JPH02269767A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To improve the heat distortion resistance, impact strength, oil resistance, and blow moldability by compounding a polyphenylene ether, a polyamide, a specific copolymer, and a rubberlike material. CONSTITUTION:20-70wt.% polyphenylene ether having the repeating units of formula I-III (wherein R1-R6 are each a monovalent group such as a 1-4C alkyl except tert-butyl, aryl, and halogen, and R5 and R6 are not simultaneously H), 25-70wt.% polyamide of which 30wt.% or higher has a molar ratio of the terminal amino group to the terminal carboxyl group of at least 2.0, 0.05-3wt.% copolymer of 99-60wt.% styrenic compd. with 1-40wt.% alpha,beta-unsatd. dicarboxylic anhydride, and 0-30wt.% rubberlike material (e.g. styrene-butadiene block copolymer) are melted and mixed in such a way that in the continuous phase of said polyamide three other ingredients are dispersed as particles of a mean diameter of 1-3mum.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a heat-resistant resin composition that has excellent heat resistance and oil resistance and is suitable for blow molding. More specifically, polyphenylene ether, a specific polyamide, a copolymer containing a styrene compound and an α,β unsaturated dicarboxylic acid anhydride as components, and a rubbery substance are substantial constituents, and these components are specified. The present invention relates to a heat-resistant resin composition which is suitable for blow molding and can also be used for other extrusion molding.

<Prior Art> Polyamide resin has excellent mechanical strength, oil resistance, abrasion resistance, heat resistance, etc., and is used in large quantities as one of the most typical engineering plastics. However, this polyamide resin has the disadvantage that its properties such as dimensional stability, hygroscopicity, resistance to heat deformation under high loads, and impact resistance when dry are lower than those of other plastics.

On the other hand, polyphenylene ether resin is a resin with excellent dimensional stability, electrical properties, heat deformation resistance under high loads, and water resistance, and is widely used industrially in the form of a blend with polystyrene resin. However, this polyphenylene ether resin has the major drawback of poor oil resistance and molding fluidity.

In this way, by taking advantage of the respective strengths of both resins,
For the purpose of compensating for the drawbacks of both resins, attempts have been made to blend the two resins, and a large number of compositions have been proposed so far.

As such, both resins contain styrene compounds and α
Blends containing copolymers of β-unsaturated dicarboxylic acid anhydrides are disclosed in Japanese Patent Publication No. 59-33614, European Patent Publication No. 147874, and Japanese Patent Application Laid-open No. 63-23.
It is disclosed in Japanese Patent Application Laid-Open No. 5364 and Japanese Patent Application Laid-Open No. 62-273254.

The composition disclosed in Japanese Patent Publication No. 59-33614 is
The balance of oil resistance, impact resistance, heat resistance, etc. is not sufficient,
Furthermore, the composition disclosed in European Patent Publication No. 147874 has significantly poor impact resistance, and
The compositions disclosed in JP-235364 only have improved melt fluidity, and neither of them provides a resin composition suitable for blow molding. On the other hand, JP-A-62-
The compositions shown in the Examples of Publication No. 273254 do not have sufficient impact resistance because the dispersed particle size is large, and there is no specification whatsoever regarding resin compositions suitable for blow molding.

Blow molding has recently attracted particular attention because of its great cost advantages over injection molding, and there is a strong desire to develop materials suitable for blow molding, even for blends of polyphenylene ether and polyamide.

<Problems to be Solved by the Invention> Blow molding materials need to have high viscosity at low shear rates in order to prevent the drawdown phenomenon in which the extruded parison sags due to its own weight; It is necessary that the appearance of the parison does not deteriorate due to melt fracture phenomena or the like when extruded at the bottom.

In view of these circumstances, the object of the present invention is to provide a heat-resistant resin composition that is a blend system of polyphenylene ether and polyamide, has an excellent balance of heat deformation resistance, impact resistance, oil resistance, etc., and is suitable for blow molding. It is about providing.

Means for Solving the Problems〉 As a result of intensive research to achieve the above object, the present inventors have developed a method for combining polyphenylene ether, a specific polyamide, a styrene compound, and an α,β unsaturated dicarboxylic acid anhydride. We have discovered that the objective can be achieved by controlling the dispersion form of these components in a specific state in a composition comprising a copolymer and a rubber-like substance as components in a predetermined ratio, Based on this knowledge, we have completed the present invention.

That is, the present invention provides (A) polyphenylene ether 2
0 to 70% by weight, (B) 25 to 70% by weight of a polyamide containing 30% by weight or more of a polyamide with a molar concentration ratio of terminal amino groups to terminal carboxyl groups of 2.0 or more, (C) a styrene compound and α, Copolymer 0.05-3 containing β-unsaturated dicarboxylic acid anhydride as a component and having a content of α, β-unsaturated dicarboxylic acid anhydride of 1 to 40% by weight
% by weight, and (D) a rubbery substance of 0 to 30%, and the polyamide of component (B) forms a continuous phase, and components other than component (B) in this continuous phase have an average particle size of 0. .1
The present invention provides a heat-resistant resin composition suitable for blow molding, which is characterized by forming a dispersed phase of ~3 μm.

The polyphenylene ether used in the present invention is -
maximum % formula % or a different tert-carbon alkyl group excluding t-butyl group, an aryl group, a halogen, a monovalent residue such as hydrogen, and R6, R, are not hydrogen at the same time. ) as a repeating unit, and the constituent units are [■] or CI) and (II), or a homopolymer or copolymer.

Representative examples of polyphenylene ether homopolymers include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl 1,4-phenylene) ether, and poly(2,6-dimethyl-1,4-phenylene) ether. diethyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(
2-Methyl-6n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-14-phenylene) ether, poly(2-methyl-6-chlor 1.
Examples include homopolymers such as 4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly(2-methyl-6-chloroethyl 1.4-phenylene) ether.

The polyphenylene ether copolymer is orthocresol or has the general formula (where Ih, R4, Rs, Rh are ter
Monovalent residues such as alkyl groups having 1 to 4 carbon atoms, aryl groups, halogens, and hydrogen, excluding t-butyl groups, and Rs
, Rh is not hydrogen at the same time. ) represented by 2, 3
．． 6-) It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by copolymerizing with an alkyl-substituted phenol such as trimethylphenol.

The polyamide used as component (B) in the present invention may be any polyamide as long as it has a --C-N11- bond in the polymer main chain and can be melted by heating.

Typical examples include 4-nylon, 6-nylon, 6,6-nylon, 12-nylon, 6,10-nylon, polyamides made from terephthalic acid and trimethylhexamethylene diamine, and metaxylylene diamine with adipic acid. polyamides from adipic acid and azelaic acid and 2,2-his(p-aminocyclohexyl)-propane, polyamides from terephthalic acid and 4,4'-diaminodicyclohexylmethane, and copolymerized nylons thereof. It will be done. Among these, 6-nylon, 6.6-nylon, and 6-6.6 copolymerized nylon are preferably used alone or in combination.

The polyamide used as component (B) in the present invention must contain 30% by weight or more of an amino-terminated polyamide with a high molar concentration ratio of terminal amino groups to terminal carboxyl groups of 2.0 or more based on the total polyamide. . Such a high amino terminal polyamide can be easily obtained by adding an extra diamine component during polymerization. Normally, the terminal group concentration ratio of polyamide resin is 1.0. Furthermore, in polyamide for injection molding, the molecule ff
Because of the 1l1 clause, carboxylic acids are added as end-capping agents, and such polyamides have an end group concentration ratio even smaller than 1.

In the present invention, the copolymer containing a styrene compound and an α,β unsaturated dicarboxylic acid anhydride used as component (C) includes a non-rubber reinforced copolymer and an impact-resistant rubber reinforced copolymer. Includes merging. Generally, the copolymer used in the present invention can be produced by conventional bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization techniques that utilize radical polymerization.

Styrene compounds forming the copolymer used in the present invention include styrene, orthomethylstyrene, paramethylstyrene, dimethylstyrene, metaethylstyrene, chlorstyrene, isopropylstyrene, tertiary-butylstyrene, alpha-methylstyrene, and ethylvinyl styrene. Toluene etc. or mixtures thereof are used. α,
The β-unsaturated dicarboxylic anhydride may be any monomer that can be copolymerized with a styrene compound, such as maleic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, and tetrahydrophthalic anhydride. Furthermore, as a third component, a monomer copolymerizable with a styrene compound and an α,β unsaturated dicarboxylic acid anhydride may be introduced. , methacrylic acid, vinyl cyanide compounds, etc. may also be used.

The rubber-reinforced copolymers used in the present invention include polybutadiene rubber, styrene-butadiene rubber, polybutene rubber, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, polyacrylate rubber, polyisoprene rubber, It can be obtained by polymerizing the monomers described above in the presence of a rubbery polymer such as natural rubber.

Examples of suitable copolymers for use in the present invention include styrene-maleic anhydride copolymer, styrene-maleic anhydride-methacrylic ester copolymer, styrene-maleic anhydride-acrylic ester copolymer, etc. and their rubber reinforcing polymers.

Further, the copolymer as component (C) used in the present invention contains 60 to 99 ffi of a styrene compound as a component, and has a content of α, β unsaturated dicarboxylic acid anhydride of 1 to 40%.
A copolymer or styrene compound in the heavy weight range and α
, a copolymer containing β-unsaturated dicarboxylic acid anhydride as a component, 60 to 96% by weight of a styrene compound, and 2 to
30% by weight of α,β unsaturated dicarboxylic acid anhydride and 2-2
Preferably, it is a copolymer with 0% by weight of methacrylic ester or acrylic ester. In the case of a rubber-reinforced copolymer, the composition of the resin phase excluding the rubber component is preferably within the above range.

Rubbery substances used as component (D) in the present invention include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermal These include plastic polyester elastomers, ethylene-based ionomer resins, and core-shell polymers consisting of a rubbery core and a non-rubberlike polymer shell, particularly styrene-butadiene block copolymers, and those in which some or all of the butadiene moieties are hydrogen. An added styrene-butadiene block copolymer is preferred. It is also possible to use rubber-like substances modified with epoxy compounds, unsaturated carboxylic acids, derivatives thereof, and the like.

Polyphenylene ether, polyamide in the present invention,
The composition ratio of the copolymer containing a styrene compound and an α,β unsaturated dicarboxylic acid anhydride and the rubber-like substance is 20 to 20% of the total amount of polyphenylene ether
70% by weight, preferably 3°O to 60% by weight, polyamide 25 to 70% by weight, preferably 30 to 55% by weight, copolymer containing a styrene compound and α,β unsaturated dicarboxylic acid anhydride from 0.05 to 3% by weight preferably 0.2-2% by weight and rubbery substances 0-30% by weight preferably 5-2
The weight is 0%.

Furthermore, regarding the dispersion form of each component, the polyamide forms a continuous phase, and the other components are dispersed in the continuous phase to form a dispersed phase with an average particle diameter of 001 to 3μ, preferably 0.2 to 2μ. It is necessary to be present.

In addition, if the polyamide is less than 25% by weight or the total amount of the three components other than polyamide exceeds 75% by weight with respect to the total amount of the four components, under any cross-wire conditions, the polyamide will form the continuous phase when the other components Unable to form a dispersed phase. On the other hand, if the polyamide content is more than 70% by weight or the polyphenylene ether content is less than 20% by weight, the composition will have poor heat deformation resistance under high loads, which is not preferable.

The copolymer containing a styrene compound and an α,β unsaturated dicarboxylic acid anhydride as component (C) is necessary to increase the melt viscosity of the resin composition and improve the blow moldability. If the styrene content of the copolymer is less than 60% by weight, or if the α,β-unsaturated dicarboxylic acid anhydride is 40% by weight or more, the mechanical properties such as impact resistance of the resin composition will deteriorate. If the amount of the α,β-unsaturated dicarboxylic acid anhydride is less than 1%, the effect of increasing the melt viscosity of the resin composition is small, and a resin composition suitable for blow molding cannot be obtained. Furthermore, if the amount of the copolymer is less than 0.05% by weight with respect to the total amount of the four components constituting the present invention,
Blow moldability is poor, and a content of 3% by weight or more is undesirable as it adversely affects the heat distortion temperature and the appearance of the melt extrudate.

Further, the copolymer of the high amino terminal polyamide of the component (B) and the component (C) improves blow moldability due to a synergistic effect, and the molar concentration ratio of the amino group and the carboxyl group at the polyamide terminal is 2. A sufficient synergistic effect can be obtained when the ratio is 0 or more, preferably 2.5 or more. It is also possible to use a high amino terminal polyamide with a molar concentration ratio of terminal amino groups to terminal carboxyl groups of 2.0 or more and a polyamide with a low terminal amino group concentration. Unless the terminal polyamide is used in an amount of 30% by weight or more, preferably 50% by weight or more, a sufficient synergistic effect cannot be obtained.

A rubber-like substance is necessary for improving impact resistance, and may be blended as necessary, but if it exceeds 30% by weight, the heat distortion temperature and other mechanical strengths are significantly reduced.

In addition, setting the dispersion form of each component as described above is important for improving oil resistance of the composition when polyamide forms a dispersed phase or when both polyamide and a component other than polyamide form a continuous phase. If the average particle diameter of components other than polyamide is 3 μm or more, the impact resistance will decrease and the appearance of the melt-extruded product will be poor. Moreover, if the thickness is less than 0.1 μm, the impact resistance and the appearance of the melt extruded product are not particularly improved, and 0.1 μI
It is difficult to control the shearing force below the mechanical shearing capacity of the processing machine, so it is not necessary.

Next, a general method for producing the composition of the present invention will be described, but of course other production methods can be used as long as the above conditions are satisfied.

That is, the composition of the present invention comprises polyphenylene ether,
Polyamide, a copolymer containing a styrene compound and an α,β unsaturated carboxylic acid anhydride, and a rubbery substance, based on the total amount thereof, 20 to 70% by weight and 25 to 7% by weight, respectively.
0 heavy view%, weight 05-3% by weight and 0-3.0% by weight
It is obtained by melt-kneading at a ratio of .

As for the kneading method, the four components may be kneaded all at once, or the remaining components may be kneaded into a blend obtained by pre-kneading two or more components.

During melt kneading, α, β unsaturated dicarboxylic acids and derivatives thereof,
0.1 to 2% by weight of vinyl silane compound, saturated aliphatic polycarboxylic acid and its derivatives based on the total amount of the three components
Can be added.

Representative examples of such compounds include maleic acid, maleic anhydride, maleimide, vinylmethoxysilane, T-aminopropylmethoxysilane, citric acid, and malic acid.

Furthermore, instead of these compounds, a modified polyphenylene ether to which these compounds have been added can also be blended, and (A
) A part or all of the component polyphenylene ether can also be a modified polyphenylene ether.

The temperature and time for melt-kneading vary depending on the type of polyamide used and the composition ratio of polyamide and polyphenylene ether, but usually the temperature is in the range of 240 to 350°C, preferably 260 to 320°C; 2-1
A kneading time of about 0 minutes, preferably 0.5 to 5 minutes is used. As the melt-kneading device, an extruder, a kneader, a roll, etc. can be used, but an extruder is particularly suitable.

The composition of the present invention may optionally contain other polymer plasticizers, flame retardants, or fillers such as glass fibers, carbon fibers, potassium titanate fibers, carbon black, mica, talc, silica, and clay. It can be added within the range that does not impair the purpose. The other polymer is preferably a polymer that is substantially compatible with the polyphenylene ether phase, such as polystyrene, rubber-modified polystyrene, and the like.

In addition, the dispersion form and the dispersed particle diameter in the present invention can be determined by electron microphotography, and the dispersed particle diameter can be calculated as follows.

That is, a transmission electron micrograph (photo magnification: 4000 times) of an ultrathin section cut from the molded article is adjusted, the dispersed particle diameter di and particle n are determined, and the average diameter of the dispersed phase is calculated by the following formula.

In this case, if the particle shape cannot be regarded as spherical, its short axis and long axis were measured, and the sum of the two, 2, was defined as the particle diameter. Furthermore, to calculate the average particle diameter, the diameters of at least 2000 particles are measured.

<Effects of the Invention> The heat-resistant resin composition of the present invention not only has an excellent balance of physical properties such as oil resistance, impact resistance, and heat deformation resistance, but also has a high melt viscosity at low shear rates and a high melt viscosity at high shear rates. Because of its excellent appearance during melt extrusion, it can provide a material suitable for professional molding as well as other extrusion molding.

<Example> Next, the present invention will be explained in more detail with reference to Examples. The properties of the materials in the Examples were evaluated by the following test methods.

Melting characteristics: L/
The apparent melt viscosity (rl mal t) was measured using an orifice with D = 2 and a shear rate of I 5ec-' at 260"C unless otherwise specified.
The appearance and sag of the melt extrudate under a shear rate of -' were evaluated by visual inspection: if it was smooth due to the degree of melt fracture, it was considered good, and if there was significant melt fracture, it was judged to be poor.

Izotsu impact strength (with notch); JIS K
7110 heating deformation temperature; JIS K 7207 weight 18.6 kg/c+a Examples 1 to 2 and Comparative Example 1 Poly(2,6-dimethylphenylene) having an intrinsic viscosity of 0.54 (25°C, in chloroform) 44.5% by weight of 6-nylon, which has a relative viscosity of 2.5 (25°C in concentrated sulfuric acid) and an end group concentration ratio shown in Table 1 as a polyamide, Styrene-maleic anhydride copolymer (manufactured by ARCO Chemical Co., Ltd., trade name; Dylark 232, maleic anhydride approximately 10% by weight) 1% by weight, styrene-butadiene block copolymer (manufactured by Asahi Kasei Corporation, trade name; Toughblane A) 10-weight compound and 0.5 parts by weight of maleic anhydride as a dispersion particle regulator were added to 100 parts by weight of the total amount. Twin-screw extruder with screw diameter 53 marks (Werner & Pflederer)
manufactured by ZSK-53) at 290°CC120O
The mixture was extruded and kneaded at rp to form pellets.

Then, the melting properties using pellets and the physical properties using injection molded test pieces were evaluated. The results are shown in Table 1.

Comparative Example 2 The blending amounts of polyphenylene ether and 6=nylon in Example 1 were each 39.5% by weight, and styrene-
Except for blending 10i% of maleic anhydride copolymer,
The same operations as in Example 1 were performed to obtain the results shown in Table 1.

Table 1 Examples 3 to 4 and Comparative Examples 3 to 5 The blending amounts of polyphenylene ether and polyamide in Example 1 were changed to the ratios shown in Table 2, and the polyamide was different from the 6-nylon used in Example 1. The same operations as in Example 1 were performed, except that the 6-nylon used in Comparative Example 1 was used in half a tatami mat, and the results shown in Table 2 were obtained. However, in Comparative Example 5, kneading was performed using a twin-screw extractor with a screw diameter of 30M.

Table Examples 5 to 6 and Comparative Examples 6 to 7 In place of the rubbery substance and styrene-maleic anhydride copolymer in Example 2, the rubbery substance and styrene-maleic anhydride copolymer shown in Table 3 were used. The same operation as in Example 2 was carried out except for using , and the results shown in Table 3 were obtained.

Table 1) SMAlooO: Styrene-maleic anhydride copolymer containing about 50% by weight of maleic anhydride (manufactured by ARCO Chemical) 2) Toughtic H1271; Hydrogenated styrene-butadiene block copolymer manufactured by Asahi Kasei Corporation 3) Tuffrene 200; Styrene-butadiene block copolymer manufactured by Asahi Kasei Kogyo ■

Claims (1)

[Scope of Claims] (A) 20 to 70% by weight of polyphenylene ether, (B
) The molar concentration ratio of terminal amino group to terminal carboxyl group is 2.
．． 25 to 70% by weight of polyamide containing 0 or more polyamide at 30% by weight or more based on the total polyamide; (C) containing a styrene compound and α,β unsaturated dicarboxylic acid anhydride as components; 0.05 copolymer with an unsaturated dicarboxylic acid content of 1 to 40% by weight
3% by weight and (D) a rubbery substance 0 to 30% by weight, and component (B) forms a continuous phase in which components other than component (B) have an average particle size of 0.5% by weight. 1~3μ
A heat-resistant resin composition characterized by existing as a dispersed phase of m.