JPS6090255A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved molding properties, dimensional stability, and rigidity strength, obtained by blending a polyphenylene ether with talc having adjusted particle diameters. CONSTITUTION:(A) 100pts.wt. polyphenylene ether resin obtained by subjecting one or more monocyclic phenols shown by the formula (R1 is 1-3C alkyl; R2 and R3 are H, or 1-3C alkyl) to polycondensation or graft copolymer of the polyphenylene ether and a vinyl aromatic compound (including one blended with other resin component and/or elastomer) is blended with (B) 5-150pts.wt., preferably 10-120pts.wt. talc having 50% weight-average particle diameter adjusted to <=10mu, preferably <=6mu.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition containing talc. More specifically, polyphenylene ether resin has a weight of 50% (average particle size of 10μ or less).
Polyphenylene ether-based tree 1ff with improved rigidity strength and dimensional stability blended with C particle size controlled talc
Concerning the IIal product.

Polyphenylene ether resin is disclosed in U.S. Patent No. 5506
No. 874, No. 5406875, No. 3257557,
It is a known resin disclosed in various known documents such as the specifications of No. 5257558 and No. 4011200 or Japanese Patent Application Laid-open No. 126800/1983. Although polyphenylene ether resin has excellent heat resistance, it requires extrusion and molding at high temperatures.

Extrusion and engraving at high temperatures lead to deterioration of the polyphenylene ether resin, and as a result, the excellent performance inherent to the polyphenylene ether resin is impaired.

As a method to improve this drawback, for example, US Pat.
No. 586,455 discloses a resin composition containing polyphenylene ether and a vinyl aromatic resin. However, in this resin composition, the excellent properties originally possessed by polyphenylene ether, such as rigidity strength and heat resistance represented by heat distortion temperature, are impaired.

Fillers are used to improve this drawback or to more effectively exhibit the inherent characteristics of polyphenylene ether. Commonly used fillers include glass fibers, glass vi-x, carbon fibers, asbestos, titanates and their whiskers, silicates, calcium carbonate or silica. For example, JP-A-52-125
μM+1 discloses a composition consisting of polyphenylene/ether, styrene resin and calcium silicate; JP-A-53-84049 discloses a composition consisting of polyphenylene ether resin alone or in combination with an impact modifier. A composition comprising a polyphenylene ether resin mixture, a mineral filler, and a plasticizer; Publication No. 57-501966 contains a polyphenylene ether resin, an impact-resistant rubber-modified polystyrene, a non-iron oxide mineral filler, and an effective amount of plasticizer. Compositions containing the agents are each disclosed.

Conventionally, in polyphenylene ether resin compositions,
Glass fiber is generally used as a filler that increases rigidity strength represented by flexural modulus and heat resistance represented by heat distortion temperature. The use of glass fibers certainly achieves the intended purpose and has the advantage of reducing molding shrinkage in the direction of the molding flow. On the other hand, the molding shrinkage rate in the direction perpendicular to the molding flow direction is hardly improved.
Anisotropy occurs in molding shrinkage rate.

Further, glass fiber is relatively expensive, and the moldability of the resin composition itself is not good.

On the other hand, with the improvement of molding technology, there has been an increasing demand for thinner or finer molded products, and dimensional stability during molding has become an important factor to consider. Filler-containing polyphenylene ether resin compositions are no exception. However, as mentioned above, when glass fiber, which is a general-purpose filler, is used, anisotropy occurs in the molding shrinkage rate, so from the viewpoint of dimensional stability, glass fiber is not necessarily a satisfactory filler. In cases where such rigidity and strength as to necessitate the inclusion of glass fibers are not required, and where dimensional stability or good formability is required, glass fibers are rather unsuitable. Therefore, in response to such requests, it is desirable to use fillers other than glass fiber, but if calcium carbonate is used, for example, the molding shrinkage rate will not be improved;
Furthermore, the degree of improvement in rigidity and strength σ] is also small. Further, when using wollastonite, the above-mentioned requirements are satisfied to a certain extent, but the dimensional stability still has anisotropy and is not necessarily an era name.

In addition, 1 conventionally commonly used talc, 0
．． When using talc, which is a mixture of various particles with a particle size in the range of 1 to 60μ, and has a wide particle size distribution and coarse particles with a weight average particle size of more than 10μ, the above-mentioned Almost all requests are met.

However, in this case, the rigidity strength does not reach the level of blending glass fiber, and therefore, an improvement is desired in which the rigidity strength can also be simultaneously improved by using a refrigerant.

As a result of intensive studies aimed at achieving such improvements, the present inventors have found that by using grain size-adjusted tar, polyphenylene resin has good moldability, excellent dimensional stability, and high rigidity and strength. It has been found that an ether-based resin composition can be obtained.

That is, the present invention is a polyphenylene ether resin composition comprising a polyphenylene ether resin and talc whose particle size is adjusted to have a 50% weight average particle diameter of 10 μm or less.

The particle size controlled talc used in the composition of the present invention is
Coarse particles with a particle size of 15μ or more are removed from conventional commercially available talc, and the content of particles with a particle size of 15μ or more is 5% or less, and
Talc whose particle size has been adjusted so that the 0% weight average particle size is 10μ or less. As K, talc whose particle size is adjusted to have a weight average particle size of 5096 of 6 μm or less is more preferably used.

The "5096 ffi amount average particle diameter" defined by the talc used in the present invention can be determined by determining the ffi amount particle particle size distribution. An example of a device for measuring the particle size distribution of heavy speckle particles is a light transmission type particle size distribution measuring device. In the case of talc, a 0.2% sodium pyrophosphate aqueous solution is used as a dispersion medium to appropriately disperse the talc. After performing centrifugal sedimentation for a predetermined period of time, the light transmittance of the dispersion liquid is repeatedly measured. Interpret or calculate the particle size and weight cumulative distribution from the relationship between centrifugal sedimentation time and light transmittance, and draw a cumulative particle size distribution map.
96-grain average particle diameter is t'J. The above-mentioned light transmission type particle size distribution analyzer is commercially available from Seishin Enterprise Co., Ltd.

The grain size-controlled talc used in the present invention can be used as is, but it can also be treated with a surface treatment agent such as a silane cabblinob agent typified by r-7 minobrovir silane. A better improvement effect can be achieved by using .

The above-mentioned particle size-adjusted talc used in the present invention is, for example, the product name "Microcut" (Hayashi Kasei Co., Ltd.), the product name "Micron White #5υυO5" (Hayashi Kasei Co., Ltd.), the former product name "Zybrabond" ( Kaai Co., Ltd.), product name [Mistron Talc 1100J (Tatsumori Co., Ltd.) or product name [Mistron Talc 5076J]
(Tatsumura Co., Ltd.) and can be easily obtained commercially.

The amount of talc blended in the resin composition of the present invention is not particularly limited as long as the rigidity and strength of the resulting resin composition is improved, but it is usually 5 to 150 parts by weight based on 100 parts by weight of the resin component. The amount may be selected within the range of 10 to 120 parts by weight. If the amount exceeds the upper limit, the workability and crosstalk will decrease, and if the amount is less than the lower limit, no improvement in rigidity or strength will be observed in the resin composition obtained.

The polyphenylene ether resin used in the composition 9 of the present invention refers to polyl-1 obtained by polycondensing one or more monocyclic phenols represented by the general formula (1) (herein, R1 is carbon 1d'1 ~3 lower alkyl groups,
1 and R5 are hydrogen atoms or lower alkyl groups having 1 to 6 carbon atoms, and a lower alkyl 14 substituent must always be present at the ortho position of at least one of the hydroxyl groups.
'x. ) Phenylene ether: refers to a graft copolymer having polyphenylene ether as its base obtained by graft polymerizing a vinyl aromatic compound to this polyphenylene ether. This polyphenylene ether may be a homopolymer or a copolymer. Furthermore, the definition of polyphenylene ether resin in the present invention also includes a composition obtained by mixing the polyphenylene ether with other resin components and/or elastomer components (details of these components will be described later). .

Examples of the monocyclic phenol represented by general formula (1) inJ include 2,6-dimethylphenol, 2,6-
Dimethylphenol, 2,6-dipropylphenol,
2-methyl-6-ethylphenol, 2-methyl-6-
Propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2.5-dimethylphenol,
2゜6-dimethylphenol, 2,6-dipropylphenol, 2-methyl-5-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-methylphenol, 2-ethyl-6-p Pirphenol, 2
-propyl-6-methylphenol, 2-propyl-5
-Ethylphenol, 2,5.6-)dimethylphenol, 2,5.6-driethylphenol, 215.6-
) Dipropylphenol, 2,6-dimethyl-6-ethyl-phenol, 2,6-dimethyl-6-butylphenol, and the like. Examples of polyphenylene ether 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-dibu-
Pyr-1,4-phenylene) ether, poly(2-methyl-6-ether)/L'-1,4-phenylene) ether, poly(2-methyl-6-7'p pyl-1,4-phenylene) ) ether, poly(2-ethyl-6-bropyru-1,4-phenylene) ether, 2,6-dimethylphenol/2,5.6-)limethylphenol/-, 2. +5-dimethyl 7er/-el/2,5.6-)!
+Ethylphenol copolymer, 2.6-ethylphenol/2,5.6-)limethylphenol copolymer, 2
, 6-diprobylphenol/2,5.6-drimethylphenol copolymer, graft copolymer of styrene grafted onto poly(2,6-dimethyl-1°4-7enylene)ether, 2,6- Dimethylphenol/2
, 5.6-) Graft copolymers in which styrene is graft-polymerized to trimethylphenol copolymer a. In particular, poly(2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol/2,5゜6
-dolimethylphenol copolymer and a graft copolymer in which styrene is graft-polymerized to each of the former two are preferable as the polyphenylene ether resin used in the misfire 1IIJ.

The other resin components and other elastomer components mentioned above to be mixed with the polyphenylene ether include the following. A vinyl aromatic resin is particularly suitable as the resin component, and the monomer structural unit represented by the following general formula (II) is incorporated into its polymer 4 (wherein, R4 is a hydrogen atom or a lower alkyl group, and Z is a halogen atom or lower alkyl group, and p t! is 0 or a positive integer from 1 to 6), and is a resin containing at least 25% by weight or more, such as polystyrene, rubber-modified polystyrene (impact-resistant polystyrene), styrene, etc. Norbutadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-acrylic acid rubber
Examples include 7-acrylonitrile copolymer, styrene-α-methylstyrene copolymer, styrene-butadiene-Plutz copolymer, etc., and two or more of these may be used as a mixture.

The elastomer component is an elastomer in the general sense, for example A, V, Tobolsky
Author + Properties and 5tructure
es of Po1y-111erS'' (Job
n Wiley & 5ons, Inc., 1960
You can cite the definition adopted on pages 71 to 78 (2013),
Elastomer has a Young's modulus of 105 to 10 at room temperature.
' dynes/cm□ (o, 1~10'20
%) "'C" means a certain polymer. Specific examples of elastomers include A-B-* type elastomeric block copolymers, A-B-A' type elastomeric block copolymers in which the double bond of the polybutadiene portion is hydrogenated,
Polybutadiene, polyisoprene, copolymer of diene compound and vinyl aromatic compound, radial teleblock copolymer, nitrile vinyl A1 ethylene-propylene copolymer, ethylene-propylene-diene copolymer (EPDM)
), thiocol rubber, polysulfide rubber, acrylic acid rubber, polyurethane rubber, graft products of butyl rubber and polyethylene, polyester elastomer, poly7mide elastomer, polyurethane elastomer, and the like. In particular, A-B-x type elastomeric block copolymers are preferred. The terminal blocks A and N 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. , the molecular weight of the B block is preferably greater than the combined molecular weight of the A and N blocks.

The terminal blocks A and N 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 vinylaromatic compounds include styrene, (I-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylenetalene and mixtures thereof. The central block B is a conjugated diene hydrocarbon, such as 1. Elastomeric polymers derived from 5-butadiene, 2,6-dimethylbutadiene, isoprene and 1,5-pentadiene and mixtures thereof. Each terminal block A
and A' preferably have a molecular weight of about 2,000 to about i
oo, ooo, while the molecular weight of central block B is preferably about 25. ODD ~ about i, ooo, ooo
is within the range of

When the resin composition of the present invention contains the above-mentioned vinyl aromatic resin and/or elastomer as a resin component in addition to polyphenylene ether, the proportion of polyphenylene ether in the resin component may vary depending on the purpose of producing the resin composition. Although it varies, it is usually 5% by weight or more.

The resin composition of the present invention may contain various additives, fillers, and other components depending on the purpose. for example,
Sterically hindered phenols, organic phosphites, phosphites, phosphonaceous acids, cyclic phosphonites, hydrazino derivatives, amine derivatives, carbamate derivatives,
Stabilizers such as thioethers, phosphoric triamides, benzimidazole derivatives, metal sulfides; ultraviolet rays such as hesozotriazole derivatives, benzophenone derivatives, salicylate derivatives, sterically hindered amines, oxalic acid diamide derivatives, organic nickel complexes, etc. Absorbent: Olefin wax as a lubricant such as polyethylene wax or polypropylene wax; Triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, phosphate obtained from an alpha compound of isopropylphenol and phenol Phosphate flame retardant plasticizers represented by dimers of cresyl diphenyl phosphate; decabromo biphenyl, pentapromotole/, thecabromo biphenyl ether, brominated bisphenol A1 derived from brominated bisphenol A Brominated flame retardants such as polycarbonate oligomers and brominated polystyrene; pigments such as titanium oxide, zinc oxide, and carpon plastic; glass fibers, glass peas, asbestos, wollastonite, mica, Inorganic fillings represented by clay, calcium carbonate, silica, etc. Metal flakes represented by full flakes such as copper, nickel, aluminum, zinc, etc. Metal fillings represented by aluminum fibers, aluminum alloy fibers, brass fibers, stainless steel fibers Examples include organic filler phases typified by carbon fiber and aromatic polyamide fiber. The addition i of these other components varies depending on the type of component used or the purpose of addition.

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 Examples 1-4 2.6-2 methylphenol (95 mol%)/with intrinsic viscosity o, s2dWg (in chloroform at 25 °C)
65 parts of 2,5.6-)limethylphenol (5 mol%) copolymer, impact-resistant polystyrene (intrinsic viscosity of polystyrene matrix measured at 25°C using chloroform as solvent, 95 dg/g , gel content prepared using a methyl ethyl ketone-acetone mixture as a solvent 17.1 weight 96) 55 parts, triphenyl phosphate 14 parts, hydrogenated bisphenol A7 osphite resin 0.4 parts, 21z-methylene-bis(4-methyl -6-tert-butylphenol) 0.6 part and 50% weight talc whose particle size is adjusted to 6.9μ (manufactured by Hayashi Kasei Co., Ltd., trade name "Microcut")
49.6 parts were thoroughly mixed using a Henschel mixer. The resulting mixture was pelletized by extrusion using an AS-50 twin-screw extruder (manufactured by Nakadai Kikai Seisakusho) with the maximum cylinder temperature set at 290°C, and then the maximum cylinder temperature was set at 280°C. 5J-65B type injection molding comb (name 82% production! Injection pressure 1υ50
A test piece was molded using a mold.

The molding shrinkage of a 4-inch diameter disc in a direction parallel to and perpendicular to the resin flow was measured and used as a measure of dimensional stability. In addition, flexural modulus was measured as a representative of rigidity strength. Furthermore, as a measure of moldability, the melt flow value was measured using a Koka type flow tester.

The same operation as in Example 1 was performed except that talc was not used (Comparative Example 1). Furthermore, in the operation of Example 1, 4936 parts of glass fiber (Comparative Example 2), 49.5 parts of wollastonite (Comparative Example 5), or 49.6 parts of calcium carbonate (Comparative Example 4) was used in place of talc. Similar operations were performed using

Characteristics (I) are shown in Table 1.

As is clear from the results in Table 1, the resin composition of the present invention exhibits good dimensional stability, flexural modulus, and moldability.

In addition, the tensile strength in Example 1 was 735~, and the bending strength was 1075%.

Examples 2 to 6 and Comparative Examples 5 and 6 In Example 1, instead of talc having a 50% weight average particle diameter of 5.9μ, various talcs as shown in Table 2 were used,
Similar operations were performed using the same composition as in Example 1 (Examples 2 to 3).
6).

Further, in Example 1, the 50% weight average particle diameter was 6.
In place of the 9 μm talc, a conventionally widely used talc whose particle size had not been adjusted was used, and the same operation was performed with the same composition as in Example 1 (Comparative Examples 5 and 6).

The results are also shown in Table-2.

As is clear from the results in Table 2, it is clear that the composition of the present invention has improved tensile strength, bending strength, and bending elastic modulus compared to using talc whose particle size is not adjusted.

Examples 7 and 8 In Example 1, the content of talc was changed to 49.6 parts (50%
) to 12.8 parts (1096) (Example 7).

Further, Example 1 was repeated except that the content of talc in Example 1 was changed from 49.3 parts to 115 parts (50%) (Example day).

The results are shown in Table 6 together with the results of Example 1.

Example 9 2,6-dimethylphenol/2, used in Example 1
5.6-) 100 parts of 11-methylphenol copolymer,
4 parts of triphenyl phosphate, tetrakis (2,4
-4,4'-biphenylene diphosphonite (0.4 part), 0.6 part of 2.6-di-tert-butyl-p-cresol, and the talc used in Example 1 49.5 parts were thoroughly mixed using a Henschel mixer. The resulting mixture was pelletized by extruding AS-10 with a cylinder maximum temperature of 310°C using a twin-screw extruder, and then 5J-15B with a cylinder maximum temperature of 520°C.
A test piece was molded using a mold injection molding machine under conditions of 105°B. The physical properties measured using the obtained test piece were as follows:
It is as follows.

Tensile strength: Made from 820 Bending strength: Made from 1210 Flexural modulus: Made from 67500 Example 10 2,6-dimethylphenol/2, used in Example 1
5.6-)! The same operation as in Example 1 was repeated, except that 40 parts of the 1-methylphenol copolymer and 60 parts of the high-impact polystyrene used in Example 1 were used, and triphenyl phosphate was not used.

The results are as follows.

Tensile strength: 660~ Bent strength: 110011 Flexural modulus: 64300~ Patent applicant Mitsubishi Gas Chemical Co., Ltd. Representative Nagano (11Kichi)

Claims (1)

[Claims] A polyphenylene ether resin composition comprising a polyphenylene ether resin and talc whose particle size has been adjusted to 5 (single ffi average particle size of 10μ or less).