JPH0345651A - Antistatic polyphenylene ether resin molding - Google Patents

Abstract

PURPOSE:To obtain a resin molding excellent in mechanical characteristics and having persistent antistatic properties by incorporating a specified polyamide-imide elastomer into a mixture of a polyphenylene ether resin with a styrene resin and molding it. CONSTITUTION:A molding obtained from a resin composition prepared by mixing 100 pts.wt. resin mixture (A) comprising 20-80wt.% polyphenylene ether resin and 80-20wt.% styrene resin with 3-30 pts.wt. polyamide-imide elastomer (B) which is made from caprolactam (a), a tribasic or tetrabasic aromatic polycarboxylic acid (b) capable of forming at least one imide ring, and a component (c) comprising a polyoxyethylene glycol or a polyoxyalkylene glycol mixture consisting mainly of a polyoxyethylene glycol, which contains 40-80wt.% component (c), and which has a relative viscosity at 30 deg.C of 1.5 or higher. The molding thus obtained has a surface resistivity of less than 1.0X10<14>OMEGA/square.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a novel antistatic polyphenylene ether system v
4 fat-bottomed body, more specifically, a polyphenylene ether resin composition containing poly7-ethylene ether resin, styrene resin, and polyamideimide elastomer as basic resin components, which has excellent mechanical properties and The present invention relates to an antistatic polyphenylene ether resin molded article that has a lasting antistatic property and is suitable for use as housings and cases for electronic/electrical equipment, OA equipment, etc.

BACKGROUND OF THE INVENTION Recently, 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 and cases of OA equipment, electronic/electrical equipment, etc., there are drawbacks such as generation of static electricity, adhesion of dust due to charging, and problems such as discharge. Therefore, there has been 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.
．． No. 384.078), polyphenylene ether resins are imparted with antistatic properties by nuclear substitution with groups such as sulfonate groups to form certain ionic derivatives (US Pat. No. 3.078). No. 529,520 IF), p-) Certain bis-
It is known that ethoxylated quaternary ammonium salts are useful as antistatic agents for polystyrene, polyesters, polyamides, polycarbonates, polyolefins, ABSI # resins, etc. (U.S. Pat. No. 3,933,779). There is. 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 has been proposed that uses a polyether ester amide and a vinyl copolymer containing a carboxyl group (Japanese Patent Application Laid-Open 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 has been proposed 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. 1983-1982-1). 2
61359), this composition also has insufficient long-term antistatic properties. In addition, for thermoplastic resin,
Acrylic ester elastomer (JP-A-63-48
Attempts have also been made to impart antistatic properties by blending styrene-acrylic acid copolymer (Japanese Patent Application Laid-open No. 156-1981) or styrene-acrylic acid copolymer (Japanese Unexamined Patent Publication No. 156-1981). 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.

By the way, in order to impart antistatic properties to polyphenylene ether resins, conventionally, 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 disadvantage is that the effect of imparting antistatic properties is not necessarily sufficient.On the other hand, the method of blending a conductive filler can impart excellent antistatic properties, but when carbon black is blended, for example, it becomes darkly colored. It cannot be used when a material with a bright color is required, and adding metal powder reduces moldability, impairs the appearance of the molded product, and impairs physical properties such as impact resistance. There are disadvantages such as a decrease in

Problems to be Solved by the Invention Under these circumstances, the present invention has permanent antistatic properties and has excellent mechanical properties, moldability, appearance, etc., and is suitable for use in electronic/electrical equipment and OA. The purpose of this invention is to provide a polyphenylene ether resin molded body suitable for housings, cases, etc. of equipment.

Means for Solving the Problems The present inventor has conducted various studies in order to impart antistatic properties to a resin mixture of polyphenylene ether resin and styrene resin; A polyamideimide elastomer whose hard segment is a polyamideimide dicarboxylic acid obtained from caprolactam and an aromatic polycarboxylic acid capable of forming at least one imide ring such as trimellitic acid or pyromellitic acid is polyphenylene ether. It is compatible with resin mixtures of resins and styrenic resins, and is also heat resistant, and when incorporated in relatively small amounts into resin mixtures, it can provide long-lasting properties without sacrificing its desirable properties. We have discovered scales that impart antistatic properties, and have completed the present invention based on this knowledge.

That is, the present invention comprises (A) (a) 20 to 80% by weight of polyphenylene ether resin and (b) 80% by weight of styrene resin.
For 100 parts by weight of a resin mixture with ~20% by weight (B
) (a) caprolactam, (b) trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, (c) polyoxyethylene glycol or polyoxyalkylene based on polyoxyethylene glycol obtained from a glycol mixture and optionally used (d) at least one diamine having 2 to 10 carbon atoms;
(c) Molding a polyphenylene ether resin composition containing 3 to 30 parts by weight of a polyamideimide elastomer having an fR content of 40 to 80% by weight and a relative viscosity of 1.5 or more at a temperature of 30°C. The present invention provides an antistatic polyphenylene ether resin molded article having a surface resistivity of less than 1.0×10×10 14 Ω/□ and having continuous antistatic properties.

The present invention will be explained in detail below.

The component (A) in the component (A) of the composition used in the molded article of the present invention, that is, the polyphenylene ether resin, is a polyphenylene ether resin used in a resin composition made from a known polyphenylene ether resin and a styrene resin. You can choose any one from among them. As such, for example, those represented by the general formula (R1 and R1 in the formula 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) (R3, R4, R6 and R' in the formula 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) R1 and R6 cannot be hydrogen atoms at the same time).

Typical examples of borifinisine ether homopolymers include:
Poly(2,6-cystyl(,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2,6-danityl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-n-7'propyl-1,4-phenylene) ether, poly(2-methyl-〇n-butyl)ether 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 polyphenylene ether copolymers include alkyl-substituted phenols such as 2,3,6-trimethylphenol represented by the general formula (R1, R4, R% and R% in the formula have the same meanings as above); Examples include polyphenylene ether copolymers mainly composed of a polyphenylene ether structure obtained by copolymerizing monoalkylphenols such as cresol.

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 this modified polyphenylene ether resin is kneaded with the polyamideimide elastomer of CB)l&, a good antistatic effect is exhibited. Although the mechanism thereof is not necessarily clear, it is preferable to use a modified polyphenylene ether resin that does not cause delamination and has an appropriate degree of compatibility to the extent that it is not completely compatible.

When modifying polyphenylene ether resin by introducing a carboxyl group, its compatibility with the polyamideimide elastomer improves, and although it varies depending on the molecular weight, composition, and ratio of terminal hydroxyl groups to terminal carboxyl groups of the polyamideimide elastomer, it is usually If the amount of carboxyl groups in the modified polyphenylene ether resin exceeds 4% by weight, the antistatic effect will decrease, which is not preferred. Therefore, in order to exhibit the desired antistatic effect, the amount of modification by carboxyl groups in the modified polyphenylene ether resin is preferably 4% by weight or less, more preferably 2% by weight or less.

Preferred modified polyphenylene ether resins used in the present invention include, for example, in the presence of a radical initiator,
It is produced by melt-kneading unsaturated carboxylic acid or its functional derivative with polyphenylene ether resin and reacting the mixture. In this case, by coexisting styrenic monomer,
This can be included in the structural unit, or the modified styrenic resin can be made to coexist with a styrene resin and used as it is contained.

The unsaturated carboxylic acid or its functional derivative includes:
For example, maleic acid, 7-malic acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo(2,2,1)-
Examples include 5-heptene-2,3-dicarboxylic acid, acid anhydrides, esters, amides, and imides of these dicarboxylic acids, as well as acrylic acid, methacrylic acid, and esters and amides of these monocarboxylic acids. It will be done. 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.

On the other hand, the styrene resin used as the (original) component in the component (A) may be arbitrarily selected from among the styrene resins used in known resin compositions consisting of polyphenylene ether resins and styrene resins. I can do it. As such, for example, the general formula (wherein R1 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, and n is an integer of 1 to 5; When n is 2 or more, RI may be different from each other.

Examples of such styrene resins include styrene homopolymers such as polystyrene, polygumethylstyrene, and polychlorostyrene, modified polystyrenes such as rubber-modified polystyrene, styrene-acrylonitrile copolymers (AS), and styrene-butadiene. copolymer (SB), styrene-acrylonitrile-butadiene copolymer (AB
S), styrenic copolymers such as ethylvinylbenzene-shynylbenzene lt amalgamation. One type of these styrene resins may be used, or two or more types may be used in combination.

Further, in the present invention, as the styrene resin, a styrene resin having a carboxyl group introduced therein may also be used. Such carboxyl group-modified styrenic resins can be prepared by copolymerizing styrene and vinyl hexamer containing carboxyl groups, or by diluting this copolymer with polystyrene, rubber-reinforced polystyrene, etc. can. The amount of modification of the styrene resin by carboxyl groups is preferably 41i% or less, more preferably 21i% or less.

Next, (B) If in the composition used for the molded article of the present invention
f, that is, the polyamideimide elastomer has (a
) caprolactam, (b) a trivalent or tetravalent polycarboxylic acid, and (c) a mixture with polyoxyethylene glycol or a polyoxyalkylene glycol mainly composed of polyoxyethylene glycol, and (a)
A polyamide-imide serving as a hard segment is obtained from the fR component and the component (b), and this is a multi-block copolymer connected to the glycol of the soft segment (c) ff through an ester bond.

As this component (b), a trivalent or tetravalent aromatic polycarboxylic acid capable of reacting with an amino group to form at least one imide ring, or an acid anhydride thereof is used.

Specifically, the trivalent tricarboxylic acid used as component (b) includes 1,2.4-1-limellitic acid, 1.2
．． 5-su7talenttricarboxylic acid, 2,6.7-naphthalenetricarboxylic acid, 3.3',4-diphenyltricarboxylic acid, benzophenone-3,3', 4-tricarboxylic acid, diphenylsulfone-3,3',4 -tricarboxylic acid, diphenyl ether-.

Specifically, the tetravalent tetracarboxylic acid includes pyromellitic acid, diphenyl-2.2', 3.3'
-Tetracarboxylic acid, benzophenone-2.2'. 3.
3'-Tetracarboxylic acid, diphenylsulfone-2.2
',3,3'-tetracarboxylic acid, diphenyl ether-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 20 to 60% by weight. It is necessary. If the content is less than 20% by weight,
This is not preferable because the strength of the elastomer becomes low and the impact strength becomes low when it is kneaded with polyphenylene ether resin, and if it exceeds 60% by weight, the compatibility becomes poor and the antistatic effect becomes low, so it is not preferable. do not have.

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 the polyamide-imide is less than 500, the melting point will be low and the heat resistance will be reduced, and if it exceeds 3000, the compatibility with the polyphenylene ether resin will be low, which is not preferable.

In the composition, when diamine (d) is used in combination to further introduce an imide ring into polyamideimide in order to improve heat resistance, the polycarboxylic acid is a glycol component (c) and a diamine component (d). It 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 used is preferably at most 1 mole of the glycol component (c); if it is used in an amount larger than this, it becomes difficult to obtain a homogeneous elastomer and the compatibility with the polyphenylene ether resin decreases, which is not preferable. .

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 elastomer,
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, −(cHz
) Examples include those in which a-0- is partially replaced with -R-0-. Here, R is an alkylene group having 2 to IO carbon atoms, such as ethylene group, 1,2-propylene group, l,
Examples include 3-propylene group, 2-methyl-1,3-propylene group, 2,2-dimethyl-1,3-propylene group, pentamethylene group, hexamethylene group, and the like. There is no particular restriction on the amount of modification, but it is usually selected within the range of 3 to 50% by weight. Further, the amount of modification and the type of the alkylene group are appropriately selected depending on the required properties of the poly(7-modylene 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 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) and (
c) The ingredients are mixed in a substantially equimolar ratio, and the water content in the rawhide polymer is maintained at 0.1-1% by weight at 150-300°C, more preferably at 180-280°C.
This is a method of polymerization. In this method, the reaction temperature can 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 poly-7-ethylene ether-based resin, and when kneaded with polyphenylene ether-based resin, exhibits excellent antistatic effect 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 of the reaction system within the range of 0 and 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 present invention can be arbitrarily changed as necessary, but the relative viscosity measured at 30°C at 0.5% (weight/volume) in metacresol is 1.5 or more. It is preferable to do so.

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 step or in two steps. The former consists of caprolactam (a), polycarboxylic acid component (b), glycol component (c), and diamine component (d
) are simultaneously prepared and reacted. The latter is a method in which the polycarboxylic acid component (b) and the diamine component (d) are first reacted, and then the caprolactam (a) and the glycol component (c) are reacted together.

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,
Phosphorous compounds such as metaphosphoric acid; Tetraalkylorthotitanates such as tetrabutyl orthotitanate; Tin-based catalysts such as dibutyltin oxide and dibutyltin laurate; Manganese-based catalysts such as manganese acetate; Antimony-based catalysts such as antimony dioxide; Lead acetate, etc. A lead-based catalyst or the like 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, stabilizers such as various heat-resistant anti-aging agents and antioxidants can be used. May be added. It can also be added after polymerization and before mixing with the polyphenylene ether resin.

Examples of the heat stabilizer include N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxycinnamic acid amide), 4,4'-bis(2,6-di-t-t-butyl-4-hydroxycinnamide), −
butylphenol), 2,2'-methylenebis(4-
Various hindered phenols such as ethyl-6-t-butylphenol; N,N'-bis(β-naphthyl)
-p-phenylenediamine, N,N'-diphenyl-p
- Aromatic amines such as phenylenediamine and poly(2,2,4-trimethyl-1,2-dihydroquinoline):
Examples include copper salts such as copper chloride and copper iodide; sulfur compounds such as dilaurylthiodipropionate; and phosphorus compounds.

In the composition used for the molded article of the present invention, the above (B)J
The blending amount of polyamideimide elastomer for ffi is:
The amount is selected within the range of 3 to 30 parts by weight based on 1001i parts of the resin mixture of component (A) (a) polyphenylene ether resin and (b) styrene resin. If this amount is less than 3 parts by weight, a sufficient antistatic effect cannot be obtained;
If the weight exceeds 1 part, the rigidity will be insufficient.

It has been found that when a polyamideimide elastomer and an electrolyte such as sodium dodecylbenzene sulfonate are used together in the composition, a remarkable synergistic effect is exhibited in the antistatic effect.

Organic electrolytes that exhibit such effects include organic compounds having acidic groups, metal salts thereof, and ammonium salts 1. Examples include Uhiro phosphonium salts.

Examples of the organic compound having an acidic group or its metal salt include dodecylbenzenesulfonic acid sp-toluenesulfonic acid, dodecyl diphenyl ether disulfonic acid, naphthalenesulfonic acid, a condensate of naphthalenesulfonic acid and formalin, and polystyrenesulfonic acid. Alkyl sulfonic acids such as aromatic sulfonic acids and lauryl sulfonic acids, organic carboxylic acids such as stearic acid, lauric acid, and polyacrylic acid, organic phosphoric acids such as diphenyl phosphite and diphenyl phosphate, their alkali metal salts, and alkalis. Examples include earth metal salts.

Although it is effective even in the form of a free acid, it is preferable to use it in the form of an alkali metal or alkaline earth metal salt.
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, and trioctylmethylammonium bromide; examples of organic phosphonium salts include Examples include quaternary phosphonium salts such as amyltriphenylphosphonium bromide and tetrabutylphosphonium bromide.

On the other hand, examples of the inorganic electrolyte include AgNOs.

Be5Oa, CaCl2. Ca(NO3), Cd
ct! , cd(No,),.

CoC1, CrC15, CsC1, CuC1, Cu
(No, ), CuSO4゜FeC1z, KBr,
KH*POoKNC3, KNO3, LiC1, LiO
H.

LiNOs* MgCl*, Mg(NOs)x+ M
g5Oa, MnClt, MnSO4゜NH4Cl,
NH4NO3, (NH*)tsO4, NaBr, N
a1CO3゜NaHz PO4r NaN03 ,N
I SO4, Pb(No s )s + P rC13
*RbCl +RbN0), Zn(NO3)2.
Examples include Zn5Oa.

The amount of these electrolytes added is the total amount of component (A) and component (B) 100! The amount is usually selected from 0.01 to IO parts by weight, preferably from 0.1 to 5 parts by weight, based on i parts.

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, the appearance of mold deposits, and a deterioration of the appearance, so it is preferable. do not have.

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

The composition used for the molded article of the present invention may contain various additive components as desired, such as pigments, dyes, reinforcing agents, fillers, heat stabilizers, antioxidants, and nucleating agents, as long as the object of the present invention is not impaired. , a lubricant, a plasticizer, an antistatic agent, a mold release agent, other polymers, etc. can be contained in any process such as a kneading process or a molding process.

The composition is prepared by mixing a mixture consisting of the above-mentioned components (A), (B), an electrolyte used as necessary, and various additive components using a known method such as extrusion using a Banbury mixer, mixing roll, spindle or two-wheel extrusion. rIR can be produced by kneading using a machine or the like. The kneading temperature at this time is preferably in the range of 180 to 28()°C.

The polyphenylene ether resin composition thus obtained can be processed by known methods generally used for molding thermoplastic resins, such as injection molding, extrusion molding, blow molding, etc.
It is molded into a desired molded body by a method such as vacuum forming.

The molded article of the present invention is characterized in that it has a surface resistivity of less than 1.0×10 Ω/mouth and exhibits sustained antistatic properties.

This surface resistivity was measured according to ASTM D-257. In addition, in the present invention, having sustained antistatic property means that the surface moisture is removed after being left under conditions of 23°C and 150% RH for 90 days or more after molding, or after immersing it in running water for 10 minutes after molding. °C150%RH
This means that the surface resistivity does not exceed 1000 times, preferably 5.0 times, its initial value even after being maintained under these conditions for 24 hours.

There is no particular restriction on the shape of the molded product of the present invention, for example, Fine Chemical Report No. 1 published by Chunichisha Co., Ltd.
, 10R New Trends in Glastic Materials for Electrical and Electronic Equipment (Published September 20, 1985)■, Equipment Compilation 14~
It can be formed into any of the shapes of equipment parts described on page 114.

Examples of such items include, for example, the top cover of a copying machine;
Document holding cover, internal cover, front cover, operation surface cover, charging insulator, paper storage box, paper storage box cover, paper guide, copy paper tray, etc., TV cushioning,
Speaker boxes, terminal ports, etc., telephone housings, handset cases, etc., semiconductor device IC/
<packages, cases for micro 70 disks, cartridges for optical disks, etc., exterior housings for office printers, display panels, paper guides, connectors,
Examples include platen knobs and printer bodies.

Recently, there has been a demand for higher performance of the above-mentioned equipment and its parts, and there is also a strong demand for excellent antistatic properties. The challenge is to prevent dust from being charged and to prevent noise and dropouts. Furthermore, these antistatic effects are required to be sustained for a long period of time and not to be lost even when washed with water.

At the same time, it must also be lightweight and have high mechanical strength, and good appearance as a molded product is also essential.

The molded article of the present invention has all of these characteristics, and furthermore, it is possible to reduce costs, and has great industrial significance.

Effects of the Invention The antistatic polyphenylene ether resin molded article of the present invention is obtained by molding a polyphenylene ether resin composition containing a polyphenylene ether resin, a styrene resin, and a polyamideimide elastomer as basic resin components. , has excellent mechanical properties and permanent antistatic properties, such as electronic/electrical equipment and OA
Suitable for use as a material for housings and cases for equipment, etc.

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) Tensile yield strength and tensile elongation at break: ASTM
Measurements were made at 23° C. and 150% RH using a dumbbell piece with a thickness of 178 inches according to D638.

However, since many elastomers do not have a yield point, the tensile yield strength and tensile elongation at break were measured in an absolutely dry state using dumbbell pieces with a thickness of 1 il Im.

(2) Flexural modulus: Measured at 23° C. and 50% RH using a 1/4 inch thick test piece according to ASTM D790.

(3) Izot impact strength: Measured at 23° C. and 50% RH using a notched test piece having a thickness of 1/4 inch according to ASTM D256.

(4) Surface resistivity: Using a 1/8 inch thick flat plate, manufactured by Toa Denpa Kogyo Co., Ltd.
Measurement was performed using a Kyokucho Megohmmeter Model 5M-10E under the following conditions.

(a) After molding, the surface resistivity was measured after being adjusted for 24 hours at 23° C. and 50% RH (initial surface resistivity).

(b) After molding, it was immersed in running water for 10 minutes to remove surface moisture, and conditioned for 24 hours at 23° C. and 50% RH. Thereafter, it was measured (surface resistivity after washing with water).

(c) After molding, under the conditions of 23°C and 50% RH,
After being left for one day, it was measured (0 surface resistivity on the 150th day).

(5) Relative viscosity of elastomer: Measured in metacresol at 30°C and 0.5% (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"O/
Measured in minutes.

(7) Cigarette ash adhesion test The 1/8 inch thick flat plate used for surface resistivity measurement was rubbed 100 times with gauze, and as shown in the figure, a strip of cigarette ash (174 inches thick) was placed inside. 2, the flat plate 3
was evaluated according to the following criteria.

◎: No cigarette ash attached ○; A small amount of cigarette ash attached ×: A large amount of cigarette ash attached The test piece for measuring physical properties was made by molding the pellets obtained in the Examples and Comparative Examples by 1/2 in an injection molding machine. 8 inch thick flat plate (height 90mm
, 50 m+l+) in width, 1/8 inch and 1/4 inch thick test pieces were molded and used.

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; 1 sp/c -0,56 (0.5% chloroform solution) poly(2,6-dimethylphenylene-1,4-ether) (hereinafter abbreviated as PPE) Styron Q H405; Asahi Kasei Corporation Manufacturing Example 1 of High Impact Polystyrene manufactured by Co., Ltd. Manufacturing of polyamideimide elastomer (B-1) 500I equipped with a stirrer, nitrogen inlet and distillation tube
In a separable IQ flask, polyoxyethylene glycol (number average molecular weight 1980) 1349, trimellitic anhydride, 13-09, caprolactam 85.49, 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: Nylganox B 225: antioxidant) 0.49 was added, 1
The pressure was reduced to 1 Torr at 00oC, and the mixture was stirred for 1 hour to remove water in the raw materials. After that, nitrogen was introduced and
While maintaining the pressure at Torr, the temperature was raised to 260°C.
Polymerization was carried out for a period of time, 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 0.2 g of tetrabutyl orthotitanate dissolved in caprolactam 59 was added.
The pressure was reduced to rr and polymerization was carried out at the same temperature for 7 hours to obtain a light brown transparent elastomer I;.

This elastomer has a polyoxyethylene glycol content of 67 It%, a relative viscosity of 2.18, and a tensile strength and elongation of 310 kg/c1.850.
%Met.

In addition, the thermal decomposition start temperature of this elastomer, 10% weight loss temperature change, 30% weight weight loss temperature change, 353°C, respectively.
377° (!, 394°C.

Production Example 2 Production of polyamideimide elastomer (B-2) 40 g of caprolactam and polyoxyethylene glycol (number average molecular weight 2040) 9
1 g, trimellitic anhydride 11.2 g, hexamethylene diamine 1.5 g (molar ratio to polyoxyethylene glycol 0.3), phosphoric acid 0.15 g and poly(2,
0.2 g of 2,4-trimethyl-1,2-dihydroquinoline (trade name: Nicklac 224: antioxidant) was charged and heated at 260°C while flowing nitrogen at 70 mQ/min.
The reaction was allowed to proceed for 4 hours. Next, unreacted caprolactam was distilled off under reduced pressure, and then tetraisopropyl orthotitanate O,h was added and reacted at 1 Torr for 5 hours to obtain a yellow transparent elastomer.

This elastomer contains 72% by weight polyoxyethylene glycol, has a relative viscosity of 1.90, and a tensile strength of 29%.
5#9/crx", tensile elongation of 1020%, thermal decomposition start temperature, 10% weight/weight loss temperature, and 30% weight/weight loss temperature of 350°C, 403°C, and 438°C, respectively.

Examples 1 to 6 PPE, Styron QH405, stabilizer (manufactured by Adeka Argus, mark AO-30), the elastomer obtained in the production example, electrolyte, and modified resin were mixed in the proportions shown in Table 1, and a screw with a screw diameter of 301111 was mixed. Twin screw extruder (AS-3
0 type, manufactured by Nakatani Kikai Co., Ltd.], the mixture was melt-kneaded at a cylinder temperature of 250°C and a screw rotation speed of 75 rpm, and then extruded at an extrusion rate of 10 to 9/hr to form three strands. , and cooled to about 30°C with water. The cooled strands were then granulated to obtain pellets of the polyphenylene ether resin composition.

After drying this pellet in a gear oven at 80°C for 3 hours, injection molding was performed at a cylinder temperature of 260°C and a mold temperature of 60°C to prepare test pieces for measuring physical properties and surface resistivity. All exhibited excellent gloss. Each physical property of these test pieces was evaluated. The results are shown in Table 1.

In addition, the pellets were injection molded under the conditions of a cylinder temperature of 260°C and a mold temperature of 60°C to create molded products shown in Table 2, with antistatic properties, appearance, and! ! Mechanical properties were evaluated. The results are shown in Table 2.

Examples 7 to 10 Examples 1 to 10 except that the extrusion kneading temperature was 280°C, the injection molding cylinder temperature was 290°C, and the mold temperature was 90°C.
Test pieces and molded bodies shown in Table 2 were prepared in the same manner as in Example 6, and various evaluations were performed. The results are shown in Tables 1 and 2.

Comparative Examples 1 to 6 PPE, Styron Q H405, stabilizer (manufactured by Adeka Argus, mark AO-30), the elastomer obtained in the production example, electrolyte, and modified resin were mixed in the proportions shown in Table 3, and the Test pieces and molded bodies shown in Table 4 were prepared in the same manner as in Examples 1 to 6, and various evaluations were performed. The results are shown in Tables 3 and 4.

Comparative Examples 7-1O PPE, Stylon Q H-405, stabilizer, elastomer obtained in the production example, and other additives were mixed in the proportions shown in Table 3, and test pieces and Molded bodies shown in Table 4 were prepared and various evaluations were performed. The results are shown in Tables 3 and 4.

[Brief explanation of drawings]

The figure is an explanatory diagram showing a method of testing the adhesion of cigarette ash to a molded article, in which reference numeral 1 indicates cigarette ash, 2 indicates a strip, and 3 indicates a flat plate for testing.

Claims (1)

[Claims] 1 (A) (a) Polyphenylene ether resin 20-8
(B) (a) caprolactam; (b) trivalent or tetravalent resin capable of forming at least one imide ring; aromatic polycarboxylic acid and (c) polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly composed of polyoxyethylene glycol, the content of component (c) is 40 to 80% by weight, and the temperature is 3
A product made by molding a polyphenylene ether resin composition containing 3 to 30 parts by weight of a polyamideimide elastomer with a relative viscosity of 1.5 or more at 0°C, and a surface resistivity of 1.0 x 10^1^4 Ω/□ 1. An antistatic polyphenylene ether resin molded article, characterized in that it has a sustained antistatic property. 2 (A) (A) Polyphenylene ether resin 20-8
(B) (a) caprolactam; (b) trivalent or tetravalent resin capable of forming at least one imide ring; (c) a polyoxyethylene glycol or a polyoxyalkylene glycol mixture mainly composed of polyoxyethylene glycol, and (d) a diamine having 2 to 10 carbon atoms. ) component content is 40 to 80% by weight, and the temperature is 3.
A product made by molding a polyphenylene ether resin composition containing 3 to 30 parts by weight of a polyamideimide elastomer with a relative viscosity of 1.5 or more at 0°C, and a surface resistivity of 1.0 x 10^1^4 Ω/□ 1. An antistatic polyphenylene ether resin molded article, characterized in that it has a sustained antistatic property. 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 antistatic polyphenylene ether resin molded article described above. 4. The antistatic polyphenylene ether resin molded article according to claim 1, 2 or 3, wherein the polyphenylene ether resin composition contains at least one electrolyte selected from organic electrolytes and inorganic electrolytes.