JPH06240130A - Reinforced resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, excellent in heat resistance and useful as an automotive exterior trim parts, etc., by melt kneading a polyphenylene ether with a polyamide, a specific rubber-like block copolymer, a filler and a compound having a specified group in the molecule. CONSTITUTION:To resin composition is obtained by melt kneading (A) 15-60wt.% polyphenylene ether with (B) 25-70wt.% polyamide, (C) 1-10wt.% rubber-like block copolymer constructed from 30-55wt.% polymer block consisting essentially of a vinyl aromatic compound unit and a polymer block consisting essentially of an olefinic compound unit, (D) 5-50wt.% inorganic fibrous filler and (E) a compound having carboxylic acid group, epoxy group, etc., in the molecule [preferably maleic acid (anhydride)] in an amount of 0.05-5 pts.wt. based on 100 pts.wt. total amount of the components (A) to (D). Furthermore, 0.1-10wt.% modified block copolymer prepared by modifying a block copolymer containing the polymer block, etc., consisting essentially of a conjugated diene compound with an unsaturated dicarboxylic acid, etc., is preferably used.

Description

Detailed Description of the Invention

[0001]

The present invention relates to mechanical properties, heat resistance,
The present invention relates to a thermoplastic resin composition having excellent moldability.

[0002]

2. Description of the Related Art Polyphenylene ether resin is a resin excellent in dimensional stability, electrical characteristics, heat distortion resistance under high load, water resistance, etc., and is industrially blended with polystyrene resin. Although it is widely used, it has the major drawback of poor oil resistance and molding processability.

On the other hand, polyamide resin is excellent in mechanical strength, oil resistance, heat resistance and the like, and is widely used as one of the most representative engineering plastics. However, this polyamide resin has dimensional stability,
It has the disadvantage that it has lower hygroscopicity, heat distortion resistance under high load, and impact resistance when dried compared to other plastics.

Therefore, blending of both resins has been attempted for the purpose of complementing the drawbacks of the two resins by taking advantage of the respective advantages of both resins, and various compositions have been proposed so far. For example, a simple blend of both resins, especially a blended resin obtained by melt mixing, is disclosed (Japanese Patent Publication No. 45-997 and Japanese Patent Publication No. 59-4166).
3 gazette). However, the polyphenylene ether and the polyamide are essentially incompatible with each other, and such a simple blend cannot provide a molded article excellent in mechanical strength.

For this purpose, a copolymer of a styrene compound and an α, β-unsaturated dicarboxylic acid anhydride is blended as a compatibility improver together with polyphenylene ether and polyamide, and a rubber-like substance is further added as an impact resistance improver. Along with the added composition (Japanese Patent Publication No. 59-33614), polyphenylene ether and polyamide, (a) carbon-carbon double bond or triple bond and (b) carboxyl group or acid anhydride group in the molecule as other components. A composition obtained by adding a compound having a functional group such as, for example, melt-kneading (Japanese Patent Publication No. 60-11966) and a composition containing a rubber-like substance (Japanese Patent Publication No. 56-49753) are Proposed. However, even the compositions obtained by these methods cannot obtain sufficient impact strength.
On the other hand, as a method of improving impact resistance, carbon-
Carbon double bond and acid anhydride, carboxylic acid, amino group,
A method (Japanese Patent Publication No. 63-500803) has been proposed which comprises melt-mixing a polyphenylene ether functionalized with a compound having a hydroxy group and a polyamide.

Further, compositions containing glass fibers and other inorganic fillers (JP-A-63-101452 and JP-A-3-45652) have been proposed.
A resin composition composed of a polyphenylene ether resin and a polyamide resin has excellent mechanical properties, heat resistance, moldability, oil resistance, organic solvent resistance, and dimensional stability, and is used for automobile parts, electric / electronic parts. , Has been used in a wide range of fields such as machine parts. However, in order to expand such applications, save energy, and reduce costs, there is an increasing demand for lighter and thinner walls. Particularly, in automobile exterior parts, further improvement is desired in the balance of rigidity, impact resistance, and heat resistance.

However, conventional compositions containing polyphenylene ether and polyamide have some drawbacks in physical properties, and resin compositions having physical properties in which rigidity, impact resistance and heat resistance are well balanced have hitherto been available. Had not been found.

[0008]

An object of the present invention is to provide a resin composition containing polyphenylene ether or polyamide as a basic component, which is an excellent resin composition having a significantly improved balance of rigidity, impact resistance and heat resistance. Is to provide.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned objects, the present inventors have identified a polyphenylene ether, a polyamide, a specific rubbery block copolymer and an inorganic fibrous filler. It was found that the object can be achieved in a resin composition obtained by melt-mixing at a ratio of, and the present invention has been completed based on the finding.

That is, the present invention provides (A) polyphenylene ether 15 to 60% by weight, (B) polyamide 25
˜70% by weight, (C) a polymer block mainly composed of vinyl aromatic compound units and a polymer block mainly composed of olefin compound units, wherein the polymer block mainly composed of vinyl aromatic compound units is 30% by weight to 55
1% to 10% by weight of rubber-like block copolymer, 5% to 50% by weight of (D) inorganic fibrous filler, and (A) + (B) + (C) + (D) total amount 100 A resin composition obtained by melt-kneading 0.05 to 5 parts by weight per part by weight of a compound (E) having a carboxylic acid group, an acid anhydride group, an epoxy group, an amino group or a hydroxyl group in the molecule, and ( A) Polyphenylene ether 15 to 60% by weight, (B) Polyamide 25 to 70% by weight, and (C) a vinyl aromatic compound unit-based polymer block and an olefin compound unit-based polymer block. , A polymer block mainly composed of a vinyl aromatic compound unit is 30% by weight to 55% by weight, a rubber block copolymer 1 to 10% by weight, (D) an inorganic fibrous filler 5 to 50% by weight, (F) It contains at least one polymer block mainly containing a diene compound, contains at least one polymer block mainly containing a vinyl aromatic compound, and has a weight ratio of the vinyl aromatic compound and the conjugated diene compound of 60/40. A modified block copolymer obtained by modifying a block copolymer having a molecular weight of ˜97 / 3 with at least one compound selected from unsaturated dicarboxylic acids and their derivatives 0.1 to 10% by weight, and ( A) +
(B) + (C) + (D) + (F) 0.05 to 5 parts by weight per 100 parts by weight of the total amount of carboxylic acid groups in the molecule,
The present invention relates to a resin composition obtained by melt-kneading a compound (E) having an acid anhydride group, an epoxy group, an amino group or a hydroxyl group.

The present invention will be described in detail below. The polyphenylene ether used as the component (A) in the present invention has the following general formula (1):

[0012]

[Chemical 1]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ represent the same or different residues such as an alkyl group, an aryl group, halogen and hydrogen, and n represents the degree of polymerization). It is a polymer composed of repeating units. Specific examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-phenylene).
Ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-npropyl)-
1,4-phenylene) ether, poly (2-methyl-6)
-N-butyl-1,4-phenylene) ether, poly (2
-Ethyl-6-isopropyl-1,4-phenine) ether, poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) Examples thereof include homopolymers such as ether and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, and copolymers composed of repeating units thereof.

The degree of polymerization of these polyphenylene ethers, both homopolymers and copolymers, has an intrinsic viscosity [η] (chloroform solution, 30 ° C.) of 0.25 to 1.
Those in the range of 5, preferably 0.30 to 1.0 are suitably used. The polyamide used as the component (B) in the present invention has an amide bond {--NH on the polymer main chain.
Any material that has -C (= O)-} and can be heated and melted can be used.

Typical examples thereof include 4-nylon, 6-nylon, 6,6-nylon, 12-nylon, 6,10-nylon, polyamide from terephthalic acid and hexamethylenediamine, adipic acid and metaxyl. Polyamides from diamines, adipic and azelaic acids and 2,2'-bis (p-aminocyclohexyl)
-Polyamide from propane, terephthalic acid and 4,4 '
-Polyamides from diaminodicyclohexylmethane and their copolymerized nylons. Of these, 6-nylon, 6,6-nylon and 6-6,6 copolymer nylon are preferably used alone or in combination.

In the present invention, the rubber-like block copolymer of the polymer block mainly composed of vinyl aromatic compound units and the polymer block mainly composed of olefin compound units used as the component (C) is hydrogenated styrene- There are butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, ethylene-propylene-based copolymers graft-modified with styrene, etc., and hydrogenated styrene-butadiene block copolymers are particularly preferable. The rubber-like block copolymer used in the present invention has a polymer block mainly composed of vinyl aromatic compound units of 30 to 55.
It is necessary to contain it in an amount of 35% by weight, particularly preferably 35 to 50% by weight. If the polymer block mainly composed of vinyl aromatic compound units is less than 30% by weight, the rigidity is poor, and if it is more than 55% by weight, the impact resistance is inferior, so that the object cannot be achieved. The rubbery block copolymers may be used alone or in combination of two or more. Further, those having a polymer block mainly composed of vinyl aromatic compound units of less than 30% by weight and 55% by weight or more can be used in combination, and the combination ratio of the polymer blocks mainly composed of vinyl aromatic compound units is 30% by weight. It may be adjusted so that the content is about 55% by weight. Further, as these rubber-like block copolymers, those modified with an epoxy compound, an unsaturated carboxylic acid or a derivative thereof can be used.

The composition of the present invention contains 5 to 50% by weight of an inorganic fibrous filler as the component (D). In the composition of the present invention, the inorganic fibrous filler used as the component (D) is glass fiber, carbon fiber, metal fiber or the like, and glass fiber is preferable. These may be used alone, or may be used in combination of two or more kinds or further with a granular inorganic filler. Further, it is advantageous to use, as far as the object of the present invention is not impaired, those which have been subjected to a surface treatment with a silane coupling agent or a focusing treatment with a urethane or epoxy type sizing agent as desired.

A carboxylic acid group, an acid anhydride group, an epoxy group in the molecule, which is used as the component (E) in the present invention,
Specific examples of the compound having an amino group or a hydroxyl group include maleic acid, fumaric acid, chloromaleic acid, cis-
4-cyclohexene-1,2-dicarboxylic acid and their acid anhydrides, esters, half-alkyl esters, amides,
Examples thereof include imide, citric acid, malic acid, and the like.
α, β-Unsaturated dicarboxylic acids and their derivatives, specifically maleic acid and maleic anhydride are preferred. These compounds may be used alone or in combination of two or more kinds. The addition amount of the component (E) is 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A), (B), (C) and (D). It is desirable to select within the range of 1 part by weight,
When the component (F) is also used, (A), (B),
The same selection may be made for 100 parts by weight of the total amount of the components (C), (D) and (F). If the addition amount is less than 0.05 parts by weight, the dispersed particle size of polyphenylene ether becomes large, which is not preferable in terms of physical properties. Even if the addition amount exceeds 5 parts by weight, the effect is not increased.
It is economically disadvantageous.

The block copolymer which is the base of the modified block copolymer used as the component (F) in the present invention is one or more polymer blocks of an aromatic vinyl compound and one polymer block of a conjugated gen compound. It is composed of the above and may be linear, branched, radial or a combination thereof. The content of the aromatic vinyl compound in this base block copolymer is 60 to 97.
It is necessary to be in the range of% by weight. Specific examples of the base block copolymer include a styrene-butadiene block copolymer and a styrene-isoprene block copolymer.

Examples of the unsaturated dicarboxylic acid and its derivative used for modifying the base block copolymer include maleic acid, fumaric acid, chloromaleic acid,
Examples thereof include cis-4-cyclohexene-1,2-dicarboxylic acid and their acid anhydrides, esters, half-alkyl esters, amides, imides, etc., and particularly α, β-unsaturated dicarboxylic acids and their derivatives, specifically Are preferably maleic acid and maleic anhydride. The unsaturated dicarboxylic acid and its derivative may be used alone or in combination of two or more kinds. The modified block copolymer is preferably graft-modified so that the unsaturated dicarboxylic acid and its derivative are contained in an amount of 0.05 to 5 parts by weight per 100 parts by weight of the block copolymer.

Regarding the compounding ratio of (A) polyphenylene ether, (B) polyamide and (C) rubber block copolymer in the composition of the present invention, (A), (B),
Based on the total weight of the components (C) and (D), the polyphenylene ether is 15 to 60% by weight, preferably 20 to
Rubber-like block copolymer of 50% by weight, 25 to 70% by weight of polyamide, preferably 30 to 60% by weight, a polymer block mainly composed of vinyl aromatic compound units and a polymer block mainly composed of olefin compound units Is 1-10
%, Preferably in the range of 2 to 7% by weight, (D)
The content of the inorganic fibrous filler as a component is 5 to 50% by weight, preferably 2 to 7% by weight.

In the present invention, (A), (B), (C)
The amount of the three components is set to the above-mentioned mixing ratio, because when the polyphenylene ether exceeds 60% by weight or the polyamide is less than 25% by weight, it is difficult to make the polyamide a continuous phase, and the oil resistance which is a characteristic of the polyamide, This is because the moldability and the like are impaired. On the other hand, polyphenylene ether is 1
When the amount is less than 5% by weight or the amount of polyamide exceeds 70% by weight, the drawbacks of polyamide, such as water absorption and rigidity at high temperature, are not improved, which is not preferable. A rubber-like block copolymer of a polymer block mainly composed of vinyl aromatic compound units and a polymer block mainly composed of olefin compound units, which is used as the component (C), is necessary for improving impact resistance, If it is less than 1% by weight, impact resistance is poor and 1
Even if it exceeds 0% by weight, not only the effect of improving impact resistance is small, but also the rigidity and heat resistance are poor, which is economically disadvantageous. Further, the blending ratio of the modified block copolymer used as the component (F) is 0.1 based on the total weight of the components (A), (B), (C), (D) and (F). 10 to 10% by weight, preferably 0.5 to 5% by weight. 0.1% by weight
If it is less, the effect of improving mechanical properties is not exerted,
If it is more than 10% by weight, no increase in the effect due to it is observed, which is economically disadvantageous.

Next, a method for producing the composition of the present invention will be described. The composition of the present invention can be produced by using a melt-kneading device, and preferably an extruder, particularly a twin-screw extruder equipped with a device capable of side feeding from the middle. As for the kneading method, all the components may be blended together, but preferred methods include (A) polyphenylene ether and (B).
A polyamide, (C) a rubber block copolymer, (D) a compound having a carboxylic acid group, an acid anhydride group, an epoxy group, an amino group or a hydroxyl group in the molecule, and (F) a modified block copolymer are melt mixed. After that, it is obtained by further kneading (D) the inorganic fibrous filler. A more preferable method is when the modified block copolymer of the component (F) is produced, that is, when the base block copolymer and the unsaturated dicarboxylic acid or its derivative of the component (E) are kneaded and reacted in an extruder. At the same time, the polyphenylene ether as the component (A) and the rubber-like block copolymer as the component (C) are supplied, and the polyamide as the component (B) is supplied from the first intermediate supply port and kneaded, and then (D) ) It is preferable to supply the inorganic fibrous filler from the second intermediate supply port and melt-knead at once to form a composition, from the viewpoint of the performance of the obtained composition and the simplification of the process.

The temperature and time for melt-kneading differ depending on the type of polyamide used and the compounding ratio of polyamide and polyphenylene ether, but usually 240-37.
A temperature in the range of 0 ° C., preferably 280 to 340 ° C., and a kneading time of 0.1 to 10 minutes, preferably about 0.3 to 3 minutes, are suitable. As the melt-kneading device, an extruder, a kneader, a roll or the like can be used, but an extruder is particularly suitable.

If desired, other polymers or rubbery polymers, various stabilizers, plasticizers, lubricants, flame retardants, surfactants, etc. may be added to the composition of the present invention.

[0026]

EXAMPLES Next, the present invention will be specifically described with reference to Examples. The following examples are merely illustrative and do not limit the content of the present invention. The components used in the examples and comparative examples are as follows. (A) component; polyphenylene ether (PPE) Poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity of 0.54 (30 ° C. in chloroform) (B) component; polyamide B-1: 6-nylon (manufactured by Asahi Chemical Industry Co., Ltd., nylon SBR) B-2: 6,6-nylon (manufactured by Asahi Chemical Industry Co., Ltd., nylon 1300) (C) component; hydrogenated styrene-butadiene block copolymer C- 1: Styrene component 35%, number average molecular weight about 170,000 C-2: Styrene component 30%, number average molecular weight about 80,000 C-3: Styrene component 60%, number average molecular weight about 80,000 (D) component; glass fiber Chop with a diameter of 13 μm and a cut length of 3 mm (having an aminosilane-based treating agent and an epoxy-based sizing agent) (F) component; modified block copolymer 70% by weight of styrene unit That styrene - butadiene block copolymer modified with maleic anhydride products. 100 parts by weight of the styrene-butadiene block copolymer was mixed with 2 parts by weight of maleic anhydride and 0.5 part by weight of phenothiazine as a stabilizer, and the mixture was mixed with a twin-screw extruder at 290 ° C.
It was manufactured by performing melt extrusion in. When this modified block copolymer resin was dissolved in toluene and subjected to neutralization titration, the content of maleic acid residue was about 0.5%.

The resin composition obtained was evaluated according to the following method. Injection molding machine (Toshiba Machinery Co., Ltd.)
A test piece was prepared with IS80C manufactured by IS80C, a cylinder temperature of 280 ° C., and a molding cycle of 1 minute), and the following physical properties were measured and tested. (1) Izod impact strength (IZOD): ASTM
D-256 with notch (2) Tensile strength (TS): ASTM D-638 (3) Flexural modulus (FM): ASTM D-790 (4) Heat distortion temperature (HDT): ASTM D-64
8, 18.6 kg / load In the following Examples and Comparative Examples, the amounts of each component used are shown in parts by weight for easy understanding. (Table 1 shows the weight%.)

[0028]

Example 1 34 parts by weight of PPE as component (A),
C-1 hydrogenated styrene-butadiene diene block copolymer as component (C) 4 parts by weight and maleic anhydride 0.14 parts by weight as component (E) were co-rotating twin-screw with a screw diameter of 25 mm. B-1 6-nylon 42 as the (B) component supplied from the top (first stage) of the machine
Carbon black as part by weight and colorant 0.3
By supplying a part by weight from the middle of the extruder,
Pellets extruded and kneaded at 300 rpm were obtained. Then, under the same extrusion conditions, 80 parts by weight of the pellets were fed from the top of the extruder (first stage), and 20 parts by weight of the glass fiber as the component (D) was fed from the middle of the extruder (middle stage) to pellet the composition. Got Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0029]

Example 2 33 parts by weight of PPE as component (A),
4 parts by weight of C-1 hydrogenated styrene-butadiene block copolymer as component (C), 1 part by weight of modified block copolymer as component (F) and maleic anhydride as component (E) 0. 14 parts by weight was supplied from the top (previous stage) of a co-rotating twin-screw extruder having a screw diameter of 40 mm, and 6-nylon 4 of B-1 as the component (B) was used.
2 parts by weight and carbon black as colorant
After 3 parts by weight was supplied from the first intermediate supply port of the extruder and kneaded, glass fiber as the component (D) was further supplied from the second intermediate supply port and extrusion kneading was performed at 300 ° C. and 300 rpm. Then, a composition pellet was obtained. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0030]

[Comparative Examples 1 to 3] Compositions obtained by extruding and kneading the compositions obtained by mixing the components (C) and / or (D) in Example 2 under the same conditions were obtained. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0031]

Example 3 In Example 2, an unmodified block copolymer was used in place of the component (F) and extrusion kneading was performed under the same conditions to obtain a composition pellet. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0032]

Examples 4, 5 and Comparative Example 4 In Example 2,
Changing the type of component (C) to C-2 and / or C-3,
The components (A), (B) and (D) were blended in the proportions shown in Table 1 and kneaded by extrusion under the same conditions to obtain composition pellets. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0033]

[Examples 6 and 7] In Example 2, the compounding amount of the component (D) was changed to 30 parts by weight, and the kind of the component (B) was changed, and the mixture was extrusion kneaded under the same conditions to obtain a composition pellet. It was Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0034]

[Table 1]

[0035]

Industrial Applicability The resin composition of the present invention retains the excellent characteristics of the composition containing polyphenylene ether and polyamide as basic components, and greatly improves the balance between rigidity, impact resistance and heat resistance. Provide things. Therefore, the resin composition of the present invention is useful for various applications such as automobiles and electric / electronic parts, and in particular, it can be expected that the application will be expanded as automobile exterior parts.

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Claims (2)

[Claims] 1. A polyphenylene ether (A) 15-
60% by weight, (B) polyamide 25 to 70% by weight,
(C) A polymer block mainly composed of vinyl aromatic compound units and a polymer block mainly composed of olefin compound units, wherein the polymer block mainly composed of vinyl aromatic compound units is 30% by weight to 55% by weight. 1% to 10% by weight of rubbery block copolymer, 5% to 50% by weight of (D) inorganic fibrous filler, and (A) + (B)
+ (C) + (D) total amount 0.05 per 100 parts by weight
To 5 parts by weight of a compound (E) having a carboxylic acid group, an acid anhydride group, an epoxy group, an amino group or a hydroxyl group in the molecule
A resin composition obtained by melt-kneading. 2. A polyphenylene ether (A) 15-
60% by weight, (B) polyamide 25 to 70% by weight,
(C) A polymer block mainly composed of vinyl aromatic compound units and a polymer block mainly composed of olefin compound units, wherein the polymer block mainly composed of vinyl aromatic compound units is 30% by weight to 55% by weight. 1% to 10% by weight of a rubbery block copolymer, 5% to 50% by weight of (D) an inorganic fibrous filler, and (F) at least one polymer block mainly composed of a conjugated diene compound, A block copolymer containing at least one polymer block mainly composed of a vinyl aromatic compound and having a weight ratio of the vinyl aromatic compound and the conjugated diene compound of 60/40 to 97/3 is prepared by using an unsaturated dicarboxylic acid. And modified block copolymers modified with at least one compound selected from the group consisting of derivatives thereof and 0.1 to 10% by weight, and (A) + (B) + (C + Total amount 1 (D) + (F)
A resin composition obtained by melt-kneading 0.05 to 5 parts by weight per 00 parts by weight of a compound (E) having a carboxylic acid group, an acid anhydride group, an epoxy group, an amino group or a hydroxyl group in the molecule.