JPH04202256A - Antistatic polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which is permanently antistatic and excellent in strengths, moldability, etc., by compounding a polyphenylene ether resin with specified amts. of a polyamide resin and a specific polyamideimide elastomer. CONSTITUTION:100 pts.wt. resin mixture comprising 25-70wt.% polyphenylene ether resin, 25-70wt.% polyamide resin, and 0-25wt.% rubberlike material is compounded with 2-40 pts.wt. polyamideimide elastomer having a relative viscosity at 30 deg.C of 1. 5 or higher and prepd. by mixing caprolactam, an arom. tri- or tetracarboxylic acid capable of forming at least one imide ring, and polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly comprising polyoxyethylene glycol, thus giving the title compsn., which is suitable as the material of a housing, mechanical part, etc., of a mechanical section for handling coins in an automatic vending machine.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polyphenylene ether resin composition with good antistatic properties.

More specifically, the present invention uses polyphenylene ether resin, polyamide resin, and polyamideimide elastomer as basic resin components, has permanent antistatic properties,
The present invention also relates to a polyphenylene ether resin composition that has good mechanical properties and moldability and is suitable as a material for housings and mechanical parts of coin mechanism parts of vending machines.

[Conventional technology]

In recent years, polyphenylene ether resins have been widely used in various fields as engineering plastics with excellent physical properties such as heat resistance and mechanical properties.

However, this polyphenylene ether resin
When used as a material for housings or mechanical parts such as the coin mechanism of a vending machine, there are disadvantages such as generation of static electricity and malfunction of the mechanism due to charging, so in addition to the desirable properties of this material, There was a demand for the development of a molding material with antistatic properties.

By the way, various methods have been tried so far to impart antistatic properties to thermoplastic resins.

For example, an antistatic polymer can be obtained by graft polymerizing a vinyl or vinylidene monomer such as sodium styrene sulfonate to a rubber copolymer of an alkylene oxide and a conjugated diene compound (U.S. Pat.
, 384, 078), by substituting a polyphenylene ether resin with a group such as a sulfonate group,
Antistatic properties are imparted by the formation of certain ionic derivatives (U.S. Pat. No. 3,529,52).
0), certain bis-ethoxylated quaternary ammonium salts of p-toluenesulfonic acid can be used for polystyrene,
It has been disclosed that it is useful as an antistatic agent for polyester, polyamide, polycarbonate, polyolefin, ABS resin, etc. (US Pat. No. 3,933,779). However, all of these techniques have the disadvantage that they are insufficient as techniques for obtaining a sufficient antistatic effect over a long period of time.

Furthermore, an antistatic composition comprising a polyether ester amide and a carboxyl group-containing vinyl copolymer has been proposed (Japanese Unexamined Patent Publication No. 60-23435), but this composition has no practical antistatic properties. In order to obtain preventive properties,
It is necessary to increase the blending amount of polyether ester amide, which has the disadvantage that the flexural modulus inevitably decreases.

Furthermore, a composition is disclosed in which a combination of a polyoxyalkylene group-containing alkylamine, sodium alkylsulfonate, and an inorganic alkali metal salt is added as an antistatic agent to a thermoplastic resin (Japanese Patent Application Laid-Open No. 1983-1992-1). 2
61359), this composition also has insufficient long-term antistatic properties.

In addition, modified polyphenylene ethers having carboxyl groups and/or carboxylic acid anhydride structures as part of the substituents, polyamides, and aromatic vinyl A-
Although a resin composition with a B-A type block copolymer has been disclosed (Japanese Unexamined Patent Publication No. 10656/1983), its long-term antistatic properties are insufficient.

In addition, for thermoplastic resins, acrylic ester elastomers (Japanese Patent Application Laid-Open No. 63-48355) and styrene-acrylic acid copolymers (Japanese Patent Application Laid-Open No. 64-156)
It has also been attempted to impart antistatic properties by adding . However, none of these has a sufficient effect of imparting antistatic properties, and when an acrylic ester elastomer is blended, there are drawbacks such as a reduction in rigidity. Further, an antistatic composition has been disclosed in which a polyamide elastomer is added to a polyphenylene ether resin, a polyamide resin, and a rubbery polymer (Japanese Patent Application Laid-Open No. 2-167363), but the polyamide elastomer alone has sufficient antistatic properties. A large amount is required to obtain the effect.

Conventionally, in order to impart antistatic properties to polyphenylene ether resins, antistatic agents and conductive fillers such as carbon black and metal powder are generally added. However, the method of blending an antistatic agent is effective as a method of imparting antistatic properties without damaging the appearance or processability of the resin, but as mentioned above, antistatic properties, especially sustained static The method has the disadvantage that the effect of imparting antistatic properties is not necessarily sufficient, and although the method of blending an electrostatic filler can impart excellent antistatic properties, for example, when carbon black is blended, it becomes darkly colored. It cannot be used when a material with a bright color is required, and when metal powder is added, moldability decreases, the appearance of the molded product is damaged, and impact resistance etc. There are drawbacks such as decreased physical properties.

[Problem to be solved by the invention]

Under these circumstances, the present invention has a permanent antistatic property and is excellent in mechanical properties, moldability, appearance, etc., and is suitable for use as a material for mechanical parts such as the housing of the coin mechanism part of a vending machine, for example. The purpose of this study was to provide a polyphenylene ether resin composition suitable for use in the following applications.

[Means to solve the problem]

The present inventors have conducted various studies to impart antistatic properties to a resin mixture of polyphenylene ether resin, polyamide resin, and rubber-like substance. A polyamideimide elastomer whose hard segment is an aromatic polycarboxylic acid capable of forming at least one imide ring, such as mellitic acid or pyromellitic acid, and a polyamideimidedicarboxylic acid obtained from a polyphenylene ether resin, a polyamide resin, and It is compatible with and heat resistant in resin mixtures with rubber-like substances, and when incorporated in relatively small amounts into resin mixtures, it provides sustained antistatic properties without sacrificing its desirable properties. The present invention was completed based on this finding.

That is, the present invention comprises (A) (b) 25 to 70% by weight of polyphenylene ether resin and (b) 25% by weight of polyamide resin.
(B) (a) caprolactam,
(b) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring; (c) a polyoxyethylene glycol or a polyoxyalkylene glycol mixture based on polyoxyethylene glycol and optionally The content of component (c) obtained from at least one type of diamine having 2 to 10 carbon atoms (d) is 30
~85% by weight and a relative viscosity of 1 at a temperature of 30°C
．． The present invention provides a polyphenylene ether resin composition containing 2 to 40 parts by weight of a polyamideimide elastomer of 5 or more.

The present invention will be explained in detail below.

The polyphenylene ether resin used as component (A) in component (A) of the composition of the present invention is selected from polyphenylene ether resins used in known resin compositions consisting of polyphenylene ether resin, polyamide resin, and rubbery material. Can be selected arbitrarily. Such a substance is, for example, represented by the formula (in which R1 and R2 are each a hydrogen atom, a halogen atom, or a monovalent residue such as an alkyl group or an aryl group having 1 to 4 carbon atoms). A homopolymer consisting of repeating units, or a homopolymer consisting of repeating units and the general formula (wherein R3, R4, R5 and R6 are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, such as an aryl group) A copolymer consisting of a repeating unit represented by a monovalent residue (R5 and R6 cannot be hydrogen atoms at the same time) can be mentioned.

Typical examples of polyphenylene ether homopolymers include:
Poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-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-isopropyl-1,
4-phenylene) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly(2-methyl-6) -chloroethyl-1,4-
(phenylene) ether, etc.

Examples of the polyphenylene ether copolymer include an alkyl-substituted phenol such as 2,3,6-trimethylphenol represented by the formula (in which R3, R', R5 and Rh have the same meanings as above); Examples include polyphenylene ether copolymers mainly having a polyphenylene ether structure obtained by copolymerizing monoalkylphenols such as cresol.

The polyamide resin used in the present invention usually has a
(cH2), NH2 (wherein X is an integer between 4 and 12) and a linear diamine of the formula HO□C
Those produced by condensation with a linear carboxylic acid represented by -(cH2), -CO□H (in the formula, y is an integer between 2 and 12), and those produced by ring-opening polymerization of lactam. You can use the ones that have been created. Preferred examples of these polyamide resins include nylon 6.6, nylon 6.9, nylon 6.10, nylon 6.12,
Nylon 6, Nylon 12, Nylon 11, Nylon 4
, 6 etc.

Also, nylon 6/6, 6, nylon 6/6, 10, nylon 6/12, nylon 6/6.12, nylon 6/6
．． Copolyamides such as 6/6, 10 and nylon 6/6.6/12 are also used.

Furthermore, nylon 6/6. T, (T: terephthalic acid component),
Semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and meta-xylene diamine or alicyclic diamine, polyamides obtained from meta-xylene diamine and the above linear carboxylic acids, polyesteramides, and polyamides. Mention may be made of etheramides and polyesteretheramides. Note that the polyamide resin may be used alone, or two or more types of polyamide resins may be used in combination.

Examples of rubbery substances that can be used in the composition of the present invention include diene homopolymers such as polybutadiene and polyisoprene, butadiene-styrene random copolymers, butadiene-styrene block copolymers, and isoprene-styrene block copolymers. Among these, butadiene-styrene block copolymers and transpolybutadiene are particularly preferred.

The blending proportions of the polyamide resin, polyphenylene ether resin, and rubbery substance in the composition of the present invention are 25 to 70% by weight of the polyamide resin, preferably 30 to 50% by weight, and 25 to 70% of the polyphenylene ether resin, based on the total amount of these three components. % by weight preferably 40-60% and rubbery material 0-25% by weight, preferably 2-25% by weight, more preferably 5-20% by weight.

Furthermore, in the present invention, a modified polyphenylene ether resin into which a carboxyl group has been introduced can be used as the polyphenylene ether resin. When the polyamideimide elastomer (B) component is kneaded with this modified polyphenylene ether resin, a good antistatic effect is exhibited. Although the mechanism thereof is not necessarily clear, a modified polyphenylene ether resin that does not cause delamination and has an appropriate level of compatibility to the extent that it is not completely compatible is preferred. Although it varies depending on the molecular weight, composition, and ratio of terminal hydroxyl groups to terminal carboxyl groups of the polyamide-imide elastomer, it is generally not preferable that the amount of carboxyl groups in the modified polyphenylene ether resin exceeds 4% by weight because the antistatic effect decreases. Therefore, in order to exhibit the desired antistatic effect, the amount of modification by carboxyl groups in the modified polyphenylene ether resin is desirably 4% by weight or less, more preferably 2% by weight or less.

A preferred modified polyphenylene ether resin used in the composition of the present invention is produced, for example, by melt-kneading an unsaturated carboxylic acid or a functional derivative thereof with a polyphenylene ether resin in the presence of a radical initiator and reacting the resin with the polyphenylene ether resin.

The unsaturated carboxylic acid or its functional derivative includes:
For example, maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo(2,2,1]-]
5-heptene-2,3-dicarboxylic acid, acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids,
Further examples include acrylic acid, methacrylic acid, and esters and amides of these monocarboxylic acids. These may be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids and their functional derivatives, particularly maleic anhydride, are preferred.

Next, the polyamideimide elastomer as component (B) of the composition of the present invention contains (a) caprolactam, (b) trivalent or tetravalent polycarboxylic acid, and (c) polyoxyethylene glycol or polyoxyethylene glycol. It consists of a mixture with polyoxyalkylene glycol as the main component, and polyamideimide which becomes a hard segment is obtained from the components (a) and (b), and this is a soft segment.The glycol and ester bond of the component (c) It is a multi-block copolymer linked by

As this component (b), trivalent or tetravalent aromatic polycarboxylic acids which react with amino groups to form at least one imide ring, or acid anhydrides thereof are used.

Specifically, the trivalent tricarboxylic acids used as component (b) include 1,2.4-)limellitic acid, 1゜2-
．． 5-naphthalenetricarboxylic acid, 2,6.7-naphthalenetricarboxylic acid, 3.3', 4-diphenyltricarboxylic acid, benzophenone-3,3', 4-tricarboxylic acid, diphenylsulfone-3,3', 4-tricarboxylic acid acid, diphenyl ether-3,3',4-
Examples include tricarboxylic acid.

Specific examples of the tetravalent tetracarboxylic acid include pyromellitic acid, diphenyl-2,2', 3,3'-tetracarboxylic acid, and benzophenone-2,2'.

3.3'-tetracarboxylic acid, diphenylsulfone-2
, 2', 3,3'-tetracarboxylic acid, diphenyl ether-2,2', 3,3'-tetracarboxylic acid, and the like.

These polycarboxylic acids are used in a substantially equimolar amount, that is, 0.9 to 1.1 times the mole of the glycol component (c).

Polyamideimide, which is a hard segment, is involved in the heat resistance, strength, hardness, and compatibility with polyphenylene ether resin of the elastomer, and the polyamideimide content in this elastomer is 15 to 70% by weight. It is preferable.

If the content is less than 15% by weight, the strength of the elastomer will be low, and when kneaded with polyphenylene ether resin, the impact strength will be low, which is not preferable.
Exceeding this is not preferable because the affinity deteriorates and the antistatic effect decreases.

Further, the number average molecular weight of the polyamideimide is preferably 500 or more and 3000 or less, more preferably 500 or more and 2000 or less. If the number average molecular weight of polyamide-imide is less than 500, the melting point will be low and heat resistance will be lowered, and if it exceeds 3000, the affinity with polyphenylene ether resin will be lowered, which is not preferable.

In the composition of the present invention, when diamine (d) is used in combination to further introduce an imide ring into polyamideimide in order to improve heat resistance, the polycarboxylic acid contains glycol component (c) and diamine component (6). ) is used in an amount of 0.9 to 1.1 times the total number of moles.

The diamine of component (d) includes ethylene diamine, tetramethylene diamine, hexamethylene diamine,
Examples include phenylenediamine.

The amount of the second component used is preferably at most 1 mole of the glycol component (c). If more than this is used, it becomes difficult to obtain a homogeneous elastomer and the compatibility with the polyphenylene ether resin decreases, so it is preferable. do not have.

As component (c) in the polyamideimide elastomer, polyoxyethylene glycol or a mixture of polyoxyethylene glycol and polyoxyalkylene glycol other than polyoxyethylene glycol is used.

The number average molecular weight of the polyoxyethylene glycol used is not particularly limited, but is preferably within the range of 500 to 5,000. If it is less than 500, it is not preferable because the melting point may become low and heat resistance may be insufficient, although it depends on the composition of the elastomer. Also, 5000
If it exceeds, it becomes difficult to form a strong nilast marker,
When kneaded with polyphenylene ether resin, it is not preferable because it may cause a decrease in impact strength or rigidity.

The polyoxyalkylene glycol that can be used in combination with polyoxyethylene glycol is less than 50% by weight of the glycol component and has a number average molecular weight of 500 to 50%.
00 polyoxytetramethylene glycol, modified polyoxytetramethylene glycol, polyoxypropylene glycol, etc. can be used.

As the modified polyoxytetramethylene glycol, -(cHI
) 4 0- is partially replaced with -R-0-. Here, R is an alkylene group having 2 to 10 carbon atoms, such as ethylene group, 1,2-propylene group, 1
．． Examples include 3-propylene group, 2-methyl-1,3-propylene group, 2,2-dimethyl-1,3-propylene group, pentamethylene group, and hexamethylene group. There is no particular restriction on the amount of modification, but it is usually selected within the range of 3 to 50% by weight. The amount of modification and the type of alkylene group are appropriately selected depending on the required properties of the polyphenylene ether resin composition, such as low-temperature impact resistance and heat resistance.

This modified polyoxytetramethylene glycol can be produced, for example, by copolymerization of tetrahydrofuran and a diol using a heteropolyacid as a catalyst, or by copolymerization of a cyclic ether that is a diol or a condensation product of a diol and butanediol.

Regarding the method for producing the polyamide-imide elastomer used in the composition of the present invention, any method may be used as long as it can produce a homogeneous amide-imide elastomer, and for example, the following method may be used.

Caprolactam component (a), aromatic polycarboxylic acid component (b) and glycol component (c) are combined into component (b), (
c) Components are mixed in a substantially equimolar ratio, and the water content in the resulting polymer is maintained at 0.1 to 1% by weight at 150 to 300°C, preferably 180 to 280°C.
This is a method of polymerization. In this method, the reaction temperature can also be raised stepwise during dehydration condensation.

At this time, some caprolactam remains unreacted, but this is distilled off under reduced pressure and removed from the reaction mixture.

The reaction mixture after removing unreacted caprolactam can be further polymerized by post-polymerization under reduced pressure at 200-300°C, preferably 230-280°C, if necessary.

In this reaction method, esterification and amidation occur simultaneously during the dehydration condensation process to prevent coarse phase separation, thereby producing a homogeneous and transparent elastomer. This has excellent compatibility with polyphenylene ether resins, and when kneaded with polyphenylene ether resins, it exhibits excellent antistatic effects and mechanical properties.

By causing the esterification reaction and caprolactam polymerization to occur simultaneously, and controlling the rate of each reaction,
In order to obtain a transparent and homogeneous elastomer, it is necessary to remove the generated water from the system and maintain the water content in the reaction system in the range of 0.1 to 1% by weight during polymerization. is preferred. When this water content exceeds 1% by weight, polymerization of caprolactam takes priority and coarse phase separation occurs, while when the water content is less than 0.1% by weight, esterification takes priority and caprolactam does not react, resulting in an elastomer of the desired composition. I can't get it. This water content is appropriately selected within the above range depending on the desired physical properties of the elastomer.

Furthermore, in this reaction, the water content in the reaction system may be gradually reduced as the reaction progresses, if desired. This moisture content can be controlled by, for example, reaction temperature,
This can be done by controlling reaction conditions such as the flow rate of inert gas introduced and the degree of pressure reduction, or by changing the reactor structure.

The degree of polymerization of the polyamideimide elastomer used in the composition of the present invention can be changed as desired, but
Preferably, the relative viscosity, measured at 30° C. at 0.5% (weight/volume) in meta-cresol, is greater than or equal to 1.5. If it is lower than 1.5, sufficient mechanical properties cannot be exhibited, and even when kneaded into polyphenylene ether resin, the mechanical properties may be insufficient. A more preferable relative viscosity is 1.6 or more.

When diamine (d) is used in combination, the reaction can be carried out either in one stage or in two stages. The former consists of caprolactam (a), polycarboxylic acid component), glycol component (c), and diamine component (d)
This is a method of preparing and reacting at the same time.

In addition, in the latter case, the polycarboxylic acid component (b) and the diamine component (d) are first reacted, and then caprolactam (a) is reacted with the diamine component (d).
In this method, the glycol component (c) and the glycol component (c) are combined and reacted.

When producing a polyamideimide elastomer, an esterification catalyst can be used as a polymerization accelerator.

Examples of the polymerization accelerator include phosphoric acid, polyphosphoric acid,
Phosphorus compounds such as metaphosphoric acid; Tetraalkylorthotitanates such as tetrabutyl orthotitanate; Tin-based catalysts such as diptyltin oxide and dibutyltin laurate; Manganese-based catalysts such as manganese acetate; Antimony-based catalysts such as antimony trioxide; Acetic acid A lead-based catalyst such as lead is suitable. The catalyst may be added at the initial stage of polymerization or at the middle stage of polymerization.

In addition, in order to increase the thermal stability of the obtained polyamide-imide elastomer, various heat-resistant anti-aging agents and stabilizers such as antioxidants can be used.
It may be added at any stage, intermediate or final stage. It can also be added after polymerization and before kneading with the polyphenylene ether resin.

Examples of the heat-resistant stabilizer include N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxycinnamic acid amide), 4,4'-bis(2°6-di-t- −
various hindered phenols such as N,N'-bis(β-naphthyl)-P-phenylenediamine, N, N'-diphenyl-
Aromatic amines such as P-phenylenediamine, poly(2,2,4-)tumethyl-1,2-di-7droquinoline); copper salts such as copper chloride and copper iodide; dilaurylthiodipropionate, etc. Examples include sulfur compounds and phosphorus compounds.

In the composition of the present invention, the amount of the polyamideimide elastomer (B) component is 100 parts by weight of the resin mixture of (A) component (a) polyphenylene ether resin, (b) polyamide resin, and rubber-like material. The amount is selected within the range of 2 to 40 parts by weight.

If the amount is less than 2 parts by weight, a sufficient antistatic effect will not be obtained, and if it exceeds 40 parts by weight, the rigidity will be insufficient.

In the composition of the present invention, it has been found that when a polyamideimide elastomer and an electrolyte such as sodium dodecylbenzene sulfonate are used in combination, a remarkable synergistic effect is exhibited in terms of antistatic effect.

Examples of organic electrolytes that exhibit such effects include organic compounds having acidic groups, metal salts thereof, ammonium salts, and organic phosphonium salts. Examples of the organic compound having an acidic group or its metal salt include dodecylbenzenesulfonic acid, P-toluenesulfonic acid, dodecyl diphenyl ether disulfonic acid, naphthalenesulfonic acid, a condensate of naphthalenesulfonic acid and bomarin, and polystyrene sulfonic acid. Aromatic sulfonic acids such as acids, alkyl sulfonic acids such as lauryl sulfonic acid, organic carboxylic acids such as stearic acid, lauric acid, and polyacrylic acid, organic phosphoric acids such as diphenyl phosphite and diphenyl phosphate, and their alkali metals. It is effective even in the form of free acids, including salts and alkaline earth metal salts, but it is preferable to use them in the form of alkali metal or alkaline earth metal salts.
For example, sodium, potassium, lithium, magnesium, and calcium salts are preferred.

Examples of organic ammonium salts include quaternary ammonium salts such as trimethyloctylammonium bromide, trimethyloctylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, trioctylmethylammonium bromide, and organic phosphonium salts. Examples include quaternary phosphonium salts such as amyltriphenylphosphonium bromide and tetrabutylphosphonium bromide.

On the other hand, as the inorganic electrolyte, for example, AgN0. Be5O
a.

CaC1z + Ca (NOi) Z+ CdC12
+ Cd (NO:l) 2+ CoC1z, CrC
15+CsCl, CuC1, Cu (NO3) 2
1 CuSO41FeC1z, KBr+ KH2POa
IKNCS, KNO3, LiC1, LiOH, Li
N0+, MgC1□, Mg (NO:l) z.

MgSO4+ MnC1z, MnSO4, NH4Cl,
NHaNOffI(NH4)zsOa.

NaBr1Na2CO3, NaH2PO41NaNO3
, NiSO41Pb(NOf+)21PrC13+Rh
Cl, RbN0a, Zn(NO:+)z, ZnSO4
Examples include.

The amount of these electrolytes added is usually selected in the range of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B). . If this amount is less than 0.01 parts by weight, the addition effect will not be sufficiently exhibited, and if it exceeds 10 parts by weight, it will cause a decrease in impact strength, corrosion of the mold, formation of mold deposits, deterioration of appearance, etc. Undesirable.

Further, among these electrolytes, organic electrolytes are more preferable than inorganic electrolytes in terms of mold corrosion resistance and appearance.

The composition of the present invention may optionally include various additive components such as pigments, dyes, reinforcing agents, fillers, heat stabilizers, antioxidants, nucleating agents, lubricants, plasticizers, etc., to the extent that the objects of the present invention are not impaired. Agents, antistatic agents, mold release agents, other polymers, etc. can be contained in any process such as the kneading process or the molding process.

The composition of the present invention can be prepared using a known method such as a Banbury mixer, mixing roll, spindle or twin-screw mixer, for example, by mixing the mixture consisting of the component (A), the component (B), an electrolyte used as necessary, and various additive components. It can be prepared by kneading using an extruder or the like. The kneading temperature at this time is preferably in the range of 240°C to 330°C.

The polyphenylene ether resin composition of the present invention thus obtained is molded by a known method generally used for molding thermoplastic resins, such as injection molding, extrusion molding, blow molding, and vacuum forming. can do.

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.

The physical properties of the composition and elastomer were determined according to the following methods.

(1) Heating deformation temperature: JIS K 7207 load 18.6 kg/cn (2
) Flow: Short shot molding pressure when forming a dumbbell test piece at 290°C (3) Flexural modulus: Measured at 23°C and 150% RH using a test piece with a thickness of 174 inches according to ASTM D790.

(4) Izot impact strength: Measured at 23° C. and 150% RH using a notched test piece having a thickness of 174 inches according to ASTM D256.

(5) Surface resistivity: According to ASTM D257, the surface resistivity (initial (The surface resistivity of the molded product was determined after being left for 4 months at 23° C. and 150% RH.

In addition, in the present invention, a composition having sustained antistatic performance means that the composition does not substantially retain its initial value of surface resistivity even after being left in a constant temperature room at 23°C and 150% RH for 90 days or more after molding. After holding the composition or molding, immerse it in running water for 10 minutes, remove surface moisture, and heat at 23°C 150%.
This refers to a composition whose measured surface resistivity substantially maintains the initial value of surface resistivity after conditioning under RH conditions for 24 hours. Maintaining the surface resistivity substantially at the initial value means maintaining a value not exceeding 10.0 times the initial value, more preferably not exceeding 5.0 times the initial value.

(5) Relative viscosity of elastomer: Measured in metacresol at 30° C. and 10.5% by weight/volume.

(6) Thermal decomposition temperature of elastomer: The weight loss temperature was determined using a differential thermal balance at a heating rate of 10"C/
Measured in minutes.

In addition to the raw materials obtained in the production examples, the raw materials used in the present examples and comparative examples are as follows.

Polyphenylene ether; 7731)/C=0.56 (chloroform 0.5% solution) poly(2,6-dimethylphenylene-1,4-ether) (hereinafter abbreviated as PPE) 6.6-nylon resin 9 Asahi Kasei Kogyo ■Product name: Ona 1300SSB (styrene-butadiene) block polymer; Production example 1 Production of polyamideimide elastomer (B-1) 102 stainless steel reaction vessel equipped with a stirrer, nitrogen inlet, and distillation tube , polyoxyethylene glycol (number average molecular weight 1980) 2680 g, trimellitic anhydride 259.4 g, caprolactam 1707 g and pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)]. Propionate] and tris(2,4-di-t-butylphenyl) phosphite 1=1 blend product (trade name Nilganox B225: antioxidant) 8.0g was charged, and 10"
The pressure was reduced to I Torr at C and stirred for 1 hour to remove moisture in the raw materials. After that, nitrogen was introduced and the temperature was increased to 300 Torr.
While maintaining the pressure at r, the temperature was raised to 260'C for polymerization for 4 hours, and the pressure was gradually reduced at the same temperature to distill off unreacted caprolactam.

Next, nitrogen was introduced again to maintain the pressure at 200 Torr, and a solution of 4.0 g of tetrabutyl orthotitanate dissolved in 100 g of caprolactam was added.
The pressure was reduced to Torr, and polymerization was carried out at the same temperature for 7 hours. The obtained polymer was discharged onto a cooling belt and pelletized to obtain a pellet-shaped elastomer.

This elastomer is light brown and transparent, contains 67% by weight of polyoxyethylene glycol, and has a relative viscosity of 2.
．． 18, the tensile strength and elongation are each 310 kg/
C1l! , 850%.

In addition, the thermal decomposition start temperature of this elastomer, 10% weight loss temperature change temperature, 30% weight weight loss temperature change temperature, 353 ° C. 1, respectively.
The temperature was 377°C and 1394°C.

Production Example 2 Production of polyamide-imide elastomer (B-2) 500d equipped with a stirrer, nitrogen inlet and distillation tube
In a separable flask, add 1/44 g of polyoxyethylene glycol (number average molecular weight 2010), 13.7 g of trimellitic anhydride, and 68.2 g of caprolactam.
g and 0.4 g of poly(2,2,4-)trimethyl-1,2-dihydroquinoline) (trade name Nickrank 224: antioxidant) and stirred at 100"C for 30 minutes.
Dehydration was performed by reducing the pressure to below I Torr for minutes.

Next, the temperature was raised to 260° C. while nitrogen was flowing at a rate of 60 m/min, and after polymerization was carried out for 4 hours, the pressure was gradually reduced at the same temperature to distill off unreacted caplactam from the system.

Then, 0.4 g of tetrabutyl titanate was added and I
The pressure was reduced to Torr, and polymerization was carried out for 7 hours to obtain a pale yellow transparent elastomer.

This elastomer had a polyoxyethylene glycol content of 72% by weight, a polyamideimide number average molecular weight of 800, a relative viscosity of 2.25, and a tensile strength and elongation of 290 kg/C1M and 1200%. .

Also, the thermal decomposition start temperature of this elastomer is 10% weight loss and temperature change is 30% weight! The decreasing temperatures are 350℃ and 350℃, respectively.
The temperature was 425°C and 1443°C.

Note that the amount of water in the polymerization system 1.2.4 hours after starting the reaction at 260° C. was 0.7% by weight, 0.6% by weight, and 0.6% by weight.

Production Examples 3 to 5 Polyamideimide elastomer (B-3
, B-4) and polyamide elastomer (B-5) Polyamideimide elastomer and polyamide elastomer having the compositions shown in Table 1 were produced in the same manner as in Production Example 2. Table 2 shows the physical properties of the elastomer.

(Leaving space below) Example I 55 parts by weight of PPE, 35 parts by weight of 6.6-nylon, 10 parts by weight of SR block polymer of 40% bound styrene, and 10 parts by weight of elastomer (B-1) were mixed, and a NAS manufactured by Nakatani Kikai ■ was prepared. Pellets were obtained by extrusion using a twin-screw bent two extruder at a maximum cylinder temperature of 300°C, and after injection molding at 290°C, test pieces were prepared and their physical properties were evaluated. The results are shown in Table 3.

Example 2 Physical properties were measured in exactly the same manner as in Example 1, except that 1 part by weight of sodium dodecylbenzenesulfonate was added. The results are shown in Table 3.

Example 3 Physical properties were measured in exactly the same manner as in Example 2, except that 30 parts by weight of PPE and 15 parts by weight of carboxyl group-modified PPE were used as the polyphenylene ether resin. The results are shown in Table 3.

Example 4 In Example 1, P without adding SB block polymer
Physical properties were measured in exactly the same manner as in Example 1, except that the amount of elastomer (B-1) was changed to 15 parts by weight, 60 parts by weight of PE, 40Ii parts by 6.6-nylon. The results are shown in Table 3.

Example 5 Physical properties were measured in exactly the same manner as in Example 2, except that the amount of elastomer (B-1) was changed to 5 parts by weight. The results are shown in Table 3.

Example 6 Physical properties were measured in exactly the same manner as in Example 5, except that the elastomer (B-1) was changed to 3 parts by weight and the sodium dodecylbenzenesulfonate was changed to 2 parts by weight. The results are shown in Table 3.

Example 7 Physical properties were measured in exactly the same manner as in Example 2, except that the elastomer was changed to (B-2). The results are shown in Table 3.

Example 8 Physical properties were measured in exactly the same manner as in Example 2, except that the elastomer was changed to (B-3). The results are shown in Table 3.

Example 9 In Example 2, physical properties were measured in exactly the same manner as in Example 1, except that the elastomer was changed to (B-4). The results are shown in Table 3.

Example 10 The test specimen prepared in Example 1 was immersed in running water for 7 days, then vacuum-dried at 80° C. for 2 days, and then subjected to a charging voltage test. As a result, it was the same as before washing with water.

Comparative Example 1 Physical properties were measured in exactly the same manner as in Example 1, except that the elastomer (B-1) was not added. The results are shown in Table 3.

Comparative Example 2 Physical properties were measured in exactly the same manner as in Comparative Example 1, except that 1 part by weight of sodium dodecylbenzenesulfonate was added. The results are shown in Table 3.

Comparative Example 3 In Comparative Example 1, the amount of SB Pronk polymer added was 2.
The physical properties were measured in exactly the same manner as in Comparative Example 1, except that the amount was changed to 0 parts by weight. The results are shown in Table 3.

Comparative Example 4 In Comparative Example 2, physical properties were measured in exactly the same manner as in Comparative Example 2, except that 30 parts by weight of PPE and 15 parts by weight of carboxyl group-modified PPE were used as the polyphenylene ether resin. The results are shown in Table 3.

Comparative Example 5 Physical properties were measured in exactly the same manner as in Example 1, except that 1.5 parts by weight of the elastomer (B-1) and 2 parts by weight of sodium dodecylbenzenesulfonate were added. The results are shown in Table 3.

Comparative Example 6 The physical properties were measured in exactly the same manner as in Example 3, except that the elastomer (B-1) was changed by 45 parts by weight δ. The results are shown in Table 3.

Comparative Example 7 Physical properties were measured in exactly the same manner as in Example 1, except that the elastomer was changed to (B-5). The results are shown in Table 3.

(The following is a blank space) [Effects of the Invention] The polyphenylene ether resin composition of the present invention has a polyphenylene ether resin, a polyamide resin, and a polyamide elastomer as basic resin components, and has permanent antistatic properties, It has characteristics such as good mechanical properties and moldability, and is suitable for use as a material for housings and mechanical parts of coin mechanisms of vending machines, for example.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (4)

[Claims] 1. (A) (I) Polyphenylene ether resin 25-7
(B) (a) caprolactam, (b) at least one imide ring to 100 parts by weight of a resin mixture of 0% by weight and (b) 25 to 70% by weight of polyamide resin and 0 to 25% by weight of a rubbery substance. A trivalent or tetravalent aromatic polycarboxylic acid that can be formed and (c) polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly composed of polyoxyethylene glycol, the content of component (c) is 30 to 30. Polyamideimide elastomer 2 containing 85% by weight and having a relative viscosity of 1.5 or more at a temperature of 30°C
-40 parts by weight of a polyphenylene ether resin composition. 2. (A) (I) Polyphenylene ether resin 25-7
(B) (a) caprolactam, (b) at least one imide ring to 100 parts by weight of a resin mixture of 0% by weight and (b) 25 to 70% by weight of polyamide resin and 0 to 25% by weight of a rubbery substance. at least one of a trivalent or tetravalent aromatic polycarboxylic acid that can be formed, (c) polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly composed of polyoxyethylene glycol, and (d) a diamine having 2 to 10 carbon atoms. Polyamide-imide elastomer 2-2 obtained from seeds, having a content of component (c) of 30 to 85% by weight, and a relative viscosity of 1.5 or more at a temperature of 30°C
A polyphenylene ether resin composition containing 40 parts by weight. 3. Claim 1 or 2, wherein the polyphenylene ether resin is a modified polyphenylene ether resin at least partially modified with an unsaturated carboxylic acid or a functional derivative thereof.
The polyphenylene ether resin composition described above. 4. 4. The polyphenylene ether resin composition according to claim 1, comprising an electrolyte.