JPH07118519A - Antistatic polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To improve the antistatic properties of a resin mixture comprising a polyphenylene ether resin and/or a styrene resin and a resin modified with a specific compd. by compounding the mixture with an aminated polyalkylene oxide. CONSTITUTION:A resin mixture is prepd. by mixing a polyphenylene ether resin of formula I wherein R1 to R4 are each H, halogen, alkyl, etc.; and n is a degree of polymn and/or a styrene resin of formula II wherein R is R or 1-4C alkyl; and x is 0-5 and a polyphenylene ether resin modified with an acid, an acid anhydride, or an epoxy compd. (e.g. maleic acid or glycidyl acrylate) and/or a styrene resin modified as above. 100 pts.wt. resin mixture prepd. as above is compounded with 3-30 pts.wt. aminated polyalkylene oxide of formula III wherein R4 and R5 are each H or 1-4C alkyl; one of X1 and X2 is amino and the other is H, OH, etc.; 10<m+n<10,000; and p and q are each 0-5, thus giving the title compsn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antistatic polyphenylene ether (hereinafter sometimes referred to as PPE).
A resin composition.

[0002]

2. Description of the Related Art Polyphenylene ether resins have excellent heat resistance and mechanical strength, electrical properties, water resistance, flame retardancy, etc., and are used in various applications as molding resin materials. There is. However, the PPE-based resin has a great drawback that it has a poor meltability because of its high melt viscosity, and also has a poor solvent resistance and impact resistance.

In order to improve such problems, a composition obtained by blending a styrene resin with a PPE resin to improve moldability and impact resistance is known as, for example, NORYL (trademark: manufactured by General Electric Company). There is.

However, since such a composition is electrically insulative, it is charged with static electricity during use and adheres with dust to impair its appearance. Further, when it is used as a case or a part of electric / electronic equipment, it may cause malfunction or failure of the equipment due to static electricity failure.

In order to solve these problems, conventionally,
A method of kneading an antistatic agent into a resin composition has been used. As the antistatic agent, anionic, cationic, or nonionic surfactants are used. However, when these surfactants are blended, the appearance of the molded product may be impaired by the occurrence of silver streaks due to poor thermal stability of the surfactant. In addition, the antistatic effect is easily lost by washing or rubbing the molded product, and permanent antistatic property cannot be obtained.

[0006] Attempts have also been made to blend polyalkylene oxide into PPE (Japanese Patent Laid-Open No. 59-20354). However, polyalkylene oxide has poor compatibility with PPE, and therefore exhibits an antistatic effect. If the required amount is used, the strength of the molded product is reduced, the layered peeling is caused, the impact strength is reduced, and the like, which is not practical. Further, attempts have been made to blend a copolymer of polyalkylene oxide and polyamide into PPE to obtain a permanent antistatic effect (JP-A-4-246461 and JP-A-4-202256). ). However, since this copolymer is also not sufficiently compatible with PPE, if the amount required for obtaining the antistatic effect is added, it is inevitable that the impact strength and weld strength of the molded article are lowered.

Other known methods include blending conductive fillers such as conductive carbon black, metal flakes, and carbon fibers, but the molding processability is reduced, the coloring of the material is limited, and the appearance of the molded article is degraded. For that reason, its use is limited.

Therefore, an object of the present invention is to provide a polyphenylene ether resin composition having a permanent antistatic property and in which each component is well compatibilized.

[0009]

The present inventor has a permanent antistatic effect when an amino group-containing polyalkylene oxide is blended with a PPE resin or a styrene resin modified with a specific compound. The present invention has been achieved by finding that a composition was obtained, and that the composition had good compatibility with PPE, styrene and polyalkylene oxide.

That is, the present invention comprises (A) a polyphenylene ether type resin or a polyphenylene ether type resin and a styrene type resin,
At least one of the polyphenylene ether-based resin and the styrene-based resin is modified with at least one compound selected from an acid, an acid anhydride, and an epoxy compound, and (B) an amino group-containing content relative to 100 parts by weight of the resin. An antistatic polyphenylene ether-based resin composition containing 3 to 30 parts by weight of a polyalkylene oxide is provided.

The PPE resin used in the present invention has, for example, the general formula (Formula 1):

[0012]

[Chemical 1] (In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or at least two carbon atoms between the halogen atom and the phenyl ring. Represents a monovalent substituent selected from those having no tertiary α-carbon and having a haloalkyl group or a haloalkoxy group having n, and n is an integer representing the degree of polymerization)
Is a general term for the polymer represented by the formula (1), and may be a single type of the polymer represented by the above general formula or a copolymer in which two or more types are combined. In a preferred embodiment, R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms, and R ₃
And R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4)
-Phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1) , 4-phenylene) ether, and the like. As the PPE copolymer, a copolymer containing a part of alkyl tri-substituted phenol such as 2,3,6-trimethylphenol in the polyphenylene ether repeating unit can be mentioned. Also these PPE
It may be a copolymer in which a styrene compound is grafted. As the styrene compound-grafted polyphenylene ether, a styrene compound is added to the above PPE.
For example, it is a copolymer obtained by graft-polymerizing styrene, α-methylstyrene, vinyltoluene, chlorostyrene and the like.

Styrenic resins are known per se and have the general formula (Formula 2):

[0014]

[Chemical 2] (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z represents a substituent which is a halogen atom or an alkyl group having 1 to 4 carbon atoms, and x is an integer of 0 to 5. ) Must have at least 25% by weight or more of repeating structural units derived from the aromatic vinyl compound represented by the formula (1) in the polymer. Examples of such a styrene polymer include styrene and its derivatives (for example, p-methylstyrene, α-methylstyrene, α-methyl-p-
(Methylstyrene, chlorostyrene, bromostyrene, etc.)
And homopolymers of styrene, styrene copolymers obtained by mixing or modifying elastomeric substances such as polybutadiene, polyisoprene, butyl rubber, EPDM, ethylene-propylene copolymers, natural rubber, and styrene-containing copolymers. Examples thereof include styrene-acrylonitrile copolymer (SAN), styrene-butadiene copolymer, and styrene-acrylonitrile-butadiene copolymer (ABS). Preferred styrenic resins for the present invention are homopolystyrene and rubber-reinforced polystyrene (HIPS).

The above-mentioned PPE resin and styrene resin must be at least partially modified with at least one compound selected from acids, acid anhydrides and epoxy compounds. In the modification, only one of the PPE resin and the styrene resin may be modified, or at least a part of both the resins may be modified. In either case,
One or both resins may be included as unmodified resin.

The following compounds are preferred as the compound used for modifying PPE. That is, as the acid and the acid anhydride, for example, maleic anhydride, maleic acid, fumaric acid, methyl nadic acid anhydride, dichloromaleic anhydride, (meth) acrylic acid, citric acid, malic acid, agaricinic acid, itaconic acid, butene Acid, crotonic acid, vinyl acetic acid, pentenoic acid, 2-hexenoic acid, 2-octenoic acid,
2,4-hexadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, oleic acid, octacosenoic acid and the like can be mentioned. Examples of the epoxy compound include glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, and glycidyl ethers such as allyl glycidyl ether. The PPE resin can be modified by a known method. For example, the above compound and the PPE resin are melt-kneaded. Examples of the compound used for modifying the styrene resin include unsaturated acid compounds such as maleic anhydride, maleic acid, (meth) acrylic acid and butenoic acid and their anhydrides, or glycidyl methacrylate, glycidyl acrylate, vinylglycidyl. Unsaturated epoxy compounds such as ethers and glycidyl ethers of hydroxyalkyl (meth) acrylates are preferred. Such modification of the styrene resin can be performed by a known method. For example, a copolymer is produced by allowing the above compounds to coexist during styrene monomer polymerization.

The amount of modification in the case of modifying the PPE resin or styrene resin is not particularly limited, but in order to fully exert the compatibilizing effect, it is modified with a modifier compound in a proportion of at least 0.1% by weight. Preferably.

The proportion of PPE resin and PS resin in (A) is preferably 90 to 10 parts by weight of styrene resin to 10 to 90 parts by weight of PPE resin,
More preferably, 80 to 20 parts by weight of styrene resin is used with respect to 20 to 80 parts by weight of PPE resin.

Examples of the (B) amino group-containing polyalkylene oxide used in the present invention include those represented by the following formula (Formula 3) having an amino group at the terminal and having a main chain of polyalkylene oxide. To be

[0020]

[Chemical 3] (Here, R ^a and R ^b are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ₁ and X ₂ are the same when at least one of them is an amino group and not an amino group. Is any group such as a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and m and n are 10
<M + n <10000 is an integer, and p and q are each independently an integer of 0 to 5) The main chain alkylene oxide polymer is, for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, or pentylene. It may be a homopolymer of alkylene oxide such as oxide or hexylene oxide, or a copolymer of two or more of these. Among them, ethylene oxide is preferably 30% by weight or more, and particularly preferably 50% by weight or more, in the constitutional unit of the copolymer. When the ethylene oxide content is less than 30% by weight, it is difficult to obtain good antistatic property.

In the present invention, it is not always necessary that all of the polyalkylene oxide have an amino group, and if it is 30% by weight or less of the component (B), a polyalkylene oxide containing no amino group is included. You may stay.

The above-mentioned (B) amino group-containing polyalkylene oxide is mixed in an amount of 3 to 30 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of (A). If the amount of (B) is less than 3 parts by weight, a sufficient antistatic effect cannot be obtained,
On the other hand, if it exceeds 30 parts by weight, the mechanical strength and heat resistance of the molded product will deteriorate.

In the resin composition of the present invention, as long as the physical properties are not impaired, when the resin is mixed according to the purpose,
During molding, other polymers, various rubbers, conventional additives such as pigments, dyes, fillers (glass fiber, carbon fiber, carbon black, silica, titanium oxide, etc.), heat-resistant agents, oxidative deterioration inhibitors, weathering agents, Lubricants, mold release agents, crystal nucleating agents, plasticizers, flame retardants and the like can be added. Further, in order to stabilize the expression of the antistatic effect immediately after molding, another antistatic agent can be used together.

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be satisfactorily used. However, the melt-kneading method is generally preferable. The use of small amounts of solvent is possible, but generally not required. Examples of the apparatus include extruders, Banbury mixers, rollers, kneaders, etc., which are operated batchwise or continuously.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

The following compounds were used in the examples. (A): PPE-1: Intrinsic viscosity (chloroform, 25 ° C)
0.48 dl / g poly (2,6-dimethyl-1,4-phenylene)
Ether, manufactured by Japan GE Plastics (unmodified P
(Referred to as PE) PPE-2: A product obtained by mixing 1.5 parts by weight of maleic anhydride with 100 parts by weight of PPE-1 and modifying the mixture by melt-kneading (referred to as modified PPE). Impact polystyrene (HIPS): Trademark; Topolex 870-ST, manufactured by Mitsui Toatsu Chemicals, Inc. (referred to as unmodified PS) Styrene-maleic anhydride copolymer: Trademark; Dailark
232, manufactured by MTC Corp. (referred to as modified PS-1) Styrene-glycidyl methacrylate copolymer: trademark;
Mapproof 1005S, manufactured by NOF CORPORATION (modified PS
-2) (B): polyethylene oxide containing amino groups at both ends: number average molecular weight of 1000 (referred to as PEO-N) Others: antistatic agent: sodium alkylsulfonate,
Hostastat HS-1, Hoechst Examples 1-3 and Comparative Examples 1-2 Melt each component in the amounts (parts by weight) shown in Table 1 at 280 ° C. using a twin-screw extruder (screw diameter 35 mm). The mixture was kneaded and extruded to prepare pellets. Various test pieces were molded from the obtained pellets by injection molding and subjected to the following tests. (1) Surface resistance of 50 mm x 50 mm x 3 mm flat plate injection-molded product, which was conditioned at room temperature and 50% RH after molding, and washed with water (using an ultrasonic cleaner with distilled water After that, the water content was thoroughly removed, and the surface resistance was measured after humidity control for 1 hour (humidity of 50% RH at room temperature). (2) Half-life The half-life of the charge after applying a voltage of 6 KV for 1 minute was measured by a static Honest meter. The half-life after molding and after washing with water was measured in the same manner as (1) Surface resistance. (3) Appearance of molded product The appearance of the injection-molded product was visually judged.

The results of the above test are shown in Table 1.

[0028]

[Table 1]

[0029]

INDUSTRIAL APPLICABILITY The composition of the present invention exhibits a permanent antistatic effect without delamination, and can be used in various fields and is very useful.

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Claims (1)

[Claims] 1. (A) a polyphenylene ether resin or a polyphenylene ether resin and a styrene resin, wherein at least one of the polyphenylene ether resin and the styrene resin is at least one selected from an acid, an acid anhydride and an epoxy compound. An antistatic polyphenylene ether-based resin composition containing 3 to 30 parts by weight of (B) an amino group-containing polyalkylene oxide with respect to 100 parts by weight of a resin modified with a compound.