JPH0625527A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To give a resin composition containing a polyamino-phenylene ether comprising 2 kinds of specific structural units and a polyamide resin, exhibiting excellent compatibility between both the resin components to give good component dispersion, high mechanical strength and good surface appearance of the molded products. CONSTITUTION:This resin composition contains (A) a polyaminophenylene ether copolymer consisting of (i) structural units of formula I {(m) is 1 to 4; (n) is 0 to 3 where m+n<=4; J is formula II [(a) is 1 to 6; R<1> is 1 to 20C aliphatic hydrocarbon which may be substituted with halogen atoms and whose chain may be interrupted with 0 atoms, aromatic polyvalent hydrocarbon; R<2> is alkylene; R<3>, R<4> are H, 1 to 20C alkyl], when (m) is >=2, R<3> and R<4> may mutually be different; K is halogen, primary or secondary alkyl and when (n) is >=2, each may differ from one another}, and (ii) structural units of formula III (Q is H, halogen) and having a number-average polymerization degree of 25 to 500, and (B) a polyamide resin, preferably nylon-6, preferably at a A/B weight ratio of (70 to 30)/(30 to 70).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides the heat resistance, mechanical strength and dimensional accuracy of polyphenylene ether (hereinafter referred to as "PPE"), and the moldability and organic solvent resistance of polyamide resins. The present invention relates to a high-performance thermoplastic resin composition that also has the dual function. Molded articles obtained from the present thermoplastic resin composition are useful as automobile parts such as ignition coils, gears, ignition manifolds, switch sealing materials, electrical parts, mechanical parts and the like.

[0002]

2. Description of the Related Art PPE having an unsubstituted or substituted phenylene ring, particularly poly (2,6-dimethyl-1,4-phenylene ether), has excellent heat resistance and mechanical strength and is useful as a so-called engineering plastic. is there. However, it is well known that it has an undesired property that molding processing such as injection molding is difficult due to its high melt viscosity. The impact resistance and organic solvent resistance of the resin are also heat resistant engineering plastics.
It is insufficient to use this resin alone. One of the attempts when a single material cannot sufficiently satisfy the desired properties is to mix the insufficient properties with each other by mixing with other materials. For example, P
A material in which polystyrene having good compatibility with PE and good moldability is blended to improve the moldability of PPE has been widely put to practical use (Japanese Patent Publication No. 43-17812). However, in this case, both components have poor organic solvent resistance, and as a result, the molded product obtained from the mixed composition also has insufficient organic solvent resistance.

On the other hand, polyamide resin is widely used as one of the typical engineering plastics which are excellent in moldability, organic solvent resistance, heat resistance and the like. However, this resin has drawbacks in that it is inferior in properties such as dimensional stability, hygroscopicity, heat distortion resistance under high load, and impact resistance, so its application is limited. Therefore, P
If a composition that combines the good properties of PE and polyamide resin and that complements the undesirable points of each resin can be obtained, it will be possible to provide an excellent resin material with a wide range of applications, and its industrial significance will be very high. large.

Therefore, for the purpose of providing a molding material in which the disadvantages are complemented without impairing the advantages of both, a composition obtained by simply melt-mixing both resins is disclosed in US Pat. No. 3,379,792.
No. 4338421, each specification, Japanese Patent Publication No. 45-997
No. 59-41663. However, in such a simple blend system, PPE
Since the polyamide resin and the polyamide resin are inherently poor in compatibility,
These two phases are difficult to form a uniform and finely dispersed form, and when shear stress is applied during molding processing such as injection molding, delamination is likely to occur, and the two-phase interface of the obtained molded product is defective. Therefore, a composition having excellent mechanical strength and impact resistance cannot be obtained.

One of the general methods that can be considered to solve the above problems is to modify each resin with functional groups that react with each other in order to improve the mutual affinity of the two components, and melt at high temperature. It is a method of obtaining a block or graft copolymer through a chemical bond by reacting. If chemically inactive PPE can be modified with a functional group that reacts with polyamide resin, PPE can be obtained by melting and reacting at high temperature.
A block or graft copolymer product consisting of the above and a polyamide resin is obtained.

However, no compounding of PPE modified with an amino group and a polyamide resin has been made so far.

[0007]

DISCLOSURE OF THE INVENTION The present invention has improved compatibility between PPE and a polyamide resin, has a fine dispersion structure, and has mechanical strength, heat resistance, dimensional accuracy, moldability and organic solvent resistance. An object is to provide a thermoplastic resin composition having excellent properties.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a resin composition containing a polyaminophenylene ether and a polyamide resin, which are novel resins, has the above-mentioned object. The inventors have found that the above can be achieved and reached the present invention.

That is, the present invention is a thermoplastic resin composition containing the following components (A) and (B).

(A): General formula (I)

[Chemical 3]

(Where m is an integer of 1 to 4, n is an integer of 0 to 3 and satisfies m + n≤4. J is {(R ³ ) (R
_{^{4) N} a -R 1 -SR}} 2 - represents, here, a is 1
Represents an integer of 6. R ¹ represents an aliphatic polyvalent hydrocarbon group having 1 to 20 carbon atoms or an aromatic polyvalent hydrocarbon group which may be interrupted with an unsubstituted or halogen-substituted oxygen atom, and R 1
² represents an alkylene group, and R ³ and R ⁴ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group. When m is 2 or more, J may be different from each other.

K represents a halogen atom, a primary or secondary alkyl group or a phenyl group, and when n is 2 or more, K may be different from each other and a structural unit represented by the general formula (II )

[Chemical 4]

(Wherein Q is a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an alkenyl group,
Aromatic group, haloalkyl group, hydrocarbon oxy group, aminoalkyl group or halohydrocarbon oxy group)

A copolymer composed of structural units represented by
Polyaminophenylene ether having a number average degree of polymerization of 25 to 500

(B): Polyamide resin

The composition containing the polyaminophenylene ether (A) and the polyamide resin (B) according to the present invention is remarkably improved in the compatibility between the two resins, and is excellent in the characteristics of PPE and the characteristics of the polyamide resin. It is a very effective molding material having mechanical properties, molding processability, dimensional accuracy, and organic solvent resistance. Hereinafter, the constitution of the thermoplastic resin composition of the present invention will be described in detail.

<Polyaminophenylene ether (A)>
Polyaminophenylene ether (A) used in the present invention
Is a novel PPE having an amino group introduced. The polyaminophenylene ether (A) can be produced by the following method.

(A) Copolymerization Formula (III)

[Chemical 5] (Wherein, m, n, J, and K have the same meanings as described above), and 0.01 to 99.99 mol% of one or more phenol derivatives having an amino group.

General formula (IV)

[Chemical 6] (In the formula, Q has the same meaning as described above) One or two or more phenol derivatives of 99.99 to 0.01
Copolymerized with mol%.

Specific preferred examples of the phenol derivative having an amino group represented by the formula (III) include 2- [3- (2
-Aminoethylthio) propyl] -6-methylphenol, 2- [3- (2-aminoethylthio) propyl]-
6-ethylphenol, 2- [2- (2-aminoethylthio) propyl] -6-methylphenol and the like can be mentioned. Further, preferable specific examples of the phenol derivative represented by the formula (IV) include 2,6-dimethylphenol and 2
-Methyl-6-ethylphenol, 2,6-dipropylphenol, 2,3,6-trimethylphenol, 2,
6-benzylphenol, 2-chlorophenol, 2-
Allyl-6-methylphenol, 2,6-diphenylphenol, 2,6-diethylphenol and the like, or mixtures thereof.

The polyaminophenylene ether copolymerization method can be carried out in the same manner as the ordinary oxidative polymerization of PPE,
For example, U.S. Pat. Nos. 3,422,062 and 3,30687.
No. 4, No. 3306875, No. 3365422, No. 3369656, and No. 3642669. The catalyst used for the oxidative polymerization is not particularly limited, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, or cobalt, usually in combination with various other substances.

The polyaminophenylene ether as the component (A) may be a random copolymer or a block copolymer. The number average degree of polymerization is 25 to 500. When it is less than 25, the mechanical properties of the composition are not good, and when it exceeds 500, it is not easy to handle such as deterioration of molding processability due to increase of melt viscosity.

Among them, the preferable one is 2- [3- (2-
Aminoethylthio) propyl] -6-methylphenol 0.05 to 50 mol%, preferably 0.5 to 40 mol%
And 2,6-dimethylphenol 99.95 to 50 mol%, preferably 99.5 to 60 mol%. The number average molecular weight is 3,000 to 50,000.
Is more preferable, and 5,000 to 30,000 is more preferable. This polymer is composed of the number x of structural units of the formula (V) and the number y of structural units of the formula (VI), and x and y satisfy the following formula. 0.05 ≦ 100x / (x + y) ≦ 50

[0024]

[Chemical 7]

[0025]

[Chemical 8]

(B) Addition of a thiol compound having an amino group to PPE having an olefinic substituent on the side chain

As another method for producing the polyaminophenylene ether (A) of the present invention, it can be produced by reacting a PPE having an olefinic substituent on the side chain with a thiol compound having an amino group or a salt thereof. Examples of the salt of the thiol compound having an amino group include hydrochloride, hydrobromide, sulfate, paratoluenesulfonate, acetate and the like. 2-Aminoethanethiol is preferred, especially its hydrochloride or paratoluenesulfonate. The reaction is preferably carried out in the presence of a radical initiator or UV irradiation. Further, it can be produced by neutralizing with an alkali compound after the reaction.

The olefinic substituents include, for example, allyl, 3-methyl-2-butenyl and geranyl groups, and the radical initiators include, for example, dibenzoyl peroxide and di-t-butyl peroxide. , Dicumyl peroxide, t-butyl peroxybenzoate and other organic peroxides; and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. This reaction can be carried out in a solvent such as benzene, toluene, xylene, chlorobenzene, trichlorobenzene or N-methylpyrrolidone, but an extruder, Banbury mixer, kneader or Laboplast mill (Bravender) was used. It can also be carried out by melt-kneading.

<Polyamide Resin (B)> The polyamide resin (B) used in the present invention has --CO in the polymer main chain.
It has an NH-bond and can be melted by heating. Typical examples are nylon-4, nylon-6, nylon-6,6, nylon-4,6, nylon-12,
Nylon-6, 10 and the like can be mentioned. In addition, a low crystalline or amorphous polyamide containing a monomer component such as a known aromatic diamine or aromatic dicarboxylic acid, transparent nylon or the like, or a mixture thereof can also be used. . The preferred polyamide resin (B) used in the present invention is nylon-6, nylon-6,6 or amorphous polyamide. The polyamide resin (B) used in the present invention preferably has a relative viscosity of 2.0 to 8.0 (measured at 25 ° C. in 98% concentrated sulfuric acid, according to JIS K6810 test method).

<Thermoplastic Resin Composition> (1) Blending Ratio In the thermoplastic resin composition of the present invention, the blending ratio of the components (A) and (B) is determined by the required performance of the molded product. Moldability, mechanical strength, solvent resistance, dimensional accuracy,
In many cases, properties such as high-temperature rigidity can be adjusted by the characteristics of each constituent component and the mixing ratio thereof, but it is often difficult to achieve both properties that conflict with each other such as rigidity and impact strength. For practical purposes, it is usually carried out from the viewpoint of appropriate harmonization of various properties such as moldability, mechanical strength and high temperature rigidity. Therefore, the composition ratio of the polyaminophenylene ether (A) and the polyamide resin (B) in the present invention is well mixed in any case, but when PPE is the main component, molding processability and appearance are improved. When the polyamide resin is the main component, the heat distortion resistance, hygroscopicity and dimensional accuracy of the polyamide resin are improved.

The mixing ratio of the polyaminophenine ether (A) and the polyamide resin (B), in which the characteristics of these two components are obtained in harmony, is 90:10 to 10:90, preferably 70. The range is 30 to 30 to 70. The component (A) used in the present invention may be polyaminophenylene ether alone or a mixture of polyaminophenylene ether and unmodified PPE. The mixing ratio of polyaminophenylene ether and unmodified PPE can be set arbitrarily. Usually, the mixing ratio of polyaminophenylene ether and unmodified PPE is 100: 0.
The range of 20 to 80% by weight is preferred. When the mixing ratio of the polyaminophenylene ether is less than 20% by weight, the effect of compatibility is reduced, which is not preferable.

(2) Additional components The thermoplastic resin composition according to the present invention may contain other additional components. For example, 20 weight% of an antioxidant, a weather resistance improver, a nucleating agent, a flame retardant, a slip agent, a plasticizer, a styrene resin, a fluidity improver, a release agent, a pigment, a dispersant, etc. in a resin composition. It can be blended in a ratio of not more than%. Further, organic / inorganic fillers such as glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate and silica may be contained in an amount of 50% by weight or less, and a colorant dispersant may be included in an amount of 5% by weight or less. it can. Further, various elastomers may be added in a proportion of 5 to 25% by weight for the purpose of improving impact resistance. As such an elastomer, for example, a styrene-butadiene block, a random copolymer, a hydrogenated product thereof, an ethylene-propylene- (diene) copolymer, or the like can be used. They can be modified by known methods such as acid modification, hydroxy modification and epoxy modification in order to improve the lack of affinity with the constituents.

(3) Method for producing thermoplastic resin composition The mixing method for obtaining the thermoplastic resin composition of the present invention is as follows:
With respect to the thermoplastic resin composition, a method which has been generally put into practical use can be adopted. For example, powdery, granular,
Each of the fibrous components, if necessary, together with the composition described in the section of additional components, are uniformly mixed with a stirrer such as a Henschel mixer, and then a single-screw or multi-screw extruder, or a plastomill kneader (Bravender). A typical method is to melt and knead the mixture by using the above method. Further, the final composition can be obtained by sequentially mixing the respective components in accordance with the designed mixing ratio without mixing them all together. This method is effective when it is necessary to control the miscibility and adjust the kneading history of a specific component to control the deterioration and deterioration of the resin. Further, mixing all or part of the constituents in a solution state is an effective method for the same purpose.

[0034]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Parts are parts by weight unless otherwise specified.

Reference Example 1; Production of polyaminophenylene ether (1) (1) 2- [3- (2-aminoethylthio) propyl]
Synthesis of -6-methylphenol Under a nitrogen gas atmosphere, 4360 parts of 2-allyl-6-methylphenol and 456 parts of 2-aminoethanethiol hydrochloride were dissolved in 2360 parts of ethanol. At a reflux temperature, 2430 parts of a 2.9% ethanol solution of 2,2′-azobisisobutyronitrile was added dropwise and reacted for 10 hours. After removing ethanol with an evaporator, it was washed with diethyl ether. The hydrochloride was neutralized with an aqueous solution of sodium hydroxide and then extracted with diethyl ether to obtain the desired 2- [3- (2-aminoethylthio) propyl] -6-
Methylphenol was obtained. The production yield was 84% with respect to the theoretical production amount of this monomer.

(2) Production of polyaminophenylene ether 192 parts of the phenol derivative obtained in the above (1), 2,6-
Dimethylphenol 900 parts and sodium hydroxide 20
Parts were dissolved in 2890 parts of xylene and 766 parts of methanol. Next, diethanolamine (40 parts), dibutylamine (12.6 parts), and manganese chloride tetrahydrate (0.96 parts) dissolved in methanol (316 parts) were added in this order. The polymerization reaction was divided into two stages, and the temperature was kept at 40 ° C. in the former stage, and oxygen gas was introduced at a rate of 0.8 liter / min to carry out the reaction to precipitate a solid. In the latter stage, the temperature was kept at 30 ° C., and oxygen gas was introduced at a flow rate of 0.8 liter / minute and 8 liter / minute to reach the point where polymer precipitation stopped. After the polymer was precipitated and washed with methanol to deactivate the catalyst, the target polyaminophenylene ether was obtained. The production yield of the polymer was 95%. The content of amino groups in this polymer was measured by elemental analysis and nuclear magnetic resonance analysis. As a result, it was 1.4 mol% based on the number of repeating units of the polymer. Furthermore, when the molecular weight of this polymer was measured by gel permeation chromatography, the number average molecular weight in terms of polystyrene was about 10,200 (number average degree of polymerization: 85). The polyaminophenylene ether thus obtained is referred to as polyaminophenylene ether (1).

Examples 1 to 6 and Comparative Examples 1 to 3 Polyaminophenylene ether (1) obtained in Reference Example, polyamide resin (nylon-6 manufactured by BASF Corporation,
Product name Ultramid KR4411) and unmodified PPE
(Manufactured by Nippon Polyether Co., intrinsic viscosity 0.3 dl / g measured at 30 ° C. in chloroform), using a plastomill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 ml, the composition shown in Table 1,
The mixture was melt-kneaded for 5 minutes under the conditions of 250 ° C. and a rotation speed of 180 rpm. Each of the obtained thermoplastic resin compositions was added with 28
Press molding was carried out under the condition of 0 ° C. to prepare a sheet having a thickness of 2 mm. Various test pieces were cut out from this sheet, and the physical properties were evaluated by the following methods.

(1) Izod impact strength In accordance with JIS K7110, three notched Izod impact strengths at 23 ° C. were measured by stacking three 2 mm thick test pieces.

(2) Dispersion Morphology In order to examine the two-phase dispersion state of the obtained mixture, the cross section was observed with an S-2400 scanning electron microscope manufactured by Hitachi Ltd.

(3) Appearance of Molded Article A test piece having a length of 47 mm, a width of 5.3 mm and a thickness of 2.6 mm was injection-molded and evaluated mainly on delamination.

The above results are shown in Table 1. As is clear from this result, the composition containing the polyaminophenylene ether of the present invention and the polyamide resin has a very fine P content.
Dispersion of the PE resin was recognized, the impact strength was significantly improved, and the appearance of the molded product was excellent.

[0042]

[Table 1]

[0043]

INDUSTRIAL APPLICABILITY As described above, the thermoplastic resin composition of the present invention is remarkably improved in compatibility between the two resins, and as shown in Table 1, both components exhibit excellent dispersion morphology and are excellent. It has excellent mechanical strength and surface appearance of the molded product.

Claims (1)

[Claims] 1. A thermoplastic resin composition comprising the following components (A) and (B). (A): General formula (I) (In the formula, m is an integer of 1 to 4, n is an integer of 0 to 3, and m +
It satisfies n ≦ 4. J is {(R ³ ) (R ⁴ ) N} _a −R
¹ -SR ² - represents, here, a is an integer of 1-6. R ¹ represents an aliphatic polyvalent hydrocarbon group having 1 to 20 carbon atoms or an aromatic polyvalent hydrocarbon group which may be interrupted by an unsubstituted or halogen-substituted oxygen atom, R ² represents an alkylene group, R ³ and R ⁴ are each a hydrogen atom and have 1 to 1 carbon atoms.
20 represents an alkyl group or an aryl group. When m is 2 or more, J may be different from each other. K represents a halogen atom, a primary or secondary alkyl group, or a phenyl group, and when n is 2 or more, K may be different from each other) and a structural unit represented by the general formula (II) 2] (In the formula, Q represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an alkenyl group, an aromatic group, a haloalkyl group, a hydrocarbonoxy group, an aminoalkyl group or a halohydrocarbonoxy group). A polyaminophenylene ether (B) having a number average degree of polymerization of 25 to 500, which is a copolymer composed of structural units represented by