JPH02265961A - Low odor polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether resin composition which is low odor and is useful as a packaging material or the like by mixing a mixture of a polyphenylene ether resin with optionally a styrene resin with a specified copoly mer and 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 desirably a (polybutadiene-modified high-impact) PS (b). 100 pts.wt. component A is mixed with 0.1-15 pts.wt. copolymer (B) comprising 51-80wt.% aromatic vinyl compound units and 49-20wt.% alpha,beta-unsaturated cyclic anhydride units and 0.1-10 pts.wt. at least either (C) of 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 magnesia-silica inorganic additive (d) of a specific surface area (BET method) 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 low-odor polyphenylene ether resin composition. 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 in packaging materials, etc. be.

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, and electrical properties.

However, this polyphenylene ether resin
A strange odor is emitted during granulation and injection molding that involve melting operations.
In addition to having a significant negative impact on the working environment, it also gradually emits an unpleasant odor even at room temperature, and when used in packaging materials, it traps unpleasant odors and contaminates the packaged items.

In order to improve the off-odor in such polyphenylene ether resin, one of the catalyst components is added when producing the resin.
A method has been proposed in which a special amine is used as an amine.
No. 2), even with this method it is not possible to completely remove the off-odor.

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 invention was made for the purpose of providing a low-odor poly-72-dylether resin composition.

Means to Solve the Problems As a result of intensive research to develop a low-odor polyphenylene ether resin composition, the inventor has discovered that polyphenylene ether resin or a mixture of this and styrene resin has a specific proportion. A copolymer consisting of an aromatic vinyl compound unit and an α,β-unsaturated cyclic anhydride unit, and a specific alumina-silica-based inorganic compounding agent or magnesia-silica-based inorganic compounding agent are blended in predetermined proportions. By doing so, they discovered that the object could be achieved, and based on this knowledge, they completed the present invention.

That is, the present invention includes (B) aromatic vinyl compound units in an amount of 51 to 80% by weight based on 100 parts by weight of a mixture of (A) polyphenylene ether resin or polyphenylene ether 14t IIW and styrene resin.

0.1 to 15 parts by weight of a copolymer consisting of 49 to 20% by weight of β-unsaturated cyclic anhydride units, and (C) (a) Al2
O3/Sin, weight ratio 0.1~(], 8, B IE
An alumina ricin inorganic compound with a specific surface area of 200 to 90 axes'/g and an average particle diameter of 1 (] μm or less, as measured by the T method, and (b) a MgO/SiO□ weight ratio of 0.1 (~0.7).
, specific surface area measured by BET method: 500-901)
+x2/9, red sea bream with an average particle diameter of 10 μm or less, nr-
At least one selected from silica-based inorganic compounding agents0
．． The object of the present invention is to provide a low-odor polyphenylene ether resin composition containing 1 to 10 parts by weight.

The present invention will be explained in detail below.

In the composition of the present invention, polyphenylene L/1-thyl-based [IIW] or a mixture of polyphenylene ether-based resin and styrene-based resin is used as component (A). The Borif J-nylene ether resin has the general formula (R1 and R2 in the formula are a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms or an aryl group, respectively, with an intervening butyl group). A homopolymer consisting of a repeating unit represented by monovalent residues such as , 1 carbon number excluding 10 gene atoms or t-butyl group
-4 monovalent residues such as alkyl groups and aryl groups, and R5 and R6 cannot be hydrogen atoms at the same time).

A typical example of a polyphenylene ether homopolymer is poly(2,6-dimethyl-14-7.-elm/)1-
ethyl, poly(2-methyl-6-nityl-1.4-7 dinilene) ether, poly(2,6-ethyl-1.4-7
enylene) ether, poly(2-even-6-n-butylene-1,4-phenylene) ether, poly(2,
f5-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,,4-phenylene) ether, poly(2-ethyl-[j-inzolopyl-1, Poly(2-methyl-6-chloro-1,4-phenylene) ether, Poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, Poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, -methyl-6-chloroethyl-1,4-phenylene) ether and the like.

Examples of polyphenylene ether copolymers include alkyl-substituted phenols such as 2,3,6-trimethylphenol represented by the general formula (R', R', R' and R'' in the formula have the same meanings as above); Examples include polyphenylene ether-based copolymers mainly composed of a polyphenylene ether structure obtained by copolymerizing 0-cresol and the like.

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. Al.

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, 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 an aromatic vinyl compound 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-acrylonide-lylubutadiene 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 mixture in an amount of 1 (Ntftg) 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 aromatic vinyl compounds represented by the general formula (IV).

On the other hand, the monomer forming the σ,β-unsaturated cyclic anhydride unit has the general formula (where R is a hydrogen atom, an alkyl group or alkenyl group having 1 to 12 carbon atoms, and m is 0 or l is an integer of −1,0). Specific examples of such compounds include maleic anhydride, citraconic anhydride,
Examples include itaconic anhydride and aconilla anhydride, and among these, maleic anhydride is preferred.

In the copolymer of component (B), the content ratio of aromatic vinyl compound units and α,β-unsaturated cyclic anhydride units is selected within the range of 51:49 to 80:20 by weight; If it deviates from the range, the object of the present invention cannot be fully achieved. 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 about 1000 to about 200.
It is a low molecular weight styrene-maleic anhydride copolymer in the range of 0.

In the composition of the present invention, the aromatic vinyl compound-α,β-unsaturated cyclic anhydride copolymer as the component (B) is contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the component (A). ,
Preferably, it is necessary to mix it in a proportion of 0.5 to 7 parts by weight. If this blending amount deviates from the above range, the effects of the present invention will not be fully exhibited.

In the composition of the present invention, at least one selected from alumina-silica-based inorganic additives and magne-arsilica-based inorganic additives is used as the inorganic additive for component (C). As the alumina-silica inorganic compounding agent,
Al1,0. /SiO□ weight ratio is in the range of 0.1 to 0.8, and the specific surface area measured by the BET method is 20
0 to 900 m"/g and an average particle diameter of 10 μm or less. Examples of such alumina-silica-based inorganic compounding agents include activated clay and synthetic zeolite, but in particular Synthetic zeolites of type and type Y are preferred.These alumina-silica based inorganic formulations are readily available on the market.

On the other hand, as a magnesia-silica-based inorganic compounding agent, MgO
/5iOh weight ratio is in the range of 0.3 to 0.7, and the specific surface area measured by the BET method is 500 to 900I.
12/9 and an average particle diameter of IOpm or less is used. Such a magnuar silica-based inorganic compounding agent is easily available on the market, and for example, a commercially available product is Mizuriki Life P-1 (manufactured by Mizusawa Chemical Industry Co., Ltd., trade name).

In the present invention, one type of the alumina-silica-based inorganic compounding agent may be used, or two or more types of the above-mentioned inorganic compounding agent may be used in combination.
One species may be used, or two or more species may be used in combination. Furthermore, one or more types of alumina-silica-based inorganic compounding agent and 1
It may be used in combination with one or more magnesia-silica based inorganic compounding agents. The inorganic compounding agent of component (C) needs to be blended at a ratio of 0.1 to IO parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of component (A). . If this blending amount deviates from the above range, the effects of the present invention will not be fully exhibited.

A feature of the present invention is that the aromatic vinyl compound-α,β-unsaturated cyclic anhydride copolymer with a high content of σ,β-unsaturated cyclic anhydride units of the component (B) is used as the odor-lowering component. and the alumina-silica-based inorganic compounding agent and the magnesia-silica-based inorganic compounding agent of the component (C) are used in combination. That is, when using only the above-mentioned compounding agent as a low-odor component, in order to obtain a sufficiently satisfactory low-odor effect, it is necessary to increase the amount of the compound, and as a result, the resulting resin composition A problem arises in that impact resistance is reduced. On the other hand, in the present invention, the inorganic compounding agent includes
By using a combination of an aromatic vinyl compound with a high content of α, β-unsaturated cyclic anhydride units and an α, β-unsaturated cyclic anhydride copolymer, the synergistic effect provides excellent odor reduction effect. It is possible to exhibit this and suppress a decrease in impact resistance.

If desired, the composition of the present invention may contain elastomers known as impact modifiers, such as polybutadiene-based elastomers, sudien-based compound-conjugated diene-based compound conjugates, to the extent that the object of the present invention is not impaired. Polymers and their hydrides can be blended, and known resin additives such as colorants, flame retardants, fillers, plasticizers, stabilizers, ultraviolet absorbers, blowing agents, etc. can also be blended. I can do it.

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 is prepared by mixing the components, component (C), and various additive components used as necessary, and melt-kneading this mixture using a roll mill, Banbury mixer-1 extruder, etc. can do.

Effects of the invention In the production of polyphenylene ether, a method using a combination of metal salts and various amines as a catalyst (Japanese Patent Publication No.
18692, Japanese Patent Publication No. 39-29373, Japanese Patent Publication No. 42-3195, Japanese Patent Publication No. 45-23555, etc.), but the amine used at that time is incorporated into the polyphenylene niemil, It is presumed that the release of the amine component by melt processing or heat at room temperature is the cause of the off-odor of the polyphenylene ether resin.

Alumina with a relatively large surface area used in the present invention
Since the silica-based inorganic compounding agent and the magnesia-silica-based inorganic compounding agent have a large adsorption ability on their surfaces, it is thought that they effectively adsorb and retain the amine component that is presumed to be the cause of the off-odor. Furthermore, since the copolymer of component (B) used in the present invention has a free acid anhydride group in its molecule, it also has the property of adsorbing and retaining an amine component.

When the inorganic compounding agent is added to the polyphenylene ether resin, the odor is reduced, but as the amount of the additive increases, the impact resistance decreases. However, when used in combination with the copolymer according to the present invention, the synergistic effect results in a higher odor reduction effect than the sum of the respective odor reduction effects, and furthermore, a decrease in impact resistance is suppressed.

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 sealing of unpleasant odor, and the Things are not contaminated with unpleasant odors.

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.

1. Off-odor and physical properties were evaluated using the following methods.

(+) Off-odor evaluation method (A) At a position 50 cm from the die exit of the extruder during extrusion processing,
Five testers rated the intensity of the off-odor according to the following criteria and made sensory judgments.

1 point: I strongly sense a strange odor.

2 points: I felt a slightly strong odor.

3 points: I feel a strange odor.

71 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) The pellets IOh of the obtained resin composition were sealed in a 350 m12 mayonnaise bottle, left in a hot air dryer at 100°C for 24 hours, taken out, and cooled at room temperature for 20 minutes. -,
. Five testers visually judged the strange odor. The criteria are the same as above.

(3) Izotsu impact strength ASTM D256 (6,411+i thickness, with non-stop)
The resin composition was injection molded in accordance with the above, and the impact strength at 23°C was determined.

Further, the properties of the SMA resin and inorganic compounding agents used in the Examples and Comparative Examples are shown in Tables 1 and 2, respectively.

Table 1 [Main 1] SMA 10f) OA ~3000^: Dilarc 232, manufactured by Atochem Co., Ltd.: Table 1, Migariki Rye 7P-1, manufactured by Arco Chemical Co., Ltd., easily undergoes secondary aggregation, and has a secondary agglomeration diameter.

Activated clay: Galleon Earth [manufactured by Mizusawa Chemical Industry Co., Ltd., trade name JX type zeolite, Mizuriki Thieves [manufactured by Mizusawa Chemical Industry Co., Ltd., trade name J Mizukarai'; yp-1 [bO-5]
iQt series, Mizusawa Chemical Industry Co., Ltd. Il, trade name 1 Example 1 (η sp
/c) is 0.57aI2 and 40 parts by weight of poly(2,6-dimethyl-1,4-phenylene)ether is added with a rubber-modified styrenic resin [manufactured by Asahi Kasei Corporation, trade name Meta 4].
360 parts by weight of 0F and hydride of styrene-conjugated butadiene elastomer [manufactured by Asahi Kasei Corporation, trade name 277]
7733 parts by weight of SMA resin (manufactured by Atochem Co., Ltd., trade name: SMA 3000^) and 13 parts by weight of activated clay (manufactured by Mizusawa Chemical Co., Ltd., trade name: Galleon Earth) were mixed in a mixer, and 30IIlII was mixed with the shaft. Extruder/manufactured by Nakatani Kikai Co., Ltd. (LID=32, full flight screw,
Cylinder temperature 300°C 1 screw rotation speed 70 r
pm), and the strands were cut with a pelletizer to obtain a pellet-shaped resin composition of the present invention. The obtained resin composition was evaluated for off-odor, and also subjected to shota molding and measured for Izot impact strength. The result is the third
Shown in the table.

Example 2 A resin composition was obtained and evaluated in the same manner as in Example 1, except that X-type synthetic zeolite (manufactured by Mizusawa Chemical Industry Co., Ltd., trade name, Mizuriki Thieves) was added instead of activated clay. t;.

The evaluation results are shown in Table 3.

Comparative Examples 1 to 3 Resin compositions were obtained and evaluated in the same manner as in Example t, except that the SMA resin and activated clay were each added alone or both were not added. The evaluation results are shown in Table 3.

Table [Sho] PPIE: Polyphenylene ether PS: Rubber modified polystyrene! (In T'I, styrene-conjugated butadiene elastomer is lignified.As can be seen from Table 3, the SMA resin/inorganic compound combination system has a lower odor reduction effect than the one using each alone. is large, and the drop in impact resistance due to the addition of inorganic additives is also small.

Example 3 Instead of activated clay, magnesia-silica-based inorganic compound [
A resin composition was obtained and evaluated in the same manner as in Example 1, except that Mizusawa Chemical Industry Co., Ltd., trade name: Mizuriki Life P-1 was added. The evaluation results are shown in Table 4.

Examples 4-5 Instead of SMA 100OA, SMA 2000^ with a slightly lower maleic anhydride content than SMA 1.00OA,
A resin composition was obtained and evaluated in the same manner as in Example 3, except that SMA3000A (manufactured by Atochem) was added. The results are shown in Table 4.

Comparative Example 4 A resin composition was obtained and evaluated in the same manner as in Example 3, except that, in place of SMA 100OA, Dylark 232 (Arco Chemical Co., Ltd.), which contained even lower maleic anhydride content, was added. The results are shown in Table 4.

Comparative Example 5 A resin composition was obtained and evaluated in the same manner as in Example 3, except that SMA 100OA was not added.

The results are shown in Table 4.

/ / \′ \ 7/

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
80% by weight and 49-20 α,β-unsaturated cyclic anhydride units
0.1 to 15 parts by weight of a copolymer consisting of % by weight, and (
C) (a) Al_2O_3/SiO_2 weight ratio 0.1~
0.8, specific surface area measured by BET method 200-90
0 m^2/g, an alumina-silica-based inorganic compound with an average particle diameter of 10 μm or less, and (b) MgO/SiO_2 weight ratio 0.3 to 0.7, specific surface area 50 measured by BET method.
A low-odor polyphenylene ether resin composition containing 0.1 to 10 parts by weight of at least one selected from magnesia-silica inorganic compounding agents having a particle diameter of 0 to 900 m^2/g and an average particle diameter of 10 μm or less. thing. 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.