pellet HOOg of the obtained resin composition was sealed in a 350-toge mayonnaise bottle and placed in a hot air dryer at 100°C for 1 hour.
After being left for 20 minutes, it was taken out and cooled at room temperature for 20 minutes. 5
A human measurer judged the odor by sense. The criteria are the same as above.

Further, Table 1 shows the properties of the inorganic compounding agents used in the Examples and Comparative Examples.

[1 Lord 11) Mizuriki Life P-1 causes secondary aggregation. Because it is easy to The diameter is t2.

Activated clay: Galleon Earth [manufactured by Mizusawa Chemical Co., Ltd., trade name I Co., Ltd., product name] Powdered alumino/licade: Nruton AMT [Mizusawa Chemical Co., Ltd., product name 1 Mizuriki Life P-I MgO/Sin, system [Mizusawa Chemical Co., Ltd., product name] j Example 1 [η sp
, /c) is 0.57 da, and 40 parts by weight of poly(2,6-dimethyl-1,4-phenylene) ether is added with a styrene resin [manufactured by Asahi Kasei Corporation, trade name Meta 40216].
0 parts by weight and 32 parts by weight of activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., trade name: Galleon Earth) were mixed in a mixer, and then mixed using a 30ai-twin screw extruder/manufactured by Nakayo Kikai Co., Ltd. (
LID-32, full 7 light screw, cylinder temperature 300°C, screw rotation speed 70 rpm) was used to perform melt cross-extrusion, and the strands were cut with a pelletizer.
A pellet-shaped resin composition of the present invention was obtained. The off-odor evaluation results are shown in Table 2.

Example 2 Except that X-type synthetic zeolite [manufactured by Mizusawa Chemical Industry Co., Ltd., trade name: Mizuriki Thieves] was added instead of activated clay,
A resin composition was obtained in the same manner as in Example 1. The off-odor evaluation results are shown in Table 2.

Example 3 A resin composition was obtained in the same manner as in Example 1, except that instead of activated clay, Y-type synthetic acid zeolite 1-C (manufactured by Mizusawa Chemical Industry Co., Ltd., trade name: Mizuka/-Bus) was added. Ta. The off-odor evaluation results are shown in Table 2.

Example 4 Instead of activated clay, Magunanrica-based inorganic compounding agent [
A resin composition was obtained in the same manner as in Example 1, except that Mizusawa Chemical Industry Co., Ltd. (trade name: Mizuriki Life P-1) was added.

The off-odor evaluation results are shown in Table 2.

Comparative Example 1 A resin composition was prepared in the same manner as in Example 1, except that activated clay was not added. Star. The off-odor evaluation results are shown in Table 2.

Comparative Example 2 A resin composition was prepared in the same manner as in Example I, except that powdered alumino/licade (manufactured by Mizusawa Chemical Industry Co., Ltd., trade name: JILTON AMT:l) was added instead of activated clay. The off-odor evaluation results are shown in Table 2.

Examples 5 to 9 40 parts by weight of the polyphenylene ether of Example 1, 601i parts of rubber-modified styrenic resin [manufactured by Asahi Kasei Corporation, trade name: STY 1 CON], 1.3.5 parts of activated clay of Example 1
．． A resin composition was obtained in the same manner as in Example 1 by blending 7.10 parts by weight. The resulting resin composition was evaluated for off-odor,
It is also injection molded to achieve Izotsu impact strength (ASTM D).
The thickness was measured at 2566.4 mm. The results are shown in Table 3.

Comparative Example 3 A resin composition was obtained in the same manner as in Example 5, except that activated clay was not added, and the off-odor evaluation and Izot impact strength were determined. The results are shown in Table 3.

Claims (1)

[Claims] 1 (A) Polyphenylene ether resin or mixture of polyphenylene ether resin and styrene resin 10
For 0 parts by weight, (B) (a) Al_2O_3/SiO
_2 weight ratio 0.1 to 0.8, specific surface area measured by BET method 200 to 900 m^2/g, average particle diameter 10 μm
The following alumina-silica-based inorganic compound and (b) MgO
/SiO_2 weight ratio of 0.3 to 0.7, specific surface area of 500 to 900 m^2/g measured by BET method, and at least one type selected from magnesia-silica-based inorganic compounding agents having an average particle size of 10 μm or less. .1 to 10 parts by weight of a polyphenylene ether resin composition free of bad odor. 2 The polyphenylene ether resin is poly(2,6-
A composition according to claim 1, which is dimethyl-1,4-phenylene) ether. 3. The composition according to claim 1 or 2, wherein the styrenic resin is polystyrene, polybutadiene-modified high-impact polystyrene, or a mixture thereof.