JPS60108450A - Polyphenylene ether resin composition having suppressed electrostatic charge - Google Patents

Abstract

PURPOSE:To reduce the titled composition having practically acceptable antistaticity, by compounding a boric acid ester of a fatty acid monoglyceride to a resin composition composed of a polyphenylene ether resin and a vinyl aromatic hydrocarbon resin. CONSTITUTION:The objective composition can be produced by compounding (A) 100pts.wt. of a resin composition composed of (i) 5-95wt% polyphenylene ether resin [preferably a copolymer of poly(2,6-dimethyl-1,4-phenylene)ether/2,6-dimethylphenol/2,3,6-trimeth ylphenol or a graft copolymer of the former two components with styrene] and (ii) a vinyl aromatic hydrocarbon resin (e.g. polystyrene, rubber-modified polystyrene, etc.) with (B) 1-10pts.wt., preferably 2- 7pts.wt. of a boric acid ester of a fatty acid monoglyceride of formula I or formula II (R<1> and R<2> are 4-31C alkyl, alkenyl or alkynyl), and if necessary, (C) various elastomers and additives.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition with suppressed charging.

Polyphenylene ether resin is disclosed in U.S. Patent No. 5,50
It is a known resin disclosed in various documents including No. 6,874. Although it is used as an engineering plastic with excellent heat resistance, it requires extrusion and molding at high temperatures, and deterioration of the polyphenylene ether resin is unavoidable during this process. , the excellent performance originally possessed by the resin is impaired.

In order to overcome these drawbacks, for example, US Pat. No. 5,385,435 discloses that polystyrene resin is blended with polyphenylene ether to improve the fluidity of the polyphenylene ether resin, making it suitable for extrusion and molding. Techniques have been taught to reduce the required temperatures. Also,
Polyphenylene ether resins originally have low impact strength, so by using rubber-modified polystyrene resin as the polystyrene resin or even adding an elastomer component, it is possible to simultaneously improve moldability and impact strength. is also being carried out. It is well known that polyphenylene ether resins have been put to practical use as molding materials in this way.

Polyphenylene ether-based resins inherently have excellent electrical insulation properties, and blends containing polyphenylene ether-based Wd-vinyl aromatic resins and engineered elastomers are also resin compositions with excellent electrical insulation properties. . Therefore, these resin compositions are being put into practical use in a wide variety of applications by making full use of their characteristics in fields where electrical insulation is required. However, on the other hand, in fields where electrical insulation is not required, it can cause various problems, such as 1) injury to the human body due to sparks, 11) molded products adhering to or repelling each other, resulting in unevenness. This may cause defective products. Various inconveniences occur, such as 1il) contamination of molded products due to dust collection, and IV) troubles due to adsorption of other objects. Therefore, in fields where electrical insulation is not required, it is desirable to reduce the electrical insulation.

Known techniques for reducing the electrical insulation properties of polyphenylene ether resin compositions include US Pat. No. 4,125,475.
A resin composition comprising a mixture of triethanolamine, toluenesulfonic acid, and sodium lauryl sulfate as disclosed in the specification of No.
A resin composition containing polyethylene oxide produced by anionic polymerization or a mixture thereof; a resin containing a special quaternary amine salt and polyethylene glycol ester disclosed in U.S. Pat. No. 4,684,065 compositions. However, the antistatic performance of these resin compositions is not sufficient for practical use, and the heat resistance of the compound itself to be added is not sufficient, so that they are not practically satisfactory.

By the way, the reason why the antistatic performance is improved by adding an antistatic compound to the resin is that after the resin composition is molded, the compound used migrates to the surface of the molded product and forms a conductive layer on the surface. This is mentioned. Therefore, the migration speed of the compound from the inside of the molded article to the surface has a great deal to do with the antistatic performance. Factors involved in migration to the surface include the compatibility of the resin and the compound, the molecular structure of the resin, and the glass transition temperature of the resin, and practical antistatic performance is achieved when these are appropriately balanced. Ru.

The present inventors have conducted intensive studies to obtain a polyphenylene ether resin composition that has antistatic properties that can be put to practical use by using a compound with excellent heat resistance. It has been discovered that by blending a boric acid ester of a fatty acid monoglyceride into a resin composition consisting of a hydrocarbon resin, a polyphenylene ether resin composition with suppressed charging which achieves the desired objective -t- can be obtained.

The polyphenylene ether resin used in the composition of the present invention refers to a polyphenylene ether obtained by polycondensation of one or more monocyclic phenols represented by the general formula (I); The 1 to 5 lower alkyl 5 - groups, R2 and R5 are hydrogen atoms or lower alkyl groups having 1 to 6 carbon atoms, and a lower alkyl substituent must always be present at the ortho position of at least one of the hydroxyl groups. ) Refers to a graft copolymer having polyphenylene ether as the base obtained by graft polymerizing a vinyl aromatic compound to nylene ether. This polyphenylene ether may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the general formula (I) include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-
Methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-p-pyrphenol, m-cresol, 2.6-dimethylphenol, 2゜6-diethylphenol, 2.6- Dipropylphenol, 2-methyl-5-ethylphenol, 2-methyl-
6-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl6--6-propylphenol, 2-propyl-6-methylphenol, 2-propyl-6-ethylphenol, 2
, 5.6-) dimethylphenol, 2,5.6-) dimethylphenol, 2゜5, 6-) dipropylphenol, 2,6-dimethyl-6-ethylphenol, 2.
Examples include 6-dimethyl-6-propylphenol. Examples of polyphenylene ethers obtained by polycondensation of one or more of these phenols include:
Poly(2,6-cymethyl-1,4-phenylene) ether, poly(2,6-ethyl-1,4-phenylene)
Ether, poly(2,6-dipyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1)
,4-phenylene)ether, poly(2-methyl-6
--j lopyl-1,4-phenylene) ether, poly(
2-ethyl-6-propyl-1,4-)unilene) ether, 2,6-dimethylphenol/2,5.6-dolimethylphenol copolymer, 2,6-dimethylphenol/2,5. 6-) dimethylphenol copolymer, 2.
6-dimethylphenol/2,5.6-)dimethylphenol copolymer, 2,6-diprobylphenol/2,
3.6-Dolimethylphenol copolymer, Bo1I (2,
Graft copolymer obtained by graft polymerizing styrene onto 6-dimethyl-1゜4-phenylene) ether, Graft copolymer obtained by graft polymerizing styrene onto 2,6-dimethylphenol/2,5.6-) dimethylphenol copolymer Examples include merging. In particular, poly(2,6-cymethyl-1.
4-)Unilene) ether, 2,6-dimethylphenol/2,5゜6-drimethylphenol copolymer, and a graft copolymer obtained by graft polymerizing styrene to each of the former two are the polyphenylene ether type used in the present invention. It is preferable as a resin.

The vinyl aromatic hydrocarbon resin used in the composition of the present invention is a resin having at least 25% by weight of the monomer structural unit represented by the following general formula (box) in its polymer, such as vinyl aromatic hydrocarbon resin. (Here, R4 represents a hydrogen atom or a lower alkyl group, 2 represents a halogen atom or a lower alkyl group, and p is 0 or a positive integer of 1 to 3.) Listyrene, rubber-modified polystyrene (impact-resistant polystyrene)
, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-acrylic acid rubber-acrylonitrile copolymer, styrene-α
-Methylstyrene copolymer, styrene/butadiene/
Examples include block copolymers, and two or more of these may be used in combination.

In the composition of the present invention, the resin composition consisting of a polyphenylene ether resin and a vinyl aromatic hydrocarbon resin contains 5 to 95% by weight, preferably 10 to 90% by weight of the former.
, more preferably in a proportion in the range of 60 to 70% by weight.

91 The boric acid ester of fatty acid monoglyceride used in the composition of the present invention is described in Yukagaku, Vol. 29, 896-9.
It is a compound described on page 00 (1980),
A general term for compounds represented by the following general formula (III) or (transformation). These include boric acid ester of glycerin and the following saturated or H20H CH20COR2 (herein, R1 and R2 independently represent an alkyl group, an alkenyl group, and an alkynyl group having 4 to 51 carbon atoms) are unsaturated monocarbons. Obtained by reacting with an acid. The saturated or unsaturated monocarboxylic acids used include:
Valeric acid, caproic acid, enanthic acid, caffrylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, my-10-ristic acid, pentadecylic acid, valmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid , behenic acid, lignoceric acid, cerucic acid, heptaconic acid,
Montanic acid, melisic acid, lafuselic acid, undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linuric acid,
Examples include arachidonic acid, stearic acid, and isomers thereof.

The proportion of the boric acid ester of fatty acid monoglyceride in the composition of the present invention is generally selected in the range of 1 to 10 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the resin component. If the amount is less than the lower limit, sufficient antistatic performance will not be obtained, and if the amount exceeds the upper limit, the physical properties of the resulting polyphenylene ether resin composition, such as heat distortion temperature and tensile strength, will decrease.

Any method may be used for mixing these compounds with the resin component, as long as these compounds are uniformly dispersed, and the method generally used for dispersing stabilizers or plasticizers in resins may be used. can be used. For example, the above compound in liquid or solid form is added as it is or dissolved in a solvent to polyphenylene ether resin powder, thoroughly mixed with a high-speed mixer such as a Henschel mixer, and then mixed with vinyl aromatic hydrocarbon resin. A method of extruding with a twin-screw extruder is mentioned.

If desired, various elastomers or various additives that can be generally used in polyphenylene ether resin compositions may be added to the resin composition of the present invention.

The elastomer component is an elastomer in the general sense, such as A, V, Tobol-5ky.
Author” Properties and 5tructu
res of Polymers” (John Wi
ley & 5ons, Inc.

1960) on pages 71 to 78, an elastomer is defined as having a Young's modulus of 10 to 10 at room temperature.
10 dynesA-If (0,1~1o20'!;
2) means a polymer that is A specific example of an elastomer is an A-B-A'ff elastomeric block copolymer in which the double bond of the butadiene portion is hydrogenated.
B-A type elastomeric block copolymer, polybutadiene, polyisoprene, copolymer of a diene compound and vinyl aromatic compound, nitrile rubber, NyF-L/7-brobylene copolymer, ethylene-propylene di-X Examples include EPDM copolymer ('EPDM), thiocol rubber, polysulfide rubber, acrylic acid rubber, polyurethane rubber, a graft product of butyl rubber and polyethylene, polyester elastomer, polyamide elastomer, and the like. Particularly desirable are A-B-A type elastomeric block copolymers. The terminal blocks A and A' of this block copolymer are polymerized vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block or a conjugated diene block in which most of the double bonds are hydrogenated. It is desirable that the molecular weight of the B block is larger than the combined molecular weight of the A and λ blocks. The terminal blocks A and A may be the same or different, and the block is a thermoplastic homopolymer or copolymer derived from a vinyl aromatic compound in which the aromatic moiety may be monocyclic or polycyclic. .

Examples of such vinyl aromatic compounds include styrene, alpha-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylxylene and mixtures thereof. Central block B is an elastomeric polymer derived from conjugated diene hydrocarbons such as 1,6-butadiene, 2,3-dimethylbutadiene, isoprene and 1,3-pentadiene and mixtures thereof. The molecular weight of each terminal block A and N preferably ranges from about 2,000 to about 100,000, while the molecular weight of central block B preferably ranges from about 25,000 to about 100,000.
The range is approximately 1.0oo, ooo. When an elastomer is used in the resin composition of the present invention, the proportion of the elastomer in 100 parts by weight of the resin component is 0.5 parts by weight or more.

14- Fish species additives that can be used in the composition of the present invention include known flame retardants such as organic phosphate compounds, organic phosphonate compounds, or halogen-containing organic compounds;
Known stabilizers exemplified by phenols, organic phosphite compounds, organic phosphonite compounds, hydrazine derivatives, amine derivatives, metal sulfides, etc.; benzotriazole compounds, benzophenone compounds, sterically hindered amines, UV absorbers such as acid diamide rust conductors and organic nickel complexes; lubricants such as olefin waxes such as polyethylene wax and polypropylene wax; pigments such as titanium oxide, zinc oxide, and carbon blocks; glass fibers and glass peas , asbestos, wollastonite, mica, clay, talc, RR
Examples include inorganic fillers such as calcium and silica; organic fillers such as carbon fiber, amide fiber, and heat-resistant phenol resin fiber.

Hereinafter, the resin composition of the present invention will be specifically explained with reference to Examples and Comparative Examples. The amounts and percentages of each constituent component of the resin composition are expressed on a weight basis unless otherwise specified. There is.

Example 1 and Comparative Example 1 2,6-dimethylphenol/2°3.6-dolimethylphenol copolymer with an intrinsic viscosity of 0.52 dll (25°C, in chloroform) (the latter proportion is 5 mol%) 60
parts, impact-resistant polystyrene (intrinsic viscosity of the polystyrene matrix measured at 25°C in chloroform as solvent 0.89 di/11. Gel content i 6.5% in methyl ethyl ketone as solvent) 57 parts, polystyrene-polybutadiene - a polystyrene block copolymer (with a weight ratio of polystyrene and polybutadiene moieties of 30/70 and a viscosity of a 20961-toluene solution of the copolymer measured at 25°C using a Brookfield model RVT viscometer) is 1500cps) 2 copies,
Ethylene-propylene copolymer (reduced specific viscosity 2.0, glass transition temperature -49°C, measured using decalin as a solvent, concentration 0.197100ml, temperature 165°C)
1 part, boric acid ester of stearic acid monoglyceride [trade name: "Resistat PE-139J, Dai-Kogyo Kuwa-Ku"] 6 parts, triphenyl phosphate 6 parts, titanium oxide (has a rutile crystal structure, particle size 0) .3~0.
5μ), 0.4 parts of hydrogenated bisphenol A phosphite resin, and 0.6 parts of 2.21-methylene-bis(4-methyl-6-tert-butylphenol) were mixed using a Henschel mixer. The resulting mixture was placed in an AS-
Extrusion into pellets using a 50-type twin-screw extruder (manufactured by Nakatani Seisakusho), followed by a 3J-35B injection molding machine (manufactured by Taki Seisakusho) with the maximum cylinder temperature set at 280°C.
% under the condition of injection pressure 1050kg/α+7c using
An inch thick disc was molded. 4αX4m from this disk
A plate was prepared, and the surface resistivity value was measured under the following conditions (Example 1).

17- Apparatus; Ultra-Megohmmeter SM-
104 [manufactured by Toa Denpa Co., Ltd.] Voltage: 50 DV Temperature = 23°C Humidity 7296 In the above operation, the above operation was repeated without using "Regisat PE-139" at all (Comparative Example 1).

The surface resistivity values are shown below.

Example 1 2X10 Ω Comparative Example 1 100 or more As is clear from the above results, in Example 1, the surface resistivity value is reduced by at least 10 Ω, and it is clear that the antistatic performance is improved. .

Example 2 Step 18 of Example 1 was repeated except that the amount of "Regisit PE-169" used was 5 parts. It is impossible to measure the surface resistivity value with the above device, which indicates that l is less than 10 Ω. It is said that if the surface resistivity value is 10 Ω or less, the anti-static performance is very good in practical terms.

Example 3 Example 1 except that 1 part of glycerofulboreide-laurate (trade name [Emulpon S-20J, manufactured by Toho Chemical Co., Ltd.]) was used in place of 6 parts of boric acid ester of stearic acid monoglyceride in Example 1. repeated. The surface resistivity value was 8×100.

Example 4 and Comparative Example 2 2,6-dimethylphenol/2, used in Example 1
3.6-) Limethylphenol copolymer 42 parts, impact resistant polystyrene used in Example 1 53.5 parts, polystyrene-bolybutadiene-boristyrene block copolymer used in Example 1 3.5 parts , 1 part of the ethylene-propylene copolymer used in Example 1, glycerolpolide palmitate (trade name [Emulpon S 4
0J, manufactured by Toho Chemical Co., Ltd.), 7 parts of the titanium oxide used in Example 1, 0.4 part of hydrogenated bisphenol A phosphite resin, and 2.2+-methylene-bis(4
-Methyl-6-tert-butylphenol) was mixed using a Henschel mixer. Hereinafter, a test piece was prepared in the same manner as in Example 1, and the surface resistivity value was measured (Example 4).

"The operation of Example 4 was repeated except that Emalpon S-4DJ was not used (Comparative Example 2).

The surface specific resistance value is as follows.

Example 4 8X10 Ω Comparative Example 2 100 or more Example 5 and Comparative Example 3 2,6-dimethylphenol/2, used in Example 1
3.6-drimethylphenol copolymer 68 parts, impact-resistant polystyrene used in Example 1 32 parts, glycerol borate oleate (trade name "Emulpon S-80")
4, manufactured by Toho Chemical Co., Ltd.) 5 parts, triphenyl phosphate 14 parts, titanium oxide used in Example 1 7 parts, tris(nonylphenyl)phosphite 0.4 parts and 2.6-di-tert-butyl- 0.6 part of p-cresol was mixed using a Henschel mixer.

After extruding and pelletizing under the same conditions as Example 1,
A disk having a thickness of % inch was molded using an injection molding machine with a maximum cylinder temperature of 265° C. under conditions of an injection pressure of 1050 kg and 7 m·. Using this disk, the surface resistivity was measured in the same manner as in Example 1 (Example 5)
.

[The operation of Example 5 was repeated except that Emalpon S-80J was not used (Comparative Example 3).

The surface resistivity values are as follows.

Example 5 5X10 Ω Comparative Example 3 100 or more 21 - Example 6 and Comparative Example 4 Poly(2,6-dimthyl-1,4-phenylene) ether with an intrinsic viscosity of 0.53 di/11 (in chloroform at 25°C) 35 parts, impact resistant polystyrene used in Example 1 61 parts, polystyrene-polybutadiene-polystyrene block copolymer used in Example 1 4
part, glycerol borate isostearate (trade name [Emalpon S-16DJ, manufactured by Toho Chemical Co., Ltd., +1
) 10 parts of diphenyl phosphate, 5 parts of the titanium oxide used in Example 1, 0.25 parts of hydrogenated bisphenol A phosphite resin, and 2.2'-methylene-bis(4-methyl-6-tert- butylphenol) was mixed using a Henschel mixer. After extruding and pelletizing under the same conditions as in Example 1, using an injection molding machine with the maximum temperature of the cylinder set at 240°C, the injection pressure was 1050' and 9/611' to form a % inch thick wooden circle. The board was formed. Using this disk, the 22-surface resistivity was measured in the same manner as in Example 1 (Example 6).

“Example 6 except that Emalpon S-16DJ was not used.
This operation was repeated (Comparative Example 4).

The surface resistivity values are as follows.

Example 6 4X10Ω Comparative example 4 100 or more Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Representative Kazuyoshi Nagano 23-

Claims (1)

[Claims] A polyphenylene ether resin composition with suppressed electrification, which is made by blending a boric acid ester of fatty acid monoglyceride with a resin composition consisting of a polyphenylene ether resin and a vinyl aromatic hydrocarbon resin.