JPH03152155A - Polyphenylene ether resin composition having improved odor - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether resin composition having improved odor and suitable for food-packaging material and food container by compounding a specific carboxylic acid in combination with a specific silica- alumina inorganic compounding agent or a magnesia-silica inorganic compounding agent to a base resin. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a polyphenylene ether resin or a mixture of polyphinylene ether resin and a styrene resin with (B) 0.1-10 pts.wt. of one or more kinds of carboxylic acids selected from aliphatic polycarboxylic acid (e.g. citric acid) and aromatic polycarboxylic acid (e.g. trimellitic acid) and (C) 0.1-10 pts.wt. of one or more kinds of inorganic compounding agents selected from an alumina-silica inorganic compounding agent having an Al2O3/SiO2 ratio of 0.1-0.8, a specific surface area of >=150m<2>/g and an average particle diameter of <=10mum and a magnesia-silica inorganic compounding agent having a MgO/SiO2 ratio of 0.3-0.7, a specific surface area of >=300m<2>/g and an average particle diameter of <=10mum.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-resistant resin composition that improves the odor of polyphenylene ether resins and is suitable for food packaging and container materials.

[Conventional technology and problems to be solved by the invention]

Polyphenylene ether resin has excellent heat resistance, rigidity, electrical properties, etc., and is easy to process, making it one of the useful polymer materials. However, borifuenylene ether-based resins emit a unique odor during melt processing such as granulation and injection molding, which easily harms the working environment.They also emit a weak odor even at room temperature, so when used in packaging and container materials, they produce an odor. The product may be sealed and compressed, resulting in a strong odor when opened, or the odor may transfer to the contents.

Therefore, polyphenylene ether resins with improved odor are strongly desired in the field of food packaging and container materials sensitive to odors, such as heat-resistant container materials for microwave ovens.

[Means for Solving the Problems] As a result of intensive research in order to solve this odor problem, the present inventors added a specific carboxylic acid and a specific silica/alumina based inorganic compounding agent or specific It has been discovered that when the magnesia-silica-based inorganic compounding agents are added in combination, the odor improving effect is significantly greater than when each is added alone, and the present invention has been completed.

That is, the present invention provides: (a) a polyphenylene ether resin or a mixture of a polyphenylene ether resin and a styrene resin;
0 parts by weight, one or more polycarboxylic acids selected from aliphatic polycarboxylic acids and aromatic polycarboxylic acids 011
~10 parts by weight, and the composition weight ratio of (C) A 1 zO+/SiO2 is 0
．． 1 to 0.8, specific surface area measured by BET method is 1
50 m2/g or more, an alumina-silica-based inorganic compound with an average particle size of 10 μ or less, a composition weight ratio of MgO/SiO□ of 0.3 to 0.7, and a specific surface area of 300 m2/g or more as measured by the BET method. , an odor-improved polyphenylene ether resin composition comprising 0.1 to 10 parts by weight of one or more inorganic compounding agents selected from magnesia-silica inorganic compounding agents having an average particle size of 10 μ or less. It is.

The polyphenylene ether resin that can be used in the present invention has the general formula [1], (II) (wherein R1, Rt, R1, R4, R3, and R4 are the same as -
or a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, or hydrogen, excluding a different tert-butyl group, and R% is not hydrogen at the same time. ) as a repeating unit, and a homopolymer consisting of (I) as a constituent unit or a copolymer consisting of [-1] and (II) can be used.

An example of a homopolymer of polyphenylene ether resin is poly(2,6-cymethyl-1,4-phenylene).
Ether, poly(2-methyl-6-ethyl-1,4-
phenylene) ether, poly(2,6-ethyl-1.
4-phenylene)ether, poly(2-ethyl-6-
〇-propyl-1,4-phenylene) ether, poly
(2゜6-di-n-propyl-1,4-phenylene)ether, poly(2-methyl-6-n-butyl-1,4)
-phenylene) ether, poly (2-ethyl-6-itubroby-1,4-phenylene) ether, poly (
2-Methyl-6-chloro-1,4-phenylene)ether, poly(2-methyl-6-hydroxyethyl-1,
4-)Unilene)ether, poly(2-methyl-6-
Examples include homopolymers such as chloroethyl-1,4-phenylene) ether.

Specific examples of polyphenylene ether copolymers include copolymers of 2,6-dimethylphenol and 2,3,6-methylphenol, and copolymers of 2,6-dimethylphenol and 0-cresol. Examples include polymers.

These polymers can be produced, for example, by an oxidative polymerization method in which an oxygen-containing gas is passed through a reaction solvent containing a corresponding phenol compound and a metal-amine complex catalyst (Japanese Patent Publication No. 18692/1984, etc.).

The styrenic resin that can be used in the present invention has specific examples (in the formula,
R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, chlorine and lower alkyl, and p is an integer from O to 5. ) has at least 25% by weight of polymer units derived from the compound represented by:

As used herein, the term "styrenic resin" is defined by the formula above and includes, by way of example, homopolymers such as polystyrene and polychlorostyrene, modified polystyrene,
For example, rubber-modified polystyrene as well as styrene-containing copolymers, such as styrene-acrylonitrile copolymers (
AS), styrene-pucdiene copolymer (SB),
Includes styrene-acrylonitrile-butadiene copolymer (ABS), polyα-methylstyrene, copolymer of ethylvinylbenzene and divinylbenzene, and the like.

When using a mixture of polyphenylene ether resin and styrene resin, the mixing ratio can be freely selected, but generally the polyphenylene resin is about 10 to 99% by weight and the styrene resin is about 90 to 1% by weight. It is a percentage.

Aliphatic polycarboxylic acids that can be used in the present invention include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, methylmaleic acid, methylfumaric acid, itaconic acid, citraconic acid,
Di- or tricarboxylic acids such as mesaconic acid, acetylenic acid, malic acid, methylmalic acid, citric acid, isocitric acid, tartaric acid, etc., and preferred are tricarboxylic acids, especially citric acid.

Aromatic polycarboxylic acids that can be used in the present invention include, for example, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, 1.2.3-benzenetricarboxylic acid, 1.3.
Aromatic polycarboxylic acids such as 5-benzenetricarboxylic acid, pyromellitic acid, benzenehexacarboxylic acid, naphthalene dicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, diphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, azobenzenecarboxylic acid, etc.゛ is their anhydride. Among these, benzenetricarboxylic acids are preferred, and trimellitic acid is particularly preferred.

One or more selected from these aliphatic polycarboxylic acids and aromatic polycarboxylic acids can be used. The amount used is 0.1 to 10 parts by weight per 100 parts by weight of polyphenylene ether resin or a mixture of polyphenylene ether resin and styrene resin,
Preferably it is 0.2 to 5 parts by weight. When the amount used is less than 0.1 parts by weight, the odor improving effect is small, and when it is more than 10 parts by weight, some of the good physical properties originally possessed by the polyphenylene ether resin are likely to be impaired.

The alumina-silica-based inorganic compound that can be used in the present invention has a composition weight ratio of A I-to2/Sing of o, i-0
．． 8. Specific surface area measured by BET method is 15On'
T/g or more and the average particle diameter is 10 μ or less 0
If the composition weight ratio is smaller than 0.1 or larger than 0.8, or if the specific surface area is smaller than 150rrf/g, the odor improving effect will be small. Furthermore, if the average particle size is larger than 10 μm, the odor improving effect becomes small and the surface of the molded product becomes rough and rough, which tends to cause poor appearance. Specific examples of alumina/silica-based inorganic compounding agents include acid clay, activated clay, silica/alumina, zeolite, and the like. Among these, zeolite is preferred, and X-type zeolite, Y-type zeolite, and mordenite are particularly preferred.

The magnesia-silica-based inorganic compound that can be used in the present invention has a composition weight ratio of MgO/5iOt of 0.3 to 0.7,
Specific surface area measured by BET method is 300rrr/g
The above particles have an average particle diameter of Lop or less. One or more inorganic compounding agents selected from these may be added in an amount of 0.1 to 1 part by weight per 100 parts by weight of the polyphenylene ether resin or the mixture of polyphenylene resin and styrene resin.
It is used in an amount of 0 parts by weight, preferably 0.1 to 5 parts by weight. If the amount used is less than 0.1 parts by weight, the odor improving effect will be small, and if it is more than 10 parts by weight, some of the physical properties originally possessed by the polyphenylene ether resin will be likely to be impaired.

In the present invention, a known elastomer can be included as an impact modifier. Examples include butadiene elastomers, copolymers of styrene compounds and conjugated dienes, and hydrogenated products thereof.

In the present invention, conventionally known resin additives such as colorants, fillers, dyes and pigments, plasticizers, stabilizers, ultraviolet absorbers, blowing agents, etc. can be added and blended as needed. can.

The resin composition of the present invention can be manufactured using a known method. For example, a method of melt-kneading the composition/components using a roll mill, Banbury mixer-1 extractor, etc. can be mentioned.

[Effect of the invention] In the present invention, a specific carboxylic acid and one or more selected from a specific alumina-silica-based inorganic compound and a specific magnesia-silica-based inorganic compound are used in combination. Because of this, the combined effect improves the odor by a factor of 11.
The resin composition of the present invention does not impair the working environment when melt-processing it, and even when used for packaging/container materials, etc., it does not give off a strong odor when opened, and does not transfer odor to the contents.

In addition, since the amount added can be reduced due to the combined effect, the polyphenylene ether resin can be fully utilized without impairing its inherent good physical properties.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

In addition, the evaluation in the examples was based on the following method.

(2) Odor evaluation - In order to evaluate the odor during melt processing, five testers sensory-evaluated the odor intensity at a position 50ca+ from the exit of the extruder during extrusion processing.

The evaluation criteria are as follows.

1: Strongly confused by the smell, 2: Slightly confused by the smell, 3: Sensing the smell, 4: Slightly confused by the smell, 5: Not sensing the smell.

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

■ Odor evaluation-B In order to evaluate the odor as a packaging/container material, 100g of pellets of the resin composition were sealed in a 350m mayonnaise bottle, left in a hot air dryer at 100'C for 24 hours, then taken out and placed at room temperature. The mixture was cooled for 20 minutes. Five testers conducted a sensory evaluation of the odor. The criteria are the same as above.

■ Odor evaluation-C: Odors from packaging/container materials are measured using a commercially available odor intensity meter (
Odor sensor Model X manufactured by Shin Cosmos Electric Co., Ltd.
P-329).

That is, pellets 60++d of the resin composition were placed in a glass O-shaped tube with an inner diameter of 20mm and heated to 100°C.

Clean air was flowed through one side of the U-tube at a rate of 600 d/min. The air coming out from the other side was guided to an odor sensor and measured. The blank value obtained in the same manner without adding pellets was subtracted from the value after 10 minutes of clean air circulation to obtain the odor value.

■Izotsu impact strength Testing was carried out using an ASTM mouth 2566.4 m thick notch.

Further, the properties of the inorganic compounding agents used in the examples are summarized in Table 1.

Example 1 40 parts by weight of poly(2,6-dimethyl-1,4-phenylene)ether resin with ηSP/C=0.57 (measured in chloroform at 30°C), polystyrene resin (manufactured by Asahi Kasei Corporation, commercial product) After mixing 60 parts by weight of Nistyron GP685), 0.5 parts by weight of citric acid, and 0.5 parts by weight of Y-type zeolite (see Table 1 for properties), mix in a twin screw extruder (manufactured by Nakayo Kikai ■, 30-φ) using
Melt, mix, and extrude at 0'C to form pellets (1
, 5 amφ x 1.5 mm) was obtained.

Odor evaluation was conducted during extrusion using the method ``Evaluation-8'' and using the extruded pellets using the methods ``Evaluation-B'' and ``Evaluation-C.''

Furthermore, the extruded pellets were injection molded and their Izot impact strength was measured. These results are shown in Table 2.

Comparative Examples 1 to 3 Resin compositions were obtained and evaluated in the same manner as in Example 1, except that the amounts of citric acid 1 and Y-type zeolite were increased, or both were not added.

The evaluation results are shown in Table 2.

Examples 2 to 5 Resin compositions were obtained and evaluated in the same manner as in Example 1, except that the inorganic compounding agents shown in Table 3 were used in place of the Y-type zeolite in Example 1. The evaluation results are shown in Table 3.

Comparative Example 4 A resin composition was obtained and evaluated in the same manner as in Example 1, except that a synthetic aluminosilicate was used in place of the Y-type zeolite in Example 1. The evaluation results are shown in Table 3.

Examples 6 to 8 Resin compositions were obtained and evaluated in the same manner as in Example 1, except that the polycarboxylic acids shown in Table 4 were used in place of the citric acid in Example 1. The evaluation results are shown in Table 4.

Claims (1)

[Claims] 1(a) Polyphenylene ether resin or mixture of polyphenylene ether resin and styrene resin 100
Parts by weight, (b) One or more polycarboxylic acids selected from aliphatic polycarboxylic acids and aromatic polycarboxylic acids 0
．． 1 to 10 parts by weight, and (C) Al_2O_3/Si
Composition of an alumina-silica-based inorganic compound and MgO/SiO_2 with an O_2 composition weight ratio of 0.1 to 0.8, a specific surface area measured by BET method of 150 m^2/g or more, and an average particle size of 10 μ or less Weight ratio is 0.3 to 0.7, B
One or more inorganic compounding agents selected from magnesia-silica-based inorganic compounding agents having a specific surface area of 300 m^2/g or more and an average particle size of 10 μ or less as measured by the ET method, 0.1 to 10 A polyphenylene ether resin composition with improved odor consisting of parts by weight. 2. The odor-improved polyphenylene ether resin composition according to claim 1, wherein the aliphatic polycarboxylic acid is citric acid. 3. The odor-improved polyphenylene ether resin composition according to claim 1, wherein the aromatic polycarboxylic acid is trimellitic acid. 4. The odor-improved polyphenylene ether resin composition according to claim 1, wherein the alumina-silica inorganic compounding agent is zeolite.