JPS6241539B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on polyphenylene ether (hereinafter referred to as PPE).
This invention relates to a thermoplastic resin composition mainly consisting of a rubber-reinforced high-impact polystyrene resin (hereinafter abbreviated as HIPS). The present invention relates to aromatic polyether resin compositions that have good gloss and improved crack resistance, especially in molded articles into which metals are inserted. More specifically, the present invention is a resin that is mainly composed of PPE and HIPS with controlled molecular weights and low abundance ratios of medium- and low-molecular weight molecules, and which is resistant to cracks in metal insert molded products while maintaining good gloss. Regarding the composition. The present invention also provides PPE with controlled molecular weight, low abundance of medium and low molecules, and less heterogeneous structures.
It also relates to a resin composition comprising HIPS and a styrenic resin. Furthermore, the present invention has good appearance such as good gloss and inconspicuous weld parts, and is suitable for use in large internal or external applications such as molded products with metal inserts or molded products with self-tap structure. The present invention relates to a resin composition that does not easily cause cracks even when a molded article to which stress is applied comes into contact with oil, a chemical solution, a chemical, or a gas. PPE resin is known as a resin with excellent mechanical properties, electrical properties, and heat resistance, but has poor moldability and poor impact resistance. In order to improve these drawbacks, Japanese Patent Publication No. 17812/1986 and U.S. Patent No.
No. 3383435 proposes blending polystyrene or acrylonitrile-butadiene-styrene terpolymer with PPE resin to simultaneously improve processability and impact resistance. In addition, Japanese Patent Publication No. 51-28659 states that a resin composition consisting of PPE resin and HIPS has good gloss and good impact resistance, especially when the rubber particle size is 1 to 2 μm. However, these compositions have poor stress cracking resistance and have a fatal flaw in practical use. In addition, a resin composition composed of PPE resin and polyα-olefin is disclosed in U.S. Patent No. 3361851,
-Listed in No. 7069. However, the impact resistance of this resin composition is insufficiently improved, and what is more undesirable is that as the amount of polyα-olefin added increases, the gloss of the surface of the molded product decreases. Modification of PPE resins by the addition of hydrogenated styrene-butadiene copolymers is also disclosed, for example, in JP-A-51-8358. Molded products obtained using these techniques have difficulty achieving high gloss on their outer surfaces, and molded products with structures where welds occur have long weld lines and deep weld grooves, making the appearance unsatisfactory. It cannot be said that it is something that should be done. In addition, many attempts have been made to improve compositions of PPE resin and other resins by focusing on the properties of resins other than PPE resin. In this way, most of the techniques for modifying PPE resin compositions focus on the properties of components other than the PPE component, and instead focus on the PPE component and modify the resin composition from that perspective. There are few attempts to ask questions. Examples that focus on the PPE ingredients themselves include JP-B No. 45-25992 and JP-A-48-51098.
The only technology disclosed is an attempt to improve moldability by increasing the medium/low molecular weight portion of PPE resin and broadening the molecular weight distribution. Although these techniques improve moldability and improve appearance as one of their effects, the degree of improvement is small and they have the disadvantage of lowering stress cracking resistance. In general, compositions of PPE resin and HIPS have been applied industrially, but in order to be used for a wider range of applications, it is necessary to improve appearance,
It is necessary to improve properties such as crack resistance and self-tapping property, and the realization of such improvements has been strongly desired. The ability to attach a large number of parts to a plastic molded product, for example, the ability to attach parts such as electrical parts directly to a plastic housing without using a special chassis, saves materials and reduces man-hours, which is an industrial advantage. This is a huge advantage and one of the major reasons why plastics have been widely used. To attach these parts, you can take advantage of plastic's moldability and formability to erect so-called bosses and screw them directly into them with metal screws (self-tapping), or you can use metal embedded inserts. The methods used are well known to those skilled in the art. In such a method, when self-tapping is used, the fastening force (baka screw torque) of the resin used needs to be stronger, and in the case of metal inserts, the thermal Due to differences in properties, accidents such as damage to the plastic parts around the inserts often occur during use, assembly, and sometimes during storage after molding. It is strongly desired that it be better. An object of the present invention is to provide a PPE resin composition with excellent surface gloss, appearance such as weld parts, and stress cracking resistance. If these properties could be improved, the practical value of PPE resin as an engineering resin would be dramatically improved. The present inventors focused particularly on the PPE resin component in the resin composition, and conducted extensive studies with the aim of obtaining a molding material that has a desirable appearance and excellent stress cracking resistance at the practical stage as described above. As a result, we discovered that the properties of the molding material are greatly influenced by the properties of the PPE resin itself, which is the raw material for the resin composition.As a result of various studies on the relationship between the properties of the PPE resin as a constituent component and the physical properties of the composition. , arrived at the present invention. That is, the present invention provides the following general formula

【formula】

[Formula] (R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , are the same or different alkyl groups having 1 to 4 carbon atoms excluding tertiary butyl groups, aryl groups, halogens, hydrogen, etc.) 20 to 80% by weight of polyphenylene ether (PPE) consisting of monovalent residues (R ₅ and R ₆ are not hydrogen at the same time) as a repeating unit, and the constituent units are [], or [] and [] and 80 to 20% by weight of rubber-reinforced high-impact polystyrene (HIPS), which has an intrinsic viscosity [η] (30
℃, chloroform solution) is in the range of 0.50 to 0.80, and the gel permeation chromatography (GPC) elution fraction of polystyrene molecular weight of 3000 or less is 5% by weight or less. It is something that provides something. The present invention further provides that the PPE is 20 to 80% by weight.
A composition comprising HIPS and 80 to 20% by weight of a styrene resin, wherein the [η] of PPE (30°C, chloroform solution) is in the range of 0.5 to 0.80, and
GPC with polystyrene molecular weight of PPE equivalent to 3000 or less
The present invention provides a resin composition characterized by using PPE having an eluted portion of 5% by weight or less. Further, the present invention provides the above-described composition,
PPE is poly(2,6-dimethyl-1,4-phenylene ether), and the amount of precipitation of the PPE from a dichloromethane solution containing 5% by weight of the PPE (after standing at 23°C for 5 hours) The present invention also provides a resin composition in which the amount is 70% by weight or more. Furthermore, in the above composition, the volume average particle diameter ( _v ) of the elastic phase of HIPS, which is the other component, is 1.0 to 3.5 μ, and _v and _o (number average particle size of the elastic phase The ratio ( _v / _o ) of
A resin composition using a HIPS of 3.0 or more is also included in the present invention as a preferred embodiment of the present invention. The PPE of the present invention has the general formula

【formula】

[Formula] (where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are the same or different alkyl groups having 1 to 4 carbon atoms excluding tert-butyl groups, aryl groups, halogens, hydrogen, etc.) It is a monovalent residue, and R ₅ and R ₆ are not hydrogen at the same time) as a repeating unit, and is a homopolymer or copolymer consisting of [ ] or [ ] and [ ] as constituent units. Representative examples of PPE homopolymers include poly(2,6-dimethyl-1,4-phenylene) ether and poly(2-methyl-6-ethyl-1,4-
phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-) 1,4
-phenylene)ether, poly(2-methyl-6)
-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether, poly( 2
Examples include homopolymers such as -methyl-6-hydroxyethyl-1,4-phenylene) ether and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether. Polyphenylene ether copolymer has the general formula (Here, R ₃ , R ₄ , R ₅ , and R ₆ are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, and hydrogen, excluding a tert-butyl group, and R ₅ , R ₆ is not hydrogen at the same time), a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by copolymerizing with an alkyl-substituted phenol such as O-cresol or 2,3,6-trimethylphenol. Includes coalescence. The intrinsic viscosity [η] of the PPE resin used in the present invention and the quantitative determination of the GPC eluted portion are measured by the following method based on a conventional method. The intrinsic viscosity [η] is determined using an Ubbelohde viscometer.
Measurement was carried out at 30°C using chloroform as a solvent. In addition, the GPC elution portion of PPE with a polystyrene molecular weight of 3,000 and 10,000 or less was quantified by the following method. The equipment is HLC-802UR manufactured by Toyo Soda Kogyo Co., Ltd., and the columns are G5000H, G4000H, G3000H and
G2500H, the detector is a differential refractometer, chloroform is used as the mobile phase, and the sample concentration is measured at 40℃.
Measure the GPC curve of PPE at 0.5%. When determining the relationship between elution time and molecular weight, polystyrene was used as a standard substance. From the molecular weight distribution of PPE, calculate the molecular weight 3000 and 10000 or less from the area ratio, and calculate the polystyrene molecular weight 3000 and 10000 of PPE.
The amount of eluted fractions below 10,000 was measured. In addition, when the PPE component was extracted from the composition by the method described below, the respective values were determined according to the above method. In the present invention, when [η] of PPE, which is a constituent component of the composition, is less than 0.50, stress cracking resistance is poor. Therefore, [η] is 0.50 or more, preferably
A value of 0.55 or higher is desirable. If [η] exceeds 0.80, the appearance such as gloss and welded areas will be poor. Therefore, [η] is 0.80 or less, more preferably
Desirably 0.75 or less. When [η] is in the range of 0.50 to 0.80, as the viscosity of the PPE increases, the crack resistance improves slightly, but the improvement is particularly marked when the proportion of medium- and low-molecular-weight PPE below polystyrene molecular weight 3000 is reduced. . Also, polystyrene molecular weight 10000 by GPC analysis
If the fraction of leaching exceeds 8% by weight, the moldability is improved but the stress cracking resistance is reduced. Therefore, the eluted portion having a molecular weight of 10,000 or less is preferably 8% by weight or less, more preferably 6% by weight or less. The present inventors conducted further studies to find the optimal PPE components of the present invention, and as a result, the above-mentioned
In addition to the properties of the PPE components, PPE is poly(2,6-
In the case of dimethyl-1,4-phenylene) ether, if the amount of PPE component precipitated from a dichloromethane solution containing 5% by weight at 23°C for 5 hours is less than 70% by weight, the appearance is better. It was discovered that the stress cracking resistance was not improved. Precipitation amount is 80% by weight
It is more preferable that it is above. In the present invention, when PPE is poly(2,6-dimethyl-1,4-phenylene) ether,
The properties of the PPE can also be determined by extracting it from the composition by the method described below. Add 6g of the composition to 200ml of chloroform,
After shaking at room temperature for 3 hours, centrifugation is performed at 52000G for 45 minutes to separate the insoluble portion and the solution portion. Carefully drop the solution portion into 1000 c.c. of methanol while stirring to reprecipitate. Thereafter, the precipitate is separated using a G4 mesh glass filter, and 1000 ml of methanol is poured onto the filter to wash it. Thereafter, the separate material was taken out and dried under reduced pressure at 145° C. for 1 hour in a nitrogen atmosphere to obtain Sample I. In this case, the solvent or non-solvent can be appropriately selected depending on the properties of the other resins and additives. Poly(2,6) determined by infrared spectroscopy
Sample I was dissolved in dichloromethane so that the concentration of the component was 5% by weight based on the content of -dimethyl-1,4-phenylene) ether. Thereafter, the solution was allowed to stand at -5°C for 24 hours to precipitate the poly(2,6-dimethyl-1,4-phenylene) ether component. After that, the ingredients were added to G4.
After separating using a mesh glass filter and washing with dichloromethane on the glass filter, the separated material was heated at 145℃ under a nitrogen atmosphere.
Dry under reduced pressure for 30 minutes and use as a sample. The intrinsic viscosity [η] of the sample at 30°C was determined using an Ubbelohde viscometer using chloroform as a solvent, and the intrinsic viscosity of poly(2,6-dimethyl-1,4-phenylene) ether, which is a constituent component of the resin composition, was determined. [η] can also be found. Also, poly(2,6
The amount of precipitated ether (dimethyl-1,4-phenylene) can be determined by the following method. The sample is dissolved in dichloromethane to a concentration of 5% by weight, and the solution is allowed to stand at 23°C. Poly(2,6
-dimethyl-1,4-phenylene) ether by J.
Polymer Sci, B7.205 (1969) and U.S. Pat.
It is deposited again according to the principle described in No. 3644227. After standing for 5 hours, the precipitate was separated, washed and dried using a G4 mesh glass filter, and then weighed to determine the amount of precipitate. In the present invention, the content of PPE in 100 parts by weight of the resin composition is 20 to 80 parts by weight, preferably 25 to 80 parts by weight.
A range of 70 parts by weight is preferred. If the content of PPE is less than 20 parts by weight, the improvement effect of PPE will not be sufficiently exhibited. On the other hand, if the content exceeds 80 parts by weight, the fluidity will be poor due to the properties of the PPE itself, and the appearance will not be sufficiently improved, which is not preferable. The method for producing PPE used in the present invention is not particularly limited, but it can be obtained by subjecting a specific 2,6-disubstituted phenol to an in-liquid oxidation reaction using an ordinary metal complex as a catalyst. The catalyst may be any catalyst as long as it promotes the oxidative polymerization reaction of 2,6-disubstituted phenols, but usually a metal complex consisting of a metal salt and an amine compound is used.
If necessary, a reaction accelerator such as an alkali metal hydroxide or alcohol may be present in the catalyst. As the polymerization reaction solvent, any solvent that can dissolve the 2,6-disubstituted phenols and is inert to the reaction can be used. In this case, the polymerization reaction solvent may be one that does not dissolve PPE at all, one that partially dissolves it, or one that dissolves all of it. For example, when a mixture of a good solvent for PPE such as toluene, xylene, or ethylbenzene and a non-solvent such as alcohol is used as a solvent, high molecular weight PPE precipitates in the form of particles and becomes a slurry. By controlling the solvent composition and extracting only slurry particles,
A suitable PPE can be obtained by implementing the present invention. The polymerization reactor may be of a batch type or a continuous type.
The polymerization temperature is selected to be in the range of 40 to 60°C, preferably a temperature range of 40 to 50°C is suitable for obtaining the PPE of the present invention. Preferred PPE for use in the present invention
can be produced by the method described above by selecting the purity of the raw material monomer. The rubber-reinforced high-impact polystyrene (HIPS) referred to in the present invention is one that contains polystyrene as a resin phase and a rubber-like polymer dispersed in island-like form, and in the presence of the rubber-like polymer, styrene monomer is It is produced by a method such as bulk polymerization, solution polymerization, bulk suspension polymerization, or emulsion polymerization in the presence or absence of a radical polymerization initiator. As the rubber, butadiene rubber, styrene-butadiene copolymer rubber, etc. are used. The intrinsic viscosity (30° C., chloroform solution) [η] of the polystyrene resin phase is preferably 0.6 to 1.0. As mentioned above, the ratio of PPE to HIPS is
If the PPE resin exceeds 80 parts by weight, processability will be insufficient and it will be unsuitable for many uses, and if it is less than 20 parts by weight, the heat resistance, which is a characteristic of PPE, will be significantly lost, which is not preferred in practice. In addition, the larger the amount of rubbery polymer in the resin composition, the higher the impact strength and crack resistance, but on the contrary, the self-tap properties and appearance performance, which are important properties when fastening structural parts, deteriorate. Therefore, it is not desirable. Suitably, the amount of rubbery polymer is in the range 2.5 to 10% by weight, preferably 3 to 8% by weight, based on the weight of the final composition. HIPS and non-rubber reinforced styrenic resins can be used in combination if the amount of rubbery polymer in the final composition is within the range of 2.5 to 10% by weight. For example, HIPS and polystyrene can be used in combination. In addition, the particle size of the elastic phase (rubber phase) was adjusted.
The method of manufacturing HIPS is well known industrially. For example, UK Patent No. 1174214, US Patent No.
As shown in No. 2,694,692, US Pat. No. 3,243,481, or Journal of Polymer Science, Vol. 9, p. 2887, the particle size can be adjusted by changing the stirring conditions during bulk polymerization. Alternatively, the rubber phase particle size can be adjusted by adjusting the rubber particle size in the state of rubber latex, such as emulsion polymerized SBR or polybutadiene, and adding a styrene compound to the rubber latex to carry out emulsion polymerization. Furthermore, a desired particle size and particle size distribution may be obtained by using HIPS having different rubber phase particle sizes in combination. As the particle size of the rubber phase of HIPS becomes smaller, the impact strength and gloss value improve, but on the other hand, the crack resistance decreases, which becomes a major problem in practical use. In order to improve crack resistance, it is preferable to increase the particle size, but in this case the surface gloss of the molded product will decrease. The present invention solves these problems.
That is, the particle size of the rubber phase of HIPS is set to a volume average particle size ( _v ) of 1.0 to 3.5μ, more preferably 1.0
~3.0μ, and the volume average particle diameter ( _v )/number average particle diameter ( _o ) is 3.0 or more, preferably 4.0 or more, to maintain high impact strength and surface gloss, and to improve crack resistance. This makes it possible to obtain a resin composition with excellent properties and also with a good weld line, which is an important aspect of the appearance of molded products. In the present invention, the particle size of the rubber phase is measured using an electron micrograph of an ultrathin section well known to those skilled in the art. Further, the volume average particle diameter ( _v ) was determined by the following formula. _v = ΣniRi ⁴ /ΣniRi ³ Here, ni means the number of rubber phases, and Ri means the diameter of the rubber phase particles. In addition, the number of rubber phases is at least
If more than 2,000 particles are measured and the particle shape cannot be considered spherical, measure the major axis (a) and minor axis (b) and calculate the diameter √・
This is what I wanted as a ball. The styrene resin referred to in the present invention refers to a polymer consisting of a styrene compound alone or two or more, or a styrene compound and acrylonitrile, methyl methacrylate, acrylic ester, α, β
- Refers to a copolymer consisting of a compound copolymerizable with the styrenic compound, such as an unsaturated carboxylic anhydride or an imide compound of α,β-unsaturated carboxylic acid. Specific examples of styrene compounds include styrene, α-methylstyrene, o-methylstyrene,
Examples include p-methylstyrene, dimethylstyrene, and ethylvinyltoluene. In the present invention, the α,β-unsaturated carboxylic acid anhydride that forms a copolymer with a styrene compound may be any one that copolymerizes with a styrene compound, and specific examples thereof include maleic anhydride, chloro Examples include maleic anhydride, citraconic anhydride, butenylsuccinic anhydride, and tetrahydrophthalic anhydride. In the present invention, the α,β-unsaturated carboxylic acid imide compound that forms a copolymer with a styrene compound has the general formula; (In the formula, R ₇ , R ₈ , and R ₉ represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, a phenylene group, and an alkylene group.) Specific examples include maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-
(P-methylphenyl)maleimide, N-
(3,5-dimethylphenyl)maleimide,
N-(P-methoxyphenyl)maleimide,
Examples include N-benzylmaleimide and N-(1-naphthyl)maleimide. In the present invention, it is also possible to add a small amount of polyα-olefin, if necessary. In this case, polyethylene, polypropylene, polybutene-1, etc. are used as the polyα-olefin, and the amount thereof is 0.1 to 3 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the resin composition. If it exceeds 3 parts by weight, peeling will occur and the gloss will be reduced. In addition, a styrene-butadiene copolymer, which may or may not be hydrogenated, may also be added. The method for producing the resin composition of the present invention is not particularly limited, and the resin composition can be kneaded and produced using a kneader such as an extruder, heating roll, kneader, or Banbury mixer. When kneading the resin composition of the present invention using a kneader, it is more desirable 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 stabilizers such as plasticizers, flame retardants, antioxidants or ultraviolet absorbers, or dyes and pigments. In addition, glass fiber, carbon fiber,
Fillers such as calcium carbonate and talc can be added. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Unless otherwise specified, the resin composition was injection molded to obtain a test piece, and each physical property value was measured using the following measuring method. Izotsu impact strength: JIS K6871 Tensile strength: JIS K6871 Melt flow: JIS K7210 Temperature: 250°C Deflection temperature under load: JIS K7207 Gloss: At a reflection angle of 60° using UGV-4D manufactured by Suga Test Instruments Co., Ltd. It was measured. Weld line: 150mm x 150mm as shown in Figure 1
It was determined from an injection molded flat plate for weld line evaluation of ×2 mm. Reference numeral 1 indicates a gate portion and 2 indicates a weld line, and it is preferable that the distance between 2 and 2 is short. Cracking resistance (insert breaking torque): Insert injection molding of the brass insert shown in Figure 2, which has a threaded interior to fit an M-4 screw and a knurled surface, into the boss part shown in Figure 3. After molding, cut out the boss part and soak it in n-heptane at 23℃ for 10 minutes.
It was soaked for a minute, then taken out and dried.
A material with poor crack resistance will crack a lot, and a material with excellent crack resistance will hardly crack.
In order to quantify and quantify this, M-4
The screw was inserted and the torque value until the boss part was destroyed was determined using a torque meter. In other words, those with poor crack resistance will break with a small torque value because they already have a crack, whereas those with excellent crack resistance will have a high value. Self-tapping screw torque: The boss shown in Fig. 4 was self-tapping with an M-4 screw, and the screw torque value was determined. That is, it is preferable to have a high screw torque because it means to have a strong fastening force with parts and the like. Examples 1 to 9, Comparative Examples 1 to 5 Each physical property value was measured by the above-mentioned measuring method on a test piece made by injection molding a resin composition pelletized by the method described below. (Composition manufacturing conditions) Using a 32 mmφ counter-rotating twin-screw extruder (AS-30 manufactured by Nakatani Kikai Co., Ltd., L/D = 32), using the blending ratio shown in Table 1, the following cylinder temperature was used.

[Table] It was extruded at a screw rotation speed of 60 rpm and pelletized. The amount of preparation was 10 kg in each case. When the homopolymer of PPE is poly(2,6-dimethyl-1,4-phenylene) ether, the relationship between the number average molecular weight n and the intrinsic viscosity [η] is expressed by the following equation. [η] = 1.47×10 ^-4 n ⁰ . ⁸⁵ (Here, the intrinsic viscosity is expressed in the unit dl/g,
Measured in chloroform solution at 30°C. ) Since the molecular weight of the repeating unit of the polymer is 120, the number average degree of polymerization n can be easily calculated from [η]. In the Examples, all molecular weights are expressed in terms of intrinsic viscosity. In addition, the compounding amount in Table 1 is parts by weight, and % is weight %.
shows. (The same applies hereinafter.) The measurement results of physical property values are listed in Table 1. From Table 1, the resin composition of the present invention is a well-balanced resin composition that maintains practical impact resistance, has a large insert breaking torque, has excellent insert crack resistance, and has high gloss. It turns out that.

【table】

[Table] Examples 10 to 15, Comparative Examples 6 to 9 Table 2 summarizes the results of measuring the physical properties of resin compositions obtained by the methods described below. Example 10 Using an extruder, 50 parts of poly(2,6-dimethyl-1,4-phenylene ether) and 50 parts of rubber-reinforced polystyrene containing 12% butadiene were mixed into 270 parts of poly(2,6-dimethyl-1,4-phenylene ether) using an extruder.
A composition was obtained by kneading at ℃. Example 11 50 parts of poly(2,6-dimethyl-1,4-phenylene ether), 50 parts of rubber-reinforced polystyrene containing 12% butadiene component, and 0.5 parts of 2,6-
Di-tert-butyl-p-cresol was kneaded using an extruder at 260°C under a nitrogen atmosphere to obtain a composition. Example 12 75 parts of poly(2,6-dimethyl-1,4-phenylene ether), 25 parts of reinforced polystyrene containing 24% butadiene component, and 1 part of polyethylene
A composition was obtained by kneading 0.5 part of 2,6-di-tert-butyl-p-cresol at 320° C. in a nitrogen atmosphere using an extruder. Example 13 40 parts of poly(2,6-dimethyl-1,4-phenylene ether), 59 parts of reinforced polystyrene with 12% butadiene content, 1 part of polyethylene, and 0.75 parts of tris(nonylphenyl)phosphite were kneaded at 260°C using an extruder to obtain a composition. Example 14 59 parts of poly(2,6-dimethyl-1,4-phenylene ether), 35 parts of rubber-reinforced polystyrene with a 24% butadiene content, and hydrogenated styrene with a 20% styrene content. A composition was obtained by kneading 2 parts of butadiene copolymer and 4 parts of triphenylene phosphate at 280° C. in a nitrogen atmosphere using an extruder. Example 15 35 parts of poly(2,6-dimethyl-1,4-phenylene ether), 50 parts of rubber reinforced polystyrene containing 12% butadiene component, 15 parts of polystyrene and 1 part of 2,6-dimethyl -tert-butyl-p-cresol were kneaded at 250°C using an extruder to obtain a composition. Comparative Example 6 A composition was prepared by kneading 50 parts of poly(2,6-dimethyl-1,4-phenylene ether) and 50 parts of reinforced polystyrene containing 12% butadiene at 270°C under a nitrogen atmosphere using an extruder. I got it. Comparative Example 7 Poly(2,6-xylenol) containing 0.5% o-cresol in the starting material was polymerized.
6-dimethyl-1,4-phenylene ether) 50
and 50 parts of reinforced polystyrene containing 12% butadiene were kneaded at 350°C using an extruder to obtain a composition. Comparative Example 8 85 parts of poly(2,6-dimethyl-1,4-phenylene ether), 15 parts of reinforced polystyrene containing 24% butadiene component, and 0.5 part of 2,6-di-
Using an extruder with tert-butyl-p-cresol
A composition was obtained by kneading at 310°C. Comparative Example 9 Poly(2,6-xylenol) containing 0.8% p-cresol in the starting material was polymerized.
6-dimethyl-1,4-phenylene ether) 50
1 part and 50 parts of reinforced polystyrene containing 12% butadiene component were kneaded at 290°C using an extruder to obtain a composition. From Table 2, the resin composition of the present invention is a well-balanced resin composition that maintains practical impact resistance, has a larger insert breaking torque, has excellent insert crack resistance, and has high gloss. It turns out that.

[Table] Examples 17 to 20 Poly(2,6-dimethyl-
Contains 50 parts by weight of 1,4-phenylene) ether and 8% polybutadiene, and has a volume average rubber particle diameter of
1.2μ, 2.3μ, 2.4μ, 2.8μ, and the volume average rubber particle diameter/number average rubber particle diameter are respectively
Rubber reinforced polystyrene with 3.5, 3.8, 4.4, 5.5
50 parts by weight, octadecyl-3-(3.5-ditertiary-butyl-4-hydroxyphenol) propionate (Ciba Geigy, Irganox)
1076) were uniformly mixed in a blender and kneaded in a twin-screw extruder to obtain pellets. The measurement results of physical property values are shown in Table 3. Comparative Examples 10-12 The volume average rubber particle diameter of 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, 2.1, respectively.
Table 3 shows the physical property values of resin compositions obtained in exactly the same manner as in Examples 17 to 20, except that the value was 2.4. Comparative Example 13 Table 3 shows the physical properties of a resin composition obtained in the same manner as in Example except that [η] was 0.48 and the rubber-reinforced polystyrene used in Example 18 was used. Comparative Example 14 Poly(2,6-dimethyl-
Contains 50 parts by weight of 1,4-phenylene) ether and 20% polybutadiene, volume average rubber particle size 2.9
Table 3 shows the physical properties of a resin composition obtained from 50 parts by weight of rubber-reinforced polystyrene having μ, volume average rubber particle diameter/number average particle diameter of 3.5, and 1 part by weight of Irganox 1076. From Table 3, it can be seen that the resin composition of the present invention is a truly practical resin composition with excellent quality balance.

【table】 [Brief explanation of the drawing]

1 to 4 are explanatory diagrams of the components used to measure the physical properties of the resin composition of the present invention. FIG. 1 is a plan view of an injection molded flat plate for weld line evaluation, and FIG. The insert fitting for crack resistance measurement and its dimensions are shown, and 2-1 is its plan view.
2-2 is a side view, and Figure 3 shows a cutout of the boss part for evaluating crack resistance obtained by inserting the insert fitting in Figure 2 into a resin molded product and its dimensions.
1 is a plan view thereof, 3-2 is a side view, FIG. 4 shows the boss and dimensions for self-tapping evaluation, 4-1 is a plan view of its upper end, and 4-2 is a side view. Fifth
From the figures to Figure 9, the physical property values of the examples of the resin composition of the present invention are illustrated together with comparative examples in order to make the effects easier to understand for each requirement, and the symbol E in the figures indicates the examples. The symbol R means a comparative example. 1...Gate part, 2...Weld line, 3...
...Insert metal fitting, 4...Resin.

Claims (1)

[Claims] 1 General formula [Formula] [Formula] (R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are the same or different
It is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms excluding a tert-butyl group, an aryl group, a halogen, or hydrogen, and R ₅ and R ₆ are not hydrogen at the same time. ) as a repeating unit, consisting of 20-80% by weight of polyphenylene ether (PPE) consisting of [ ], or [ ] and [ ], and 80-20% by weight of rubber-reinforced high-impact polystyrene (HIPS). The intrinsic viscosity of the composition [η] (30
℃, chloroform solution) is in the range of 0.50 to 0.80, and the gel permeation chromatography (GPC) elution fraction of polystyrene molecular weight of PPE of 3000 or less is 5% by weight or less. . 2. The resin composition according to claim 1, wherein [η] of PPE is 0.55 to 0.75. 3 Polystyrene molecular weight of PPE equivalent to 10,000 or less
The resin composition according to claim 1, wherein the GPC eluted portion is 8% by weight or less. 4 Polystyrene molecular weight of PPE equivalent to 10,000 or less
The resin composition according to claim 1, wherein the GPC eluted portion is 6% by weight or less. 5 The composition contains PPE25-70% by weight and HIPS75-30
% by weight.
The resin composition according to any one of Items 1 to 4. 6. The resin composition according to any one of claims 1 to 5, wherein the rubber content in the composition is 2.5 to 10% by weight. 7. The resin composition according to any one of claims 1 to 5, wherein the rubber content in the composition is 3 to 8% by weight. 8 The volume average particle diameter ( _V ) of the elastic phase of HIPS is
9. The resin composition according to claim 1, wherein the ratio of _V to _o (number average particle diameter of the elastic phase) (( _V / _o )) is 1.0 to 3.5μ and is 3.0 or more. The resin composition according to claim 8, wherein ( _V / _o ) is 4.0 or more. % of poly(2,6-
The intrinsic viscosity [η] of dimethyl-1,4-phenylene) ether (30℃, chloroform solution) is 0.50~
0.80, and the GPC elution portion of poly(2,6-dimethyl-1,4-phenylene) ether equivalent to polystyrene molecular weight 3000 or less is 5% by weight or less, and poly(2,6-dimethyl ―
The amount of poly(2,6-dimethyl-1,4-phenylene) ether precipitated from a dichloromethane solution containing 5% by weight of 1,4-phenylene) ether (after standing at 23°C for 5 hours) is 70% by weight. % or more. 11. The resin composition according to claim 10, wherein [η] of the poly(2,6-dimethyl-1,4-phenylene) ether is 0.60 to 0.75. 12. The resin composition according to claim 10, wherein the GPC eluted portion of poly(2,6-dimethyl-1,4-phenylene) ether having a polystyrene molecular weight of 10,000 or less is 8% by weight or less. 13. The resin composition according to claim 10, wherein the GPC elution portion of poly(2,6-dimethyl-1,4-phenylene) ether having a polystyrene molecular weight of 10,000 or less is 6% by weight or less. 14 Amount of poly(2,6-dimethyl-1,4-phenylene) ether precipitated from a dichloromethane solution containing 5% by weight of poly(2,6-dimethyl-1,4-phenylene) ether (23°C, 11. The resin composition according to claim 10, wherein the resin composition (after standing for 5 hours) is 80% by weight or more. 15 The composition is poly(2,6-dimethyl-1,4
-phenylene) ether 25-70% by weight,
The resin composition according to any one of claims 10 to 14, which comprises 75 to 30% by weight of HIPS. 16. The resin composition according to any one of claims 10 to 15, wherein the rubber content in the composition is 2.5 to 10% by weight. 17. The resin composition according to any one of claims 10 to 15, wherein the rubber content in the composition is 3 to 8% by weight. 18 Volume average particle diameter ( _V ) of elastic phase of HIPS
The resin composition according to claim 10, wherein the ratio ( _V / _o ) of _V and _o (number average particle diameter of the elastic phase) is 3.0 or more. 19. The resin composition according to claim 18, wherein ( _V / _o ) is 4.0 or more. 20 General formula [Formula] [Formula] (R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are the same or different
It is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms excluding a tert-butyl group, an aryl group, a halogen, or hydrogen, and R ₅ and R ₆ are not hydrogen at the same time. ) as a repeating unit, and 20 to 80% by weight of polyphenylene ether (PPE) consisting of [ ], or [ ] and [ ], and 80 to 20% by weight of rubber-reinforced high-impact polystyrene (HIPS) and styrenic resin. % and PPE.
The intrinsic viscosity [η] (30℃, chloroform solution) is
1. A resin composition having a gel permeation chromatography (GPC) elution fraction of PPE having a polystyrene molecular weight of 3000 or less equivalent to 5% by weight or less. 21. The resin composition according to claim 20, wherein [η] of PPE is 0.55 to 0.75. 22. The resin composition according to claim 20, wherein the GPC eluted portion of PPE having a polystyrene molecular weight of 10,000 or less is 8% by weight or less. 23. The resin composition according to claim 20, wherein the GPC eluted portion of PPE having a polystyrene molecular weight of 10,000 or less is 6% by weight or less. 24 A polymer in which the styrene resin is composed of a styrene compound alone or two or more, or a styrene compound and acrylonitrile, methyl methacrylate, acrylic ester, α,β-unsaturated carboxylic acid anhydride, α,β-unsaturated 21. The resin composition according to claim 20, which is a copolymer comprising a compound copolymerizable with the styrene compound, such as a carboxylic acid imide compound. 25 α, β- which can be copolymerized with styrene compounds
25. The resin composition according to claim 24, wherein the unsaturated carboxylic anhydride is maleic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, or tetrahydrophthalic anhydride. 26 α, β- which can be copolymerized with styrene compounds
Imide compounds of unsaturated carboxylic acids have the general formula (In the formula, R ₇ , R ₈ , and R ₉ represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, a phenylene group, and an alkylene group). 25. The resin composition according to claim 24, which is represented by: 27 The imide compound of α,β-unsaturated carboxylic acid is maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-(p-methylphenyl)maleimide. imide, N-(3,5-dimethylphenyl)maleimide, N-(p-methoxyphenyl)maleimide, N-benzylmaleimide, N-(1
27. The resin composition according to claim 26, which is maleimide (naphthyl). 28 A composition comprising 20 to 80% by weight of poly(2,6-dimethyl-1,4-phenylene) ether and 80 to 20% by weight of HIPS and styrene resin, the composition comprising poly(2,6-dimethyl-1,4-phenylene) ether The intrinsic viscosity [η] of 1,4-phenylene) ether (30°C, chloroform solution) is in the range of 0.50 to 0.80, and the poly(2,6-dimethyl-1,4-phenylene) ether has a polystyrene molecular weight of 3000. below
Poly(2,6-dimethyl-1,4-phenylene) from a dichloromethane solution in which the GPC eluted portion is 5% by weight or less and contains 5% by weight of poly(2,6-dimethyl-1,4-phenylene) ether. A resin composition characterized in that the amount of precipitated (phenylene) ether (after standing at 23°C for 5 hours) is 70% by weight or more. 29. The resin composition according to claim 28, wherein the poly(2,6-dimethyl-1,4-phenylene) ether has an intrinsic viscosity [η] of 0.60 to 0.75. 30. The resin composition according to claim 28, wherein the GPC elution portion of poly(2,6-dimethyl-1,4-phenylene) ether having a polystyrene molecular weight of 10,000 or less is 8% by weight or less. 31. The resin composition according to claim 28, wherein the GPC elution portion of poly(2,6-dimethyl-1,4-phenylene) ether having a polystyrene molecular weight of 10,000 or less is 6% by weight or less. 32 Amount of poly(2,6-dimethyl-1,4-phenylene) ether precipitated from a dichloromethane solution containing 5% by weight of poly(2,6-dimethyl-1,4-phenylene) ether (23°C, 29. The resin composition according to claim 28, wherein the resin composition (after standing for 5 hours) is 80% by weight or more. 33 A polymer in which the styrenic resin is composed of a styrene compound alone or two or more, or a styrene compound and acrylonitrile, methyl methacrylate, acrylic ester, α,β-unsaturated carboxylic acid anhydride, α,β-unsaturated 29. The resin composition according to claim 28, which is a copolymer comprising a compound copolymerizable with the styrenic compound, such as a carboxylic acid imide compound. 34 α, β- which can be copolymerized with styrene compounds
34. The resin composition according to claim 33, wherein the unsaturated carboxylic anhydride is maleic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, or tetrahydrophthalic anhydride. 35 α, β- which can be copolymerized with styrene compounds
Imide compounds of unsaturated carboxylic acids have the general formula (In the formula, R ₇ , R ₈ , R ₉ are hydrogen atoms, alkyl groups,
alkenyl group, cycloalkyl group, phenyl group,
Indicates a phenylene group and an alkylene group. Claim 33, which is expressed in
The resin composition described in . 36 α. The imide compound of β-unsaturated carboxylic acid is maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-(p-methylphenyl)maleimide, N- -(3,5-dimethylphenyl)maleimide, N-(p-methoxyphenyl)maleimide, N-benzylmaleimide, N-(1
36. The resin composition according to claim 35, which is maleimide (-naphthyl). 37. The resin composition according to claim 28, wherein the rubber content in the composition is 2.5 to 10% by weight. 38. The resin composition according to claim 28, wherein the rubber content in the composition is 3 to 8% by weight.