JPH02265959A - Low odor polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether resin composition which has low odor and is 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 copolymer. CONSTITUTION:A mixture (A) is obtained by mixing at least 10wt.% polyphinylene ether resin (a) [e.g. poly(2,6-dimethyl-1,4-phenylene)] with optionally a styrene resin (b) (e.g. PS). Separately, a copolymer (B) is obtained by copolymerizing 51-49wt.% monomer (c) which forms an aromatic vinyl compound unit (e.g. styrene) with 49-41wt.% monomer (d) which forms an alpha,beta-unsaturated cyclic anhydride unit (e.g. maleic anhydride). 100 pts.wt. component A is mixed with 0.1-15 pts.wt. component B.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel polyphenylene ether resin composition with low odor. More specifically, the present invention relates to a low-odor polyphenylene ether resin composition that does not cause environmental pollution due to unpleasant odors during granulation or molding processing, and is suitable for use as a packaging material. It is.

BACKGROUND OF THE INVENTION Conventionally, polyphenylene ether resins have been widely used as engineering resins in many fields because of their excellent heat resistance, rigidity, electrical properties, and the like.

However, this poly7E:[-/ether-based resin emits an odor during granulation or injection molding that involves melting operations, which has a significant negative impact on the working environment, and it gradually releases an odor even at room temperature. When used as a packaging material, it has the disadvantage of trapping unpleasant text and contaminating the contents.

In order to reduce the off-odor in such borea-based ether resins, a method has been proposed in which a specific amine is used as a catalyst component during the production (Japanese Patent Laid-Open No. 62
131022), it is not possible to completely remove the off-flavor even with this method.

On the other hand, a thermoplastic resin composition containing a polyphenylene ether resin and a copolymer of an aromatic vinyl compound and an α,β-unsaturated cyclic anhydride is known (Japanese Patent Publication No. 1983-1999).
25743). However, the copolymer used in this composition has 60 to 99 aromatic vinyl compound units.
wt% and α,β-unsaturated cyclic anhydride units 40-1 wt%
Although it is effective in improving the heat distortion temperature, only a very small odor reduction effect can be obtained.

Problems to be Solved by the Invention Under these circumstances, the present invention provides a method that does not cause environmental pollution due to unpleasant odors during granulation and molding processing, and is suitable for use in packaging materials, etc. This was made for the purpose of providing a polyphenylene ether resin composition with low odor.

Means for Solving the Problems As a result of intensive research to develop a polyphenylene ether resin composition with low odor, the present inventor found that a polyphenylene ether resin or a mixture of the same and a styrene resin has a specific property. The proportion of aromatic vinyl compound units and a, β-
It was discovered that the objective could be achieved by blending a copolymer consisting of an unsaturated cyclic anhydride unit, and based on this knowledge, the present invention was completed.

That is, the present invention provides 100 parts by weight of (A) a polyphenylene ether resin or a mixture of a polyphenylene ether resin and a styrene resin, and (B) 51 to 59% by weight of aromatic vinyl compound units and a,β-union. 0.1-1 copolymer consisting of 49-41% by weight of saturated cyclic anhydride units
The object of the present invention is to provide a low-odor polyphenylene ether resin composition containing 5 parts by weight of the polyphenylene ether resin composition.

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 polyphenylene ether resin and a styrene resin is used as component (A). The polyphenylene ether resin has the general formula (R1 and R2 are hydrogen atoms, halogen atoms, or monovalent residues such as alkyl groups having 1 to 4 carbon atoms, excluding L-butyl groups, and aryl groups, respectively). A homopolymer consisting of a repeating unit represented by Carbon number 1-4
is a monovalent residue such as an alkyl group or an aryl group,
R6 and R6 cannot 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-ethyl-1,4-phenylene) ether, and poly(2,6-dimethyl-1,4-phenylene) ether. -Danicil-1,11-
phenylene)ether, poly(2-ethyl-6-n-
Propyl-1,,4-phenylene) ether, poly(2
, 6-celobrobyl-1,4-7enylene) ether, poly(2-methyl-6-lobyl-1,4-7enylene) ether, poly(2-ethyl-6-inglobyl-1,4-phenylene) ether , poly(2-methyl-6=chloro-1,4-)dinidine)ether, poly(
2-Methyl-6-hytroquinethyl-1,4-phenylene)ether, poly(2-methyl-6-chloroethyl-
1,1-7 enylene) ether and the like.

Examples of polyphenylene ether copolymers include alkyl-substituted phenols such as 2,3,6-)limethylphenol represented by the general formula (R3, R4, R6 and R1 in the formula have the same meanings as above); For example, a polyphenylene ether copolymer mainly having a polyphenylene ether structure obtained by copolymerizing with 0-cresol or the like can be mentioned.

These polyphenylene ether resins may be used alone or in combination of two or more, but among these, poly(2,6-dimethyl-1,4-phenylene) ether is particularly preferred. .

On the other hand, as a styrene resin, the general formula (in the formula, R7 is a hydrogen atom, a halogen atom, or a lower alkyl group, R1 is a hydrogen atom, a halogen atom, a vinyl group, or a lower alkyl group,
n is an integer of 1 to 5, and when n is 2 or more, R1 may be different from each other) Contains at least 25% by weight of monomer units formed from aromatic vinyl compounds represented by The one that does is used.

Examples of such styrenic resins include styrene homopolymers such as polystyrene, polymethylstyrene, and polychlorostyrene, modified polystyrenes such as rubber-modified polystyrene, styrene-acrylonitrile copolymers (AS), and styrene-butadiene copolymers. Polymer (SB)
, styrene-acrylonitrile-butadiene copolymer (
ABS), ethylvinylbenzene-divinylbenzene [
Examples include styrenic copolymers such as llF.

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 mixture 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, a copolymer consisting of aromatic vinyl compound units and α,β-unsaturated cyclic anhydride units is used as component (B). Examples of the monomer forming the aromatic vinyl compound unit include the aromatic vinyl compound represented by the general formula (IV).

On the other hand, the monomer forming the α,β-unsaturated cyclic anhydride unit has the general formula (where P is a hydrogen atom, an alkyl group or alkenyl group having 1 to 12 carbon atoms, m is O or 1 -10 integer) is used. Specific examples of such compounds include maleic anhydride, citraconic anhydride,
Examples include itaconic anhydride and aconitic anhydride, and among these, maleic anhydride is preferred.

In the copolymer of component (B), the content ratio of aromatic vinyl compound units to β-unsaturated cyclic anhydride units is selected within the range of 51:49 to 59:41 by weight. If this content ratio deviates from the above range, the effects of the present invention will not be fully exhibited. Further, the copolymer may be a rubber-modified copolymer modified with an impact-resistant rubber. Such an aromatic vinyl compound-α,β-unsaturated cyclic anhydride copolymer is easily available on the market. A typical example is SMA resin sold by Atochem. This SMA resin has a number average molecular weight of approximately 1000.
2000 to about 2000.

In the composition of the present invention, the aromatic vinyl compound-a,β-unsaturated cyclic anhydride copolymer of component (B) is contained in an amount of 0.1 to 15 parts by weight based on ioo parts by weight of component (A). ,
Preferably, it is necessary to blend it in a proportion of 0.5 to 7 parts by weight. If this amount is less than 091 parts by weight, the odor reduction effect will be insufficient, and if it exceeds 15 parts by weight, gel may be generated and the appearance may be impaired.

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 melting and mixing the mixture using a roll mill, a Banbury mixer-1 extruder, or the like.

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

Since the a,β-unsaturated cyclic anhydride has a free acid anhydride group, it has the property of adsorbing and retaining amine-based odor components. However, α,β-unsaturated cyclic anhydride monomers are highly volatile, and even when melt-kneaded into polyphenylene ether resins, the monomers volatilize from the resin, resulting in insufficient odor reduction. . On the other hand, the aromatic vinyl compound-α,β-unsaturated cyclic anhydride copolymer of component (B) has free acid anhydride groups and is nonvolatile, so it can be used as a polyphenylene ether-based copolymer. It must be melted and kneaded into the resin.
It is thought that the amine component is adsorbed and retained within the resin, and no release of the amine component occurs, resulting in a desired low-bromination composition.

Therefore, since no unpleasant odor is generated, environmental pollution during granulation and molding processing is improved, and when the resin composition of the present invention is used as a packaging material, the unpleasant odor is not trapped and the contents are unpleasant. Not contaminated by odor.

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.

Incidentally, off-odor and physical properties were evaluated using the following methods.

(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) Evaluation method for off-odor (B) 350 m (l)
It was sealed in a mayonnaise bottle and left in a hot air dryer at 100°C for 120 minutes, then taken out and cooled at room temperature for 20 minutes. Five testers visually judged the strange odor. The criteria are the same as above.

Further, Table 1 shows the contents of styrene units and maleic anhydride units in the f-3M A resin used in Examples and Comparative Examples.

Table [Note] 5MA100OA~3000A: Dilarc 232 manufactured by Atochem Co., Ltd.: Arco Chemical Co., Ltd. Sediment (manufactured by Asahi Kasei Industries, Ltd., trade name Meta 40F 160 parts by weight and SMA)
Resin (manufactured by Atochem, trade name, 5MA1000A) 1
After blending parts by weight and mixing with a mixer, 30m/m
- Melt-kneading extrusion was performed using a twin-screw extruder/manufactured by Nakayo Kikai Co., Ltd. (LID = 32, full-flight screw, cylinder temperature 300°C, screw rotation speed 70 rpm), and the strands were cut with a pelletizer to form berent-shaped A resin composition of the present invention was obtained. The off-odor evaluation results are shown in Table 2.

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

Example 1 (vsp
/c) of 0.57 dQ/g to 40 parts by weight of poly(2,6-dimethyl-1.4-)J,nylene) ether with the same content of maleic anhydride units in the styrenic tree composition. A resin composition was obtained in the same manner as in Example 1, except that the resin composition was added so as to be as follows. The off-odor evaluation results are shown in Table 3.

Table (i) PPE: Polyphenylene ether PS: Polystyrene SMA: Styrene-maleic anhydride copolymer Example 2 A resin composition was prepared in the same manner as in Example 1, except that the amount of SMAv14 resin 1000A was increased to 2 parts by weight. Obtained. The off-odor evaluation results are shown in Table 3.

Comparative Examples 2 to 4 Instead of 5MA31 fat 1000^, SMA* fat having a lower maleic anhydride unit content than 1000^ was used in Example 2.
(Note) PPE: Polyphenylene ether PS: Based on the results for polystyrene, SM has a high content of 71-ynoic anhydride units.
It can be seen that resin A is particularly effective in reducing odor.

Example 3~G A resin composition was obtained in the same manner as in Example 1, except that the amount of SMA resin 1000A was increased to 5 parts by weight, 7 parts by weight, 10 parts by weight, and 15 parts by weight. Table 4 shows the odor evaluation results.

Table 4 〔note〕 Gel generation varnish] - Land surface becomes rough

Claims (1)

[Claims] 1 (A) Polyphenylene ether resin or mixture of polyphenylene ether resin and styrene resin 10
(B) aromatic vinyl compound unit 51 to 0 parts by weight
59% by weight and 49-41 a,β-unsaturated cyclic anhydride units
A low-odor polyphenylene ether resin composition comprising 0.1 to 15 parts by weight of a copolymer consisting of % by weight. 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.