JPH05279564A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] A resin composition comprising (A) 10 to 90% by weight of an amino group-containing polyphenylene ether and (B) 90 to 10% by weight of polyphenylene sulfide. [Effect] The resin composition of the present invention has a finer dispersion particle diameter, improves the compatibility of originally incompatible components, and provides an engineering plastic excellent in mechanical strength.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing an amino group-containing polyphenylene ether resin (A) and a polyphenylene sulfide resin (B). This is a thermoplastic resin composition useful for providing engineering plastics industrial materials having excellent mechanical strength, heat resistance rigidity and appearance, such as connectors, ignition manifolds, gears, bumpers, coil sealing materials and the like.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter PPS)
Abbreviated as “) is known as a heat-resistant resin having a high melting point, which is excellent in fluidity, organic solvent resistance, electrical characteristics, flame retardancy, and the like. However, when used as a molding material, it has a drawback that the polymerization degree is low and the molding stability is poor. Further, since the glass transition temperature is not so high as about 90 ° C., the decrease in rigidity at high temperature is large. Therefore, performance improvement has been carried out by compounding with inorganic fillers such as glass fiber, carbon fiber, talc, silica, etc., but in this case, the appearance of the obtained molded product deteriorates and the molded product warps. There are problems such as being easy.

On the other hand, polyphenylene ether (hereinafter referred to as PP
(Abbreviated as E) is recognized as an engineering plastic having excellent heat resistance, dimensional stability, non-hygroscopicity, and electrical characteristics, but its melt flowability is poor, molding processing is difficult, and oil resistance However, there is a drawback that the impact resistance is poor. Therefore, various compositions have been proposed for the purpose of providing a molding material which complements the drawbacks without impairing the advantages of both.

For example, a technique for improving the molding processability of PPE by blending PPS with PPE has been disclosed (Japanese Patent Publication No. 56-34032). However, although molding processability is improved, the inherent compatibility between PPE and PPS is poor, and such a simple blend system has poor affinity at the interface, resulting in phase separation during molding.
A composition having excellent mechanical strength cannot be obtained.

Therefore, some techniques have been proposed which can improve the compatibility of the two. For example, a method of blending an epoxy resin with a blended product of PPS and PPE (Japanese Patent Laid-Open No. 59-59)
-164360 and JP-A-59-213758.
No.), a method of blending a styrene polymer having an epoxy group (JP-A-2-86652 and JP-A-1-213).
No. 361) is disclosed.

In addition, a functional group is introduced into PPE to modify P
As PE, it has been proposed to improve the miscibility with PPS. JP-A-64-36645 and JP-A-2-3
No. 6261 uses a compound having an ethylenically unsaturated bond and an acid anhydride group in the molecule, specifically, an acid-modified PPE obtained by melt-kneading maleic anhydride and PPE. However, the mechanical strength of the resin composition obtained here is still insufficient.

Further, in Japanese Patent Laid-Open No. 1-259060, modified PPE, specifically, acid-modified PPE obtained by melt-modifying PPE with maleic anhydride, 2-hydroxyethyl acrylate, glycidyl methacrylate, etc., hydroxyl group modification It is disclosed that a composition having excellent mechanical strength can be obtained by the combination of PPE or PPS modified similarly to PPE modified with epoxy group. However, the miscibility of PPE and PPS cannot be said to be sufficient by any of these methods.

[0008]

The present invention is based on PPS and P
It is an object of the present invention to provide a thermoplastic resin composition having extremely excellent miscibility with PE and excellent appearance, mechanical strength, solvent resistance, and moldability of a molded product.

[0009]

The present invention provides a resin composition containing the following components (A) and (B) in the following proportions. Component (A) Amino group-containing polyphenylene ether resin 10 to 90% by weight Component (B) Polyphenylene sulfide resin 90 to 10% by weight.

The present invention will be described in more detail below. (A) Amino group-containing polyphenylene ether resin Amino group-containing PPE (A) used in the present invention is PPE.
A PPE in which an amino group is added to the terminal phenolic hydroxyl group by a functionalizing agent, for example, PPE and a functionalizing agent having an amino group are added in the presence or absence of an organic solvent capable of dissolving PPE to form a base. 50-200 using a reactive catalyst
It can be obtained by reacting at a temperature of ° C.

(I) PPE The raw material PPE has the general formula (I)

[0012]

[Chemical 1]

(Wherein Q¹Are halogen atom and primary
Alternatively, secondary alkyl group, aryl group, aminoalkyl group
Group, halohydrocarbon group, hydrocarbonoxy group or halocarbon group
Represents a hydrogen oxy group, Q²Are hydrogen atom and halogen atom
Child, primary or secondary alkyl group, halohydrocarbon group
Alternatively, it represents a halohydrocarbonoxy group. ) Structure shown by
It is a homopolymer or a copolymer having a position. Q¹and
Q²Preferred examples of the primary alkyl group of are methyl, ethyl
Ru, n-propyl, n-butyl, n-amyl, isoami
2, 2-methylbutyl, 2,3-dimethylbutyl, 2
-, 3- or 4-methylpentyl or heptyl
It Examples of secondary alkyl groups are isopropyl, sec-butyl.
It is tyl or 1-ethylpropyl. Often Q ¹
Is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms.
Q is a kill group²Is a hydrogen atom.

Specifically, poly (2,6-dimethyl-
1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-
Methyl-6-ethyl-1,4-phenylene) ether,
Poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,
4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,
6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,
Graft polymerization of styrene to 3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer, poly (2,6-dimethyl-1,4-phenylene) ether And the graft copolymer obtained by graft-polymerizing styrene to the 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer.

A preferred homopolymer of PPE is poly (2,6-dimethyl-1,4-phenylene ether). Suitable copolymers include 2,6-dimethyl-
It is a random copolymer of 1,4-phenylene ether and 2,3,6-trimethyl-1,4-phenylene ether. The molecular weight of PPE is usually such that the intrinsic viscosity at 30 ° C. in chloroform is about 0.2 to 0.8 dl / g.

PPE is usually produced by oxidative coupling of the above-mentioned monomers. Numerous catalyst systems are known for the oxidative coupling polymerization of PPE. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, and cobalt, usually in combination with various other substances, and the like.

(Ii) Process for producing amino group-containing PPE Amino group-containing PPE obtained by a functionalizing agent and PPE
Can be produced, for example, by the methods shown in the following (a) to (d). (A) PPE has the formula (II) X—R ¹ —NH ₂ (II) (wherein, X is a halogen group, and R ¹ has 1 to 3 carbon atoms).
2 represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aryl group. ) Is reacted with a halogenated alkylamine to give a compound of the general formula (III)

[0018]

[Chemical 2]

(In the formula, Q ¹ and Q ² are the same as those in the above formula (I), m is a number from 10 to 400, and R ¹ is the same as the above formula (II).) Method for producing group-containing polyphenylene ether (Japanese Patent Application No. 24-24737)
No. 8).

As the modifier represented by the formula (II), 2-
A halogenated primary amine such as chloroethylamine, 2-bromoethylamine, 3-chloropropylamine, and 3-bromopropylamine, or a hydrogen chloride salt or hydrobromide salt thereof can be used. (B) PPE with formula (IV)

[0021]

[Chemical 3]

(In the formula, R ² represents a hydrocarbon having 1 to 12 carbon atoms, a hydrocarbon / aromatic having 6 to 12 carbon atoms, a halogen atom, a hydroxyl group, or an amino group. X represents a halogen atom. Z represents a carbon atom or a nitrogen atom), and is reacted with a halogenated aminoheterocyclic compound, for example, 1-chloro-2,3-diaminotriazine to give a compound represented by the general formula (V).

[0023]

[Chemical 4]

(Wherein Q ¹ , Q ² and m are defined by the above formula (II
Same as I). R ² and Z are the same as those in the above formula (IV). )
A method for producing an amino group-containing polyphenylene ether represented by (Japanese Patent Application No. 3-280054).

The halogenated amino heterocyclic compound represented by the formula (IV) is 2-chloro-4,6-diamino-
1,3,5-triazine, 6-chloro-2,4-diaminopyrimidine, 2-amino-4-chloro-6-hydroxypyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino-4 , 6-dichloropyrimidine and the like.

(C) The terminal epoxidized polyphenylene ether is added to the general formula (VI) R ^3- (NH ₂ ) _n (VI) (wherein R ³ is an aliphatic hydrocarbon, an aromatic hydrocarbon or an aliphatic aromatic group). Represents a hydrocarbon, n represents a number of 2 to 10), and is reacted with a polyamine represented by the general formula (VII).

[0027]

[Chemical 5]

A method for producing an amino group-containing polyphenylene ether represented by the formula (wherein Q ¹ , Q ² and m are the same as those in the above formula (I) and A represents a polyamine compound residue.) 2-190436).

As the polyamine, triethylenetetraamine, tetraethylenepentamine, diethylenetriamine, ethylenediamine, 1,10-diaminodecane, 1,6-diaminohexane, 3,3'-diaminodipropylamine, N, N'- Bis (2-aminoethyl)
-1,3-Propanediamine, tris (2-aminoethyl) amine, 4,4'-diaminodiphenylmethane and the like can be used.

(D) PPE has the general formula (VIII)

[0031]

[Chemical 6]

(In the formula, R ⁴ is a divalent or higher valent carbon number 1 to 32
Represents an aliphatic hydrocarbon, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group, and p is an integer of 2 to 6. ) Is reacted with a polyisocyanate represented by the general formula (IX)

[0033]

[Chemical 7]

A method for producing an amino group-containing PPE represented by the formula (wherein Q ¹ , Q ² , m and R ⁶ are the same as those in the above formula (III)) (JP-A-4-68024). As the polyisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,
4-diisocyanato-3,3'-dimethyldiphenylmethane and the like can be used.

Among the amino group-containing PPE obtained by the above methods (a) to (d), in the present invention,
From the viewpoint of reaction activity and thermal stability, those of formula (III) are preferred. Part (80% by weight or less) of the amino group-containing polyphenylene ether of the component (A) used in the present invention may be replaced with unmodified PPE such as poly (2,6-dimethyl-1,4-phenylene ether).

(B) Polyphenylene sulfide resin (PPS) PPS of the component (B) has the general formula (X)

[0037]

[Chemical 8]

A crystalline resin containing a repeating unit represented by as a main constituent element, which is composed of the above-mentioned repeating unit, or contains 80% by mole or more, and more preferably 90% by mole or more of this constituent unit, It is preferable in terms of heat resistance. When substantially all the constituents of PPS do not consist of the above repeating unit, the rest (for example, up to 20 mol%) is copolymerizable, for example, the above (X
I) to (XVII) can be satisfied with a component consisting of repeating units.

[0039]

[Chemical 9] (In the formula, R is an alkyl group, a phenyl group, or an alkoxy group.)

[0040]

[Chemical 10]

The PPS as a raw material preferably has a substantially linear structure from the viewpoint of the physical properties of the molded product. As long as the physical properties are not substantially reduced, for example, a polymerized crosslinked product obtained by using an effective amount of a crosslinking agent (for example, trihalobenzene) at the time of polymerization, or heat treated by heat treatment of PPS in the presence of oxygen etc. Crosslinked products can also be used.

This PPS has a melt viscosity at 300 ° C. of 1
00-100,000 poise, preferably 500-5
10,000 poise, more preferably 500 to 20,
It is preferably in the range of 000 poise. Melt viscosity is 10
When it is less than 0 poise, the fluidity is too high and molding is difficult, which is not preferable. Further, even if the melt viscosity exceeds 100,000 poise, the fluidity is too low, and molding is difficult.

Although this PPS can be produced by any method, it is preferable that PPS satisfy the above conditions.
PS is, for example, a method for producing a polymer having a relatively small molecular weight as disclosed in JP-B-45-3368, JP-B-5-5.
According to the method for producing a linear polymer having a relatively high molecular weight as disclosed in No. 2-12240 or the method for heating a low molecular weight polymer in the presence of oxygen to obtain a crosslinked product, or by making necessary modifications thereto. In addition, it can be manufactured.

<Additional Components> Other additional components can be added to the resin composition according to the present invention. For example,
Antioxidant, weather resistance improver, nucleating agent, flame retardant, plasticizer,
A fluidity improver or the like can be used as an additional component. Further, addition of organic and inorganic fillers and reinforcing agents, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like is effective for improving rigidity, heat resistance and dimensional accuracy. For practical use, various known colorants and their dispersants can be used.

Further, addition of impact strength improver, especially styrene-butadiene copolymer rubber and its hydride,
Ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, and further modified products of α, β-unsaturated carboxylic acid anhydrides and modified products thereof with glycidyl ester or unsaturated glycidyl ether, and unsaturated epoxy compounds The addition of a copolymer composed of ethylene and ethylene or an unsaturated epoxy compound, a copolymer composed of ethylene and an ethylenically unsaturated compound, etc. is effective in improving the impact strength of the composition. The above impact resistance improvers may be used alone or in combination of two or more. The blending amount of the impact strength improver varies depending on the physical property value used as a guide, but in the case of improving the balance between rigidity and impact strength of the composition, for example, it is 5 to 30% by weight in the resin component of the composition.

<Composition ratio of constituents> The composition ratio of the amino group-containing polyphenylene ether of the component (A) and the PPS of the component (B) in the thermoplastic resin composition of the present invention is a balance between mechanical strength and organic solvent resistance. Therefore, the amino group-containing polyphenylene ether is 10 to 90% by weight, preferably 2
0 to 80% by weight, more preferably 30 to 70% by weight, and PPS is 90 to 10% by weight, preferably 80 to 2%.
It is 0% by weight, more preferably 70 to 30% by weight.
If the PPS content is less than 10% by weight, the organic solvent resistance is inferior, which is not preferable.

<Manufacturing Method and Molding Method of Mixed Composition> As a melt-kneading method for obtaining the thermoplastic resin composition of the present invention, a kneading method generally used for thermoplastic resins can be applied. For example, if necessary, the powdery or granular components, together with the additives described in the additional components section, are uniformly mixed by a Henschel mixer, a ribbon blender, a V-type blender or the like, and then uniaxial or multiaxial. It can be kneaded with a kneading extruder, roll, Banbury mixer, or the like. The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, blow molding, extrusion molding, thermoforming, press molding and the like. A molding method can be applied.

[0048]

EXAMPLES The present invention will be described in detail below with reference to examples. The reaction rate of the phenolic hydroxyl group at the terminal group of PPE and the confirmation of the amino group were confirmed by measuring the infrared absorption spectrum of 1.5 wt% carbon tetrachloride solution of the modified PPE using a quartz cell with an optical path length of 10 mm. Carried out. That is, the reaction rate was calculated from the value of the absorbance (3622 cm ^-1 ) of the terminal phenolic hydroxyl group of PPE before and after the reaction.

The components used are as follows. PPS: Topren PPS (trade name: Topren T
-7) was used. PPE: poly (2,6-dimethyl-1,4-phenylene ether) manufactured by Nippon Polyether Co., Ltd. (intrinsic viscosity 0.3 dl / g measured in chloroform at 30 ° C.)
Was used. Amino group-containing PPE: the above P with an intrinsic viscosity of 0.3 dl / g
400 g of PE and 4 liters of toluene were charged into a reactor and heated and stirred at 80 ° C. to dissolve PPE. Then, as a basic catalyst, 100% 50% aqueous sodium hydroxide solution is used.
g, after adding 20 g of trioctylmethylammonium chloride as a phase transfer catalyst, the temperature of the reaction mixture was raised to 90 ° C. and stirring was continued for 30 minutes. Subsequently, an aqueous solution of 40 g of 3-chloropropylamine, which is a functionalizing agent, was added over 15 minutes. Furthermore, after heating and stirring for 7 hours, methanol 15
The modified resin produced was poured into liter to precipitate. After filtering this off, it was washed with 10 liters of water and methanol 1
It was washed with 0 liter.

By heating under reduced pressure at 80 ° C., an amino group-containing polyphenylene ether was obtained. 100% yield, PPE
The reaction rate of the terminal hydroxyl group was 100%. The proton nuclear magnetic resonance spectrum revealed that the number of amine halide compounds added was one molecule. In the obtained amino group-containing polyphenylene ether, absorption attributed to the amino group was observed at 3380 cm ⁻¹ in FT-IR in a carbon tetrachloride solution.

<Example 1> P containing amino group obtained in the above example
After 50 parts by weight of PE and 50 parts by weight of PPS were dry-blended, they were kneaded for 5 minutes at a temperature of 310 ° C. and a rotor rotation speed of 180 rpm by using a Labo Plastomill manufactured by Toyo Seiki Co. After the kneading was completed, the mixture was crushed by a crusher into granules.

A test piece was prepared from the granular sample by using a CS183MMX minimax injection molding machine manufactured by Custom Scientific under the condition of a temperature of 310.degree. This test piece was heated in a hot air dryer at 120 ° C. for 4 hours, and then P
The PS was sufficiently crystallized. Upon kneading and molding, PPS used was vacuum dried at 100 ° C. for 24 hours in advance. The test pieces for physical property evaluation were evaluated after being stored in a desiccator for 2 days. (1) Heat resistance rigidity: length 47 mm, width 5 mm, thickness 2 mm
Was injection-molded and the temperature dependence of the storage rigidity (E ') was measured at a temperature of 150 ° C using a solid viscoelasticity measuring device RSAII manufactured by Rheometrics Far East Co., Ltd. under the condition of a frequency of 1 Hertz. The storage rigidity (E ') value was determined. (2) Impact strength: Custom Scientific Minimax Izod impact tester CS manufactured by injection molding a test piece having a length of 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mm.
The Izod impact strength without a notch at 23 ° C. was measured using a −138TI type.

Since the PPE shown in the comparative example could not be injection-molded due to poor fluidity, it was 280
Press molding was carried out under the condition of ° C to prepare a sheet having a thickness of 2 mm. Various test pieces were cut from this sheet and subjected to physical property evaluation. The evaluation method is as follows. Heat resistance rigidity: Measured according to the above condition (1).

Impact strength: Three test pieces each having a thickness of 2 mm were piled up and fixed with an adhesive tape "Cellophane tape (trade name)" manufactured by Nitto Denko Corporation, and then measured according to JIS K-7110. For the dispersion form, a part of the sheet is cut out and a scanning electron microscope S-2400 manufactured by Hitachi, Ltd. is used.
It was observed at a magnification of 1000 times and 5000 times. From the observed morphological photograph, SPICCAII manufactured by Nippon Avionics Co., Ltd.
The number average dispersion diameter Dn was determined by the following equation using a mold image analyzer.

Dn = Σnidi / Σni A good appearance was evaluated as ◯, a worse but practically no problem was evaluated as Δ, and a sparse surface that was practically problematic was evaluated as x. The results are shown in Table 1.

<Example 2> Dry blending was carried out according to the formulation shown in Table 1, and the same procedure as in Example 1 was carried out. The results are shown in Table 1.

<Comparative Examples 1 to 5> Dry blending was performed according to the formulations shown in Table 1 and the same procedure as in Example 1 was performed. The results are shown in Table 1.

[0058]

[Table 1]

[0059]

INDUSTRIAL APPLICABILITY The present invention combines PPS and amino group-containing polyphenylene ether to produce PPS and P
Since the compatibility of PE could be made extremely good, the appearance and impact strength of the molded product were remarkably improved.

Claims (1)

[Claims] 1. A thermoplastic resin composition comprising the following components (A) and (B) in the following proportions. Component (A) Amino group-containing polyphenylene ether resin 10 to 90% by weight Component (B) Polyphenylene sulfide resin 90 to 10% by weight.