JPS5863745A - Aromatic polyether resin composition - Google Patents

Abstract

PURPOSE:The titled composition useful as an engineering resin, having improved gloss, providing a metal inserted molded article having improved cracking resistance, obtained by blending a specific polyphenylene ether with rubber- reinforced high-impact polystyrene. CONSTITUTION:20-80wt% polyphenylene ether comprising a compound shown by the formulaIor formula II (R1-R6 are 1-4C alkyl except tert-butyl, aryl, halogen, H, etc.; R5 and R6 are not H simultaneously) as a repeating unit, having an intrinsic viscosity [eta] (30 deg.C chloroform solution) of the constitutional unit shown by the formulaIor units shown by the formulaIand formula II of 0.50-0.80, and an eluation ratio of gel permeation chromatography of a polystyrene having a molecular weight corresponding to <=3,000 of <=5wt% is blended with 80-20pts.wt. rubber-reinforced high-impact polystyrene comprising a polystyrene resin phase (preferably intrinsic viscosity of 0.6-1.0) dispersing rubber-like polymer in a state of island.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes polyphenylene/ether (hereinafter abbreviated as ppie) resin and rubber-reinforced Hii/Pakure 1 styrene resin (
The present invention relates to a thermoplastic resin composition mainly consisting of HIP8 (hereinafter abbreviated as HIP8). The present invention relates to an aromatic 4-reactor resin composition that has a good gloss and improved scratch resistance, especially in molded articles with metals inserted therein. More specifically, the present invention mainly consists of PPg and HIFB with controlled molecular weights and low abundance ratios of medium and low molecules,
This article relates to a resin composition that is less likely to cause cracking in all-steel insert molded products while maintaining good gloss.

The present invention also relates to a resin composition comprising ppg, HIPli, and a styrene resin, which has a controlled molecular weight, has a low abundance of medium and low molecular weight molecules, and has few foreign structures. In addition, the present invention has good appearance such as good gloss and hardly noticeable weld parts, and is suitable for large molded products such as molded products with metal inner parts or molded products with self-tag structure. The present invention relates to a resin composition that does not easily cause cracks even when a molded article to which internal or external stress is applied comes into contact with oil, a chemical solution, a chemical, or a gas.

PPIIIil has mechanical properties, electrical properties and resistance to 1
lIIIt! It is known as a resin with excellent E.
Poor moldability and poor impact resistance. In order to improve these shortcomings, Time 1@43-17812, USA'FF
In 'll'FII338343S, 4
Proposals have been made to blend listyrene or acrylonitrile-tutadiene-styrene terpolymer to improve processability and impact resistance at the same time. Also, in No. 1i851-284i5e, PPI resin and HIF
In particular, the resin composition consisting of B has a rubber particle size of 1 to 2.
It is stated that in the case of μ, a product with good gloss and good impact resistance can be obtained, but these compositions have poor stress cracking resistance and have a fatal flaw in practical use.

A resin composition consisting of a PPB resin and a poly-alpha-olefin is described in U.S. Pat. but,
The impact resistance of this resin composition is insufficiently improved, and what is more undesirable is that when the amount of polyα-olefin added increases, the gloss of the surface of the molded product decreases. Hydrogenated nine styrene! PPE by addition of tagene copolymer
Regarding the modification of resin, for example, Japanese Patent Application Laid-Open No. 11-551-835
It is disclosed in No. 8. Molded products obtained using these technologies have high gloss on their outer surfaces, and molded products with a structure where welds occur have long weld lines and deep weld widths. , it cannot be said that the appearance is satisfactory. In addition, numerous attempts have been made to improve compositions of ppie resin and other resins by focusing on the properties of resins other than ppg resin. In this way, most of the techniques for modifying ppg resin compositions focus on the properties of components other than the ppg component and attempt to modify the resin composition by focusing on the ppIA component. There are few attempts to modify the composition.

Examples that focus on the PPE component itself include Japanese Patent Publication No. 45-25992 and Japanese Patent Application Laid-open No. 51098-1982.
Only a technique has been disclosed that attempts to improve molding i by increasing the medium/low molecular weight portion of ppg resin and broadening the molecular weight distribution. These technologies improve moldability and
One of the effects is to improve the appearance, but number 1! It has the disadvantage of having a small degree of stress and decreasing stress cracking resistance.

In general, compositions of PPI resin and HfF4 have been applied industrially, but in addition to moldability and impact resistance, compositions of PPI resin and HfF4 have been applied industrially. Special features such as tapping properties.

The ability to attach a large number of parts to a plastic molded product, for example, the ability to attach electrical components and other parts directly to the Rusnak housing without using a special chassis, saves materials and reduces man-hours. This is a huge industrial advantage, and plastics have been used extensively. This is one of the factors.

To attach these parts, you can take advantage of the moldability and formability of plastic to create a so-called gas section and screw the metal screw directly into it (self-tapping), or you can use a method that uses metal holes. The method of using recessed inserts is well known to the nuclear industry. In such a method, when self-tapping is used, the fastening force (baka screw torque) of the resin used must be very strong, and in the case of metal inserts, the heat between the plastic and metal must be strong. Due to differences in physical properties, accidents such as damage to the plastic part of the inner wrap often occur during use, assembly, and sometimes during storage after molding. Insa,
- It is strongly desired that the cracking resistance be excellent.

An object of the present invention is to provide a 9 ppm resin composition with excellent surface gloss, appearance such as weld areas, and stress crack resistance. If these characteristics can be improved,
The practical value of PPM resin as an engineering resin will be dramatically improved.

The present inventors have focused particularly on the ppz resin component in the resin composition, and have conducted extensive studies with the aim of obtaining a molding material that has a favorable appearance and excellent stress cracking resistance at the practical stage as described above. In conclusion, we discovered that the properties of the molding material are greatly influenced by the properties of the PPX resin itself, which is the raw material for the resin composition, and variously investigated the relationship between the properties of the PPM resin as a constituent component and the physical properties of the composition. As a result, the present invention was achieved.

That is, in the present invention, the residue of the following general formula is a repeating unit in which Rs and B are not hydrogen at the same time, and the structural unit is [I], or [1) and H(
if) Colored 4-lifenylene ether (ppg)
20 to 80% by weight and rubber-reinforced Hi-In/4Kt4 Listere/(HfF4) 80 to 20% by weight, and the intrinsic viscosity of the PPE [η] (30°C, chloroform solution) is 0. 50 to 0.80, and polystyrene molecular weight a, o o o phase, r rubermeation chroma)/47 ((OP-C) elution area is 5
The object of the present invention is to provide a resin composition characterized in that it uses PPIC having a weight of less than -.

The present invention further provides the above-mentioned PPIC20 to 80% by weight and Hf
A composition consisting of F4 and a styrene resin of 80 to 20% by weight, in which the PP resin (30°C, chloroform solution) is in the range of 0.5 to O,SO, and Of! GPCI with a molecular weight of listyrene equivalent to 3,000 or less
The present invention provides a resin composition characterized in that it uses PPI having a weight of 5 or less.

(9) The present invention provides the above-mentioned composition, wherein ppi8 is poly(2,6-dimethyl-1,4-fuunisine ether), and the underarm PPE from a dichloromethane solution containing 1 weight of the ppi is The present invention also provides a resin composition in which the amount of precipitation (after standing at 23° C. for 5 hours) is 70% by weight or more.

Furthermore, in the above composition, the volume average particle diameter (II) of the elastic phase of HIFg, which is the other component,
#1.0-a, 5 fi-”e leg, and 17 and i.

A resin composition using HIPil in which the ratio (Xma/i) of the number average particle diameter of the wrinkled elastic body phase is 3.0 or more is also included in the present invention as a preferred embodiment of the present invention. It is something.

The PPM of the present invention has the general formula is not hydrogen.

is a repeating unit, and the constituent units are [1] or (1) and (11).

A typical example of a homopolymer of PPIC is Isu(2,6
-dimethyl-1,4-fuunisine) ether, poly(2
-Methyl-6-niteryl,4-phenylene)ether%Isu(2,@-/ethyl-1,4-phenylene/)ether,bori(2-ether-6-feng!ropyru1.4-y
enylene) ether, Isu(2,6-s)-mfa
di-1,4-phenylene)ether%d')(2-)
Chil-6-Otori 1,4-phenylene) ether,
/su(2-ethyl-6-isopropyl-1,4-phenylene)ether, fsu(j!-/thiru-6-chloro-1
．． 4-phenylene)ether, Isu(2-methyl-6-
Hydo o4 cyenalu 1.4-7 enylene) ether, 4
1) Homopolio-(2-methyl-6-chlorotetra-1,4-phenylene) ethers can be mentioned.

The phenylene ether copolymer has the general formula % (where Rmm Rms Ra% II- is t@rt-tutyl group (alkyl group having 1 to 4 carbon atoms, aryl group,
) 1a gun, water volume, etc. Jl, 1lss
凰- is not hydrogen at the same time. ) U-cresol represented by 2,3. @-) Includes I-refined/ether copolymers mainly consisting of a 4-7-enylene ether structure obtained by copolymerizing an alkali-substituted phenol such as trimethylphenol.

Intrinsic viscosity of PPE resin used in the present invention [η]
In addition, the quantification of the GPC eluted portion is determined by the following method based on a conventional method.

The intrinsic viscosity [η] was measured at 30° C. using an Ubbelohde viscosity needle and using chloroform as a solvent.

In addition, 4 Listile 7 molecular weight a, o o o and 10.
The following method can be used to quantify the GPC@ output portion of PPI below 000.

The device is HLC-802UR manufactured by Toyo Soda Kogyo Co., Ltd., and the column is manufactured by the company I! G5000H%04000H1G300
0H and a2s00B, the detector uses a differential refraction needle,
Using chloroform as a mobile phase, measure cpc*# at 40° C. at a sample concentration of 0.511 fPPI. When determining the relationship between elution time and molecular weight, l is used as a standard substance.
Listerene was used. Calculate molecular weights of 3,00 G and 10,000 or less from the molecular weight distribution and area ratio of PPg, and measure the amount of PPI single styrene 7 molecular weights a, o o o and eluted portions of 10,000 or less. Shimaru.

Note that even if the ppm components can be extracted from the composition by the method described below, each value can be calculated according to the method described above.

In Honjitsu IJj, the composition of PPE, which is the main ingredient, [
] is less than 150, the stress cracking resistance is poor.

This rounding [wisdom] is G, 510 or more, preferably O, SS
The above is desirable; if [ma] exceeds O or SO, the appearance such as gloss and weld portions will be poor.

This rounding [ma] is less than or equal to O, SO, more preferably 0.7
Desirably 5 or less.

When [S] is in the range of O, SO to 0.80, as the ppg viscosity increases, the crack resistance is slightly improved, but especially for medium and low molecular weights equivalent to 4 listerene molecular weight a, o o o. If the polarization is at a ppm ratio, the improvement will be even greater.

In addition, I listere 7 molecular weight 10.000 by GPC analysis
When the eluted portion of 41i or less exceeds 8 weight, the moldability is improved, but the stress cracking resistance is reduced. This rounded molecular weight is 10. The elution portion equivalent to Goo or less is preferably 8 weight or less, and more preferably the present gI4 authors have found that the P of the present invention
As a result of further investigation to find the optimum PE component, in addition to the above-mentioned characteristics of the ppm component, in the case of PPN being 4(2゜6-dimethyl-1,4-phenylene) ether, the PPM component was changed to 5. If the amount of the component precipitated from a heavy dichloromethane solution at 23°C for 5 hours is less than 70% by weight, the appearance will not be better, and the stress cracking resistance will be improved by 4 or 9. I discovered that 4 is not the case. It is more preferable that the amount of precipitation is 80% by weight or more.

In the present invention, ppm is 4 so(2,6-nomethyl-1
．． 4-Phenylene) ether with ii base metal, sapphire ppg W
The properties can be extracted from the composition and determined by the method described below.

The 6IO composition is added to 200-g of chloroform, shaken at room temperature for 3 hours, and then centrifuged at 52,0 OOG for 4 seconds to separate an insoluble portion and a solution portion. The S liquid portion was carefully dropped into 1,000 aa methanol under stirring to cause reprecipitation. Thereafter, the precipitate was separated using a 04 Messier glass filter, and 1,000 methanol was poured onto the filter to wash it. Thereafter, the P-separated material was taken out and dried under reduced pressure in a nitrogen atmosphere at 145 tl for 1 hour to prepare a sample II#l. In this case, the solvent or anti-pollution agent can be appropriately selected depending on the properties of the other resins and additives.

The content of (2,@-dimethyl-1,4-72-2) ether was determined by infrared spectroscopy, and the sample was dissolved in dichloromethane so that the concentration of this component was 5% by weight. let Thereafter, the solution was heated at -5°C for 2
The mixture was left undisturbed for 4 hours to precipitate the poly(2°6-dimethyl-1,4-phenylene)ether component. Thereafter, the components were separated using a 04-mesh glass filter, washed with dichloromethane on the glass filter, and the axillary part was dried under reduced pressure at 145C for 30 minutes in a nitrogen atmosphere to prepare sample (2).

Using an Ubbelohde viscosity needle for sample I, determine the intrinsic viscosity at 80°C using chloroform as a solvent,
The intrinsic viscosity [da] of poly(2,6-dimethyl-1,4-phenylene) ether, which is a constituent component of the resin composition, can also be determined.

Further, the amount of 4-(2,6-dimethyl-1,4-phenylene) ether precipitated from the dichloromethane solution can also be determined by the following method.

Sample according to infrared spectroscopy! 4th (2,6-
The content of dimeter-1,4-phenylene ether was determined, and the component was dissolved in dichloromethane to a concentration of 5% by weight, and the stand was left standing at 23°C. Once dissolved in dichloromethane, 94% (2,6-dimethyl-1
．． 4-722/) Ether is J, polym@r
8g1. II 7.205 (1969) and US li.
! 14I Patent No. 3,644,227 according to the well-known principle. After standing for 5 hours, the precipitate was separated using a G4 mesh glass filter, washed, dried, and weighed to determine the amount of precipitate.

In the present invention, the content of PPM in the resin composition is preferably 20 to 80 parts by weight, preferably 25 to 70 parts by weight. If the content of PPE is less than 20 parts by weight, the improvement effect of PPK will not be sufficiently exhibited. On the other hand, if the content exceeds 80 parts by weight, the properties of Pl'l itself will deteriorate in fluidity and the appearance will not be sufficiently improved, which is not desirable.

The method for producing PPN used in this study is not particularly limited, but using a normal metal complex as a catalyst,
It is obtained by subjecting a specific 2,6-disubstituted phenol to an in-liquid oxidation reaction. Any catalyst may be used as long as it promotes the oxidative polymerization reaction of 2,6-disubstituted phenols, but a metal complex consisting of a metal salt and an amine compound is usually used.

If necessary, a reaction accelerator such as p1 alkali metal hydroxide or alcohols may be present in the catalyst.
As the polymerization reaction solvent, any solvent that can dissolve the 2,6-/substituted phenol and is inert to the reaction can be used. In this case, the polymerization reaction solvent may be one that does not dissolve PPM at all, or may dissolve only a portion of it. For example, when a mixture of a good solvent for PPE such as toluene, xylene or edelpenyan and a non-solvent such as alcohol is used as a solvent, high molecular weight PPK is precipitated in the form of particles and becomes a slurry. By controlling the solvent composition and extracting only slurry particles, PPE suitable for practicing the present invention can be obtained. The polymerization reactor is a batch type and has 4 continuous types with a capacity of 4jL.

As the polymerization temperature, a temperature range of 40 to 60°C is selected, and preferably a temperature range of 40 to 50°C is suitable for obtaining the PPB of the present invention. The preferred PPE used in the present invention can be manufactured by the method described above by selecting the purity of the raw material monomer.

Rubber-reinforced high-in/4-ct 4-listerene (
HIP&) is a resin phase containing I listere/ and rubber-like polymers dispersed in island-like form.In the presence of a com-like polymer, styrene monomer is oxidized in the presence of a radical polymerization initiator. No. 9 is produced by a method such as bulk polymerization, solution polymerization, bulk suspension polymerization, or emulsion polymerization in the absence of the polymer.

As the rubber, tsutatsuencom, suderene-butadiene copolymer rubber, etc. are used.

The intrinsic viscosity f (30'c, chloroform solution) of the polystyrene resin phase is 0.6 to 1. OC) 4 is preferred.

As mentioned above, the ratio of PPM and 1iIP8~ is
If the PIC resin exceeds 80 parts by weight, processability will be insufficient and it will be unsuitable for many applications.
Since the heat resistance, which is a characteristic of M, is gradually lost, it is not practical. Additionally, the larger the amount of rubbery polymer in the resin composition, the higher the impact strength and crack resistance;
As a structural part, it is undesirable because the self-tapability and appearance performance, which are important characteristics of 060 component fastening, deteriorate.
: The amount of the comb-like polymer is suitably in the range 8 of LS-10% by weight, preferably 3 to 8% by weight, based on the weight of the final composition.

fiIPil and a non-pum reinforced sderene resin can be used in combination, provided the amount of rubbery polymer in the final composition is within the range of 2.5 to 10 wt.

For example, HfF4 and polystyrene can be used in combination.

In addition, HIP8 with adjusted particle size of the elastic phase (rubber phase)
The method for producing ttH is well known industrially. For example, UK Percentage No. 1174214, US Patent No. 269469
No. 2, US Patent No. 320,481, or Journal Otsu 4 Lima Science Vol. 9, p. 2887, the particle size can be adjusted by the stirring conditions during bulk polymerization. Alternatively, emulsion polymerization 8BR or I
I! It is also possible to adjust the particle size of grain particles by adjusting the rubber particle size in the state of rubber latex, and adding a styrene compound to this and emulsion polymerizing it, such as in the case of Hydrangeazoene. Furthermore, a desired particle size and particle size distribution may be obtained by using HfF4 having different rubber phase particle sizes together.

As the particle size of the rubber phase of HfF4 becomes smaller, the impact strength and gloss value improve, but the crack resistance decreases, which is a serious problem in practical use. It is preferable to increase the particle size for rounding to improve hook resistance, but in that case, the gloss of the molded product will decrease.

The present invention solves four of these problems.

In other words, 1iIP! l) The particle diameter of the 1'mu phase is such that the volume average particle diameter (R) is i, o ~ 3.5μ, more preferably mu 1.0 ~ JLOμ, and the volume average particle size ff1 (R
) Ma/number average particle diameter (Rn) of 3.0 or more, preferably 4.0
By doing the above, the resin composition maintains high impact strength and surface gloss, has excellent crack resistance, and is also important as an appearance element of molded products. is obtained. In the present invention, the particle size of the rubber phase is round as measured by electron micrographs of ultra-thin sections known to those skilled in the art. Further, the volume average particle 1K (R) is a round particle determined by the following formula.

71m1R1'' Here, 1 is the number of rubber phases, % i is the diameter of rubber phase particles.The number of rubber phases is measured to be at least 2000, and the particle shape is considered to be a storage body. If this is not possible, measure the major axis (&) and minor axis (b) to obtain a sphere with a diameter of 6).

The styrene resin referred to in the present invention refers to a styrene compound alone or a polymer of two or more styrene compounds, a styrene compound and acrylonitrile, methyl methacrylate, acrylic ester, g#β-unsaturation. rugonic anhydride,
α, β-unsaturated Cal? It refers to compounds that can be copolymerized with sheet styrene compounds, such as imide compounds of phosphoric acid, and other copolymers.

Specific examples of styrene compounds include styrene, α-methylstereph, o-methylstyrene, ethylvinyltoluene, and the like.

In the present invention, the α,β-unsaturated Cal/acid anhydride that forms a copolymer with a styrene compound may be one that copolymerizes with a styrene compound, and a specific example thereof is maleic anhydride. , chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, tetrahydrophthalic anhydride, and the like.

In the present invention, the iside compound of α,l-unsaturated carboxylic acid that forms a copolymer with a styrene compound has the general formula: group, alkenyl group, cycloalyl group, phenyl group, phenylene group, alkylene group, etc.). Specific examples thereof include maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-
-butylmaleimide<)', N-phenylmaleimide, N-(p-methylphenyl)malein(<)", N
-(3,5-dimethylphenyl)malei/imiVsN-
Examples include (P-methoxyphenyl)maleimide, N-benzylmaleimide, and N-(1-ester)maleimide.

In the present invention, it is possible to add a small amount of polyα-olefin, if necessary. In that case, polyethylene, polypropylene, polybutene-1, etc. are used as the polyolefin, and the amount □ is 0.1 to 3 parts by weight, preferably 0.5 to 1.5 parts by weight. If it exceeds 3 parts by weight, scratches will occur and the gloss will be reduced.

Other hydrogenated or non-hydrogenated Sderene!
Tazoene copolymers and the like can also be added.

The method for producing the resin composition of the present invention is not particularly limited, and the resin composition of the present invention can be kneaded and produced using a mixer such as a kneading machine, a heating roll, a kneader, or a Banbury mixer. When kneading the resin composition using a mixer, it is preferable to knead in the presence of an antioxidant and/or under a nitrogen atmosphere.

The resin composition of the present invention may contain other additives, such as plasticizers,
stabilizers such as flame retardants, antioxidants or UV absorbers;
Alternatively, dyes and pigments can be contained. In addition to this, there are also f) fibers and carbon fibers.

It is slowed down by adding O fillers such as calcium carbonate and Merck.

The present invention will be explained below using IAi11, but the present invention is not limited thereto. The resin composition was 1%, and a test piece was obtained by injection molding.

Measure each physical property value using the following measurement method.

Izot impact strength; JIli K6871 tensile strength; JIB K6Ji71 melt 7 * -; JIB K7!10
Temperature: 250°C Load: Deflection temperature: JIB 1 [72G? Shiny
Measured using UGV-4D manufactured by Suga Test Instruments Co., Ltd. at a reflection angle of 6 G''4'C.

Feld line: Determined from an injection molded flat plate for Feld line evaluation measuring 1150 x 150 x 2 m as shown in the figure.

1 is f-) part, 2 is weld line, short distance of 2 It is preferable to paddle.

Crack resistance: The inside is threaded to match the M-4 screw (insert breaking torque) and the surface is machined to fit the brass insert fitting shown in Figure 9N2. Inner injection molding was carried out, and after molding, the groin part was cut out, immersed in n-hebutane at 23° C. for 10 minutes, and then removed and dried.

Those with poor resistance to scratches.

The shoes are very hot and the p1 is excellent. There's almost no room for anything. child To quantify and quantify Insert the M-4 screw into the The 1st part is on the torque meter. Find the torque value until destruction. Me nine. In other words, crack resistance The one who has a bad sex is the one who has a bad sex. Smaller rounding that is already in It will be destroyed by the torque value. In contrast, things have a high value.

Cell 7 Tatsul Bakascrew Torque: As shown in Figure 4, perform self-tapping with an M-4 screw on the 9th part and find the Bakascrew torque value. In other words, having a strong screw torque means having a strong fastening force with parts, etc. Preferred Examples 1 to 9, Comparative Examples 1-5 For test pieces in which resin compositions were injection molded into pellets by the method described below. Each physical property value was measured using the measurement method described above.

(Composition manufacturing conditions) 32 wsφ tool direction rotation direction extruder (manufactured by Nakatani Kikai Co., Ltd. A
l1-30. Using L/D=32> and the blending ratio shown in Table 111, the following cylinder temperature cylinder temperature (
℃) at a screw rotation speed of 60 rpns to form a pellet.

The amount charged was 10 m for each case.

Homo I remer of PPE is 4-(2,6-y methyl-1
, 4-phenylene) ether, a average molecular weight Mn
The relationship between and the intrinsic viscosity [su] is expressed by the following formula % formula % (Here, the intrinsic viscosity is expressed in the unit di/i and is measured in a chloroform solution of 3G'C.) The molecular weight of the repeating unit of 4-rimer is 120, the number average polymerization f+1 can be easily calculated from [da]. Throughout the implementation, all molecular weights are expressed in terms of intrinsic viscosity.

In Table 9, 311, the blending amounts are parts by weight, and ``H'' indicates weight. (The same applies hereinafter.) The measurement results of physical property values are listed in Table 1.

According to Table 1, the resin composition of the present invention is a resin with good strength that maintains practical impact resistance, has a large insert breaking torque, has excellent insert crack resistance, and has high gloss retention. It turns out that it is a composition.

Examples 10 to 15, Comparative M6 to 9 The results of measuring the physical properties of the nine resin compositions obtained by the method described below are summarized in Table 2.

Example 1O A composition was obtained by kneading 50 parts of poly(2,6-nomether-1,4-phenylene ether) and 750 parts of rubber-reinforced polyester containing a 12-butadiene component at 270°C using an extruder. Ta.

Example 11 /17 (2,6-dimeter-1,4-phenylene x-7
) 50111 and 12s! Using an extruder, if
A composition was obtained by mixing at 260° C. in an atmosphere of i1.

Example 12 75 parts of Isu(2,6-nomethyl-1,4-phenylene ether), 725 parts of reinforced polyester containing 24s of tutatsuene component, 1 part of polyethylene and 0.5 part of 2,
A composition was obtained by kneading 6-di-tert-butyl-p-cresol at 320° C. in a nitrogen:a atmosphere using an extruder.

Example 13: 40 parts of 2,6-nomethyl-1,4-7enyl/x-thyl, 59 parts of rubber-reinforced 4-listerene containing a 1-tanoene component of 12-1, 1 part of polyethylene, and 0 .7
511 tris(nonylphenyl)phosphite were kneaded at 260°C using an extruder to obtain a composition.

Example 14 /! Hydrogenated styrene-tutadiene copolymer containing 59 parts of J (2,4-dimethyl-1,4-phenylene ether), 735 parts of TM-reinforced 4 Listere containing a 24S butanoene component, and a 2G-styrene component. Combined 2 parts and
A composition was obtained by kneading 4 parts O triphenylene phosphate at 280° C. in a nitrogen atmosphere using an extruder.

Example 15 3 parts of Isu(2,6-dimether-1,4-phenylene ether), 1 lI of rubber reinforced polystere/60iil containing a butadiene component, 715 parts of polystere, 1
Part of 2,6-di-tert-butyl-p-cresol was kneaded at 250°C using an extruder to obtain a composition.

Comparative Example 6 50 parts of poly(2,6-dimether-1,4-phenylene ether) and 750 parts of reinforced polyester containing 12 pieces of butadiene were kneaded at 270°C under a nitrogen atmosphere using an extruder to obtain a composition. Ta.

Comparative Example 7 2゜6- containing 0.5-〇〇-cresol in the starting material
Isu(2,6-dimethyl-1,4-phenylene ether) sol obtained by polymerizing xylenol and 750 parts of reinforced polyester containing a 12-butadiene component were kneaded at 350°C using an extruder to form a composition. Got nine.

Comparative Example 8 85 parts of poly(2,6-dimethe-1,4-phenylene ether), 715 parts of reinforced 4 Listere containing a butadiene component of 2411, and 0.5 parts of 2. A composition was obtained by kneading @-G-tert-butyl-p-cresol at 310°C using an extruder.

Comparative Example 9 2.6- containing 0.8-p-cresol in the starting material
Using an extruder, 50 parts of poly(2゜6-nomef-1.4-7 2-2-2lene ether) obtained by polymerizing xylenol and parts of reinforced I Listerene rhO containing 12% of butadiene were mixed into 290 parts by using an extruder. Knead at ℃ to obtain a composition.

According to JI21, the resin composition of the present invention maintains practical impact resistance, has high insert fracture torque, is excellent in insert crack resistance, and has high gloss. It can be seen that it is an Arashiku Tore-Kyu resin composition.

Examples 17-20 Poly(2,6-?)methyl-1 in which [da] is 0.71
, 4-phenylene) ether 50 weight [:, # Contains 8-liptadiene, volume average rubber particle diameter is 1.2μ, 2.
3 μ, 2.4 μ, 2.8 μ] and the volume average rubber particle diameter/number average rubber particle diameter is 3.5, 3, 8.4, respectively.
．． 50 parts by weight of rubber reinforcing 4-metylef, which is 4.5.5, and 1 part by weight of octadecyl-3-(3,5-ditertiary-butyl-4-hydroxyphenol) propionate (Ciba Geigy, Irganox 1076) were added. The mixture was homogeneously mixed using a twin-screw extruder, and then kneaded using a twin-screw extruder to obtain pellets. The measurement results of physical property values are shown in Table 3.

Comparative Examples 10 to 12 The volume average rubber particle diameter of the rubber-reinforced polystyrene is 0, 8μ
, 2.5μ, 3.1μ, and the volume average rubber particle diameter/number average rubber particle diameter is 2.0゜2, i s
Table 3 shows the physical property values of the nine resin compositions obtained in exactly the same manner as in Examples 17 to 20, except that the ratio was 2.4.

Comparative Example 13 The physical properties of a resin composition obtained in the same manner as in Example except that the [D] was 0.48 and the rubber reinforced I Listere used in Example 18 were used were shown in gas.

Comparative Example 14 [η] is 0.71 (2,6-nomethyl-1.
4-phenylene) ether 50 parts by weight topolyptadiene/
Contains 20 - volume average rubber particles with a volume average of 5 particle diameters and 9μ1 volume average rubber particles II! /TM reinforcement I with a number average particle diameter of 3 or 5
The physical properties of the resin composition obtained from 50 parts by weight of Listerene and 1 part by weight of Irganox 1076 are shown in the third true circle.

From the ms table, it can be seen that the resin composition of the present invention is a truly practical resin composition with excellent quality balance.

[Brief explanation of drawings]

Figures 1 to 4 are all books@F! FIG. 1 is a plan view of an injection molded flat plate for Feldline evaluation, and FIG. 2 shows an insert fitting for measuring crack resistance and its dimensions. ,
(2-1) is a plan view, (2-2) is a side view, and Figure 3 is a cutout of the boss part for evaluating crack resistance when the insert fitting in Figure 2 is inserted into a resin molded product, and its dimensions. , (3-1) is a plan view, (3-2) is a side view,
Figure 4 shows the boss and dimensions for self-tapping evaluation.
4-1) is a plan view of the upper end, and (4-2) is a side view. Figures 5 to 9 are illustrations of Examples 8:f of the resin composition of the present invention for each requirement along with comparative examples to make the effects easier to understand. H means an example, and symbol R means a comparative example. 1...Gate part, 2...Queldfin, 3...
Insert metal fittings, 4...resin. Figure 2 (2-1) (2-2) Figure 3 (3-1) (3-2) Figure 4 (4-1) (4-2) Go to Figure 5 → Glancing PPE [η ] Figure 9 With volume average material of r-mu phase (100 V) Procedural amendment (white @) December 1980 φ day Patent Office Commissioner Island 1) Spring Resin 1 Incident indication 1980 Patent application No. 162027 2. Title of the invention Aromatic polyether resin composition 3 Relationship with the case of the person making the amendment Patent applicant (Name (5930) Patent attorney 3. Haga 1) 5. Date of amendment order Spontaneous 6 Number of inventions increased by amendment 07, subject of amendment (1) Correct "U-cresol" in lines 4 to 3 from the bottom of page 21 of the Memorandum of Regulations to "0-cresol". (3) Same as above. Bond Kl'-1 for "resin composition" on the last line of the same page
Insert "001 parts". (4) Insert K "for 100 parts by weight of the resin composition" after "The amount is" on lines 5 and 6 of page 34 of the same page. (In the 7th line of the same page, ``In the case of 3 parts by weight or more'' is corrected to ``In the case of more than 3 parts by weight.'' Ether %: Jt-Mm. (7) [Polystyrene molecular weight (2) Polystyrene molecular weight (210,000411 or more F, 10,000 or more Ff) % of bath release" in the left column of Table 2 on page 45. part% "
Correct to.

Claims (1)

[Scope of Claims] (1) Polyphenylene ether (PPg) whose general formula is a repeating unit and whose structural units are [I], or (1) and [薊] 2
The intrinsic viscosity (w) of PPE is 6 with a composition of 80-200-20% by weight of rubber reinforcement and 80-200-20% of rubber reinforcement (HfF4) (30°C, chloroform solution). is o, so~o, aoost,
and polystyrene molecular weight of PPW equivalent to a, o o o or less.
) A resin composition characterized in that the amount of III released is 5% by weight or less. (2) PPEO (If) #0.55 to 0.75? The resin composition according to claim 1. (a) ppiopolis fV molecular weight 10.0004@
2. The resin composition according to claim 1, wherein the GPC elution portion of 4 or less is 8 or less by weight. (4) 6% by weight of the apc eluted portion with a molecular weight of 10.00041 or less
The resin composition according to claim 1, which is as follows. (5) The composition is PPE25-70wt- and HIF87
*Wf The resin composition according to any one of claims 1 to 4, which is composed of 5 to 30% by weight. (6) The rubber content in the composition is 2.5 to 10% by weight.
The resin composition according to any one of claims 1 to 5. (7) The resin composition according to any one of claims 1 to 5, wherein the rubber content in the composition is 3 to 8 weight. (8) Volume average particle diameter of the elastic phase of HIP B (
Rv) is 1 in the range of 1.0 to 3.5 s, and the ratio (RV/R) between i and ζ (number average particle diameter of the elastic phase) is 3.0 or more. The resin composition according to item 1. (9) The resin composition according to claim 8, wherein ("v/1lI) is 4.0 or more. (10) Poly(2,6-dimetheru-1,4-phenylene y) x-f #2.0~80wt- and HE11
80 to 20 wt.
, 6-dimethyl-1,4-phenylene) ether has an intrinsic viscosity [ma] (30°C, chloroform solution) of Q,! ! 0
~01001i], and the GPC eluted portion of the 4-listerene molecular weight of 3000 phases or less in the 2,6-dimethyl-1,4-phenylene ether is 6 weight or less, and I (2 Scissors poly(2,6-/methyl-1,4-phenylene/) from a dichloromethane solution containing 5 wt.
A resin composition characterized by the amount of precipitation of ether ((iL, Si2). 1 #S(2,6-nomethyl-1,4-phenylene)
The resin composition according to claim 810, wherein the ether has a nominal value of 0.60 to 0.75. (12) Poly(2,6-dimethyl-1,4-phenylene) ether /IJ styrene molecular weight 10 The resin composition according to claim i!i@1G, wherein the GPC11 output portion of ,000 monks or less is 8 weight or less. ) The resin composition according to claim 10, wherein the GPC eluted portion of the ether with a molecular weight of 10,000 or less is 6 weight or less. The resin composition according to claim 10, wherein the amount of precipitated (after standing at 2aC for 5 hours) ether (phenyleneenylene) is 80% by weight or more. -Simethyl-1,4-phenylene]ether 25-70 weight 11, HI pH 75
A special # that consists of ~30 weight-! Fii1 request range 18! The resin composition according to any one of Items 1θ to 14. (16) The resin composition according to any one of claims #11G to 15, wherein the rubber content in the composition is 15 to 10% by weight. (17) The resin composition according to any one of claims 1110 to 15, wherein the rubber content in the composition is 3 to 8 weight. (18) Volume average particle diameter of the elastic phase of HI P 8 (
11v) The resin composition according to claim S, wherein the ratio (RV/i) of the number average particle diameter of the body phase is 3.0 or more. (19) (''//R) Cat (Resin composition described in Section 18 of Section 18 of the above-mentioned request. Where the repeating unit is [I], or (1) and CI) -rifhenylene ether (PPE) consisting of 20
~80 Weight Yu and Pu-5 - Reinforcement High Inno Parable/)/! J Styrene (HIPli) Yohistyrene resin 80-20
A composition consisting of a weight - and an intrinsic viscosity of PPE [
da) (30'C, chloroform solution) is 0.50-0.
The polystyrene molecular weight of the PPE is within the range of 80
, ooo equivalent or less r/4-meation chromatography (GPC) # mountain portion is 5 weight or less. (21) The resin composition according to claim 20, wherein [ma] in ppg is 0.55 to 0.75. (22) The resin composition according to claim 20, wherein the opc@extruded portion having a polystyrene molecular weight of 10,000 ppm or less is 8 weight or less. (23) PPI I styrene molecular weight i o, o o
8. The resin composition according to claim 8ai2G, wherein the GPC@output portion of 0 or less is 6 weight or less. (24) The styrene resin is a polymer consisting of a styrene compound alone or two or more, and i9 is a styrene compound and a 7-acrylonitrile, methyl methacrylate, acrylic acid ester, -, β-unsaturated unsaturated carbon. -Hydroxy anhydride l-
Unsaturated Cal? 21. The resin composition according to claim 20, which is a copolymer of a compound copolymerizable with the styrenic compound, such as a hepta-acid imide compound. (25) A patent in which the α,β-unsaturated CalM/@anhydride copolymerizable with a styrene compound is maleic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, and tetrahydrotutaric anhydride. The resin composition according to claim 8, item 24. (26) The resin composition according to claim 24, wherein the imide compound of α,β-unsaturated carboxylic acid copolymerizable with the styrene compound is represented by the general formula 8. (27) g, an imide compound of β-unsaturated carbonic acid,
Maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-tutilmaL/(N-phenylmaleimide), N-(p-methylphenyl)maleimide), N-(3 , 5-dimethylphenyl)maleimide 5N=cp-methoxyphenyl)-rheinimide, N-benzylmaleimide,
27. The resin composition according to claim 26, which is N-(1-su7ter)maleimide. (28) A composition consisting of 20 to 80% by weight of poly(2,6-dimether-1.4-7dinilene) ether, and 80 to 20% by weight of HfF4 and a styrene resin, , 6-dimethyl-1°4-phenylene) ether (W) (30°C, chloroform solution) is in the range of 0.50 to o1go, and 4-risprene of 4-phenylene) ether with a molecular weight of 3000 or less, a GPC@exited portion of 5% by weight or less, and dichloromethane containing f(2,6-dimethe-1,4-phenylene)ether s by weight. The poly(2,6-cymeter) from solution 1.4
- A resin composition characterized in that the amount of precipitated (phenylene) ether (after standing at 23°C for 5 hours) is 70 kg or more. (29) The intrinsic viscosity [ma] of /su(2,6-1'methyl-1,4-7ethylene)ether is 0.60 to 0.7
5. The resin composition according to claim $28. (aO)IIls(2,6-/Mefk-1.4-ys
29. The resin composition according to claim 28, wherein the GPC elution portion of the ether having a molecular weight of 4 risprene of 10,000 or less is 8 weight or less. (31) The resin composition according to claim 28, wherein the GPC4i fraction of the /su(2,6-dimethyl-1,4-phenylene)ether having a polystyrene molecular weight of 10,000 or less is 6 weight or less. (32) #The amount of poly(2,6-dimethyl-1,4-phenylene) ether precipitated from a dichloromethane solution containing 5 weight of (2,6-dimethyl-1,4-phenylene) ether (at 23°C , after standing for 5 hours) is 80 weight or more. (33) The styrene resin is a polymer of a styrene compound alone or a combination of two or more, or a styrene compound and 7-acrylonitrile, methyl methacrylate, acrylic ester, α, β-, β-carganese Acid anhydride, α, β
- a compound copolymerizable with the styrenic compound, such as an imide compound of unsaturated caronic acid. (34) α, l-unsaturated carboxyl anhydride copolymerizable with styrene compounds, maleic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl succinic anhydride,
Claim 3 which is tetrahydrophthalic anhydride
The resin composition according to item 3. (35) The resin composition according to claim 18, item 33, wherein the ind compound of α,β-unsaturated carboxylic acid copolymerizable with the styrene compound is represented by the general formula. (36) The imide compound of α,β-unsaturated carboxylic acid is
Maleimide, N-methylmaleimide, N-cyclohexylmaleimide? N-butylmaleimide, N-phenylmaleimide; p-methoxyphenyl)maleimide, N-benzylmaleimide,
36. The resin composition according to claim 35, which is N-(1-naphthyl)maleimide. (37) The comb content in the composition is 2.5 to 10% by weight.
% of the resin composition according to claim 28. (38) The resin composition according to claim 28, wherein the shim content in the composition is 3 to 8 weight.