JPH0657124A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in heat resistance and moldability by mixing a polyphenylene ether resin with a styrene resin and a specified carboxamide wax. CONSTITUTION:The resin composition comprises 10-100 pts.wt. polyphenylene ether resin containing at least 0.01 cyclic terminal group of formula I [wherein R1 to R5 are each H, (substituted) alkyl, halogen or (substituted) aryl; R6 to R9 are each H, (substituted) alkyl, (substituted) alkenyl, (substituted) aryl, alkoxyl, carboxyl, nitrile, acyl or the like] on the average per 100 repeating phenylene ether units constituting the resin and having a number-average molecular weight of 1000-100000, 0-90 pts.wt. styrene resin and 0.1-10 pts.wt. carboxamide wax of formula II [wherein R1 and R5 are each, 10-30C (substituted) alkyl; and R2, R3 and R4 are each a 1-10C alkylene, a cycloaliphatic hydrocarbon residue or phenylene].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyphenylene ether resin composition having excellent heat resistance, impact resistance, and moldability. More specifically, heat resistance containing a carboxylic acid amide wax having a specific structure and softening point,
The present invention relates to a polyphenylene ether resin composition having improved moldability.

[0002]

2. Description of the Related Art Conventionally, polyphenylene ether resin is
Excellent heat resistance, electrical characteristics, acid resistance, alkali resistance, etc.
Moreover, although it is a resin having excellent properties such as low specific gravity and low water absorption, it also has the drawback that it is difficult to melt-mold due to its low fluidity and it is slightly brittle due to its low impact strength. And, a technique of blending impact-resistant polystyrene containing a polybutadiene component in order to improve these drawbacks at the same time is disclosed in US Pat. No. 3,383,435, but it has a drawback that heat resistance is lowered. There is.

Further, Japanese Patent Laid-Open No. 60-245666,
Further, JP-A-2-44335 discloses that a carboxylic acid amide having a specific melting point and a specific molecular weight is added in order to improve moldability. But in these cases,
Although the decrease in heat resistance is small, the effect of improving moldability is not sufficient. However, as the problem of plastic waste becomes more serious, materials are required to be thinner and lighter, and various molding methods have been developed, it is essential to further improve the molding processability.

[0004]

That is, the object of the present invention is to obtain a polyphenylene ether resin composition which has been solved by the above-mentioned means, retains impact resistance and heat resistance, and has further improved moldability. That is.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to achieve the above object, and as a result have arrived at the present invention. That is, the present invention is represented by the general formula (1) having (a) polyphenylene ether resin 10 to 100 parts by weight (b) styrene resin 0 to 90 parts by weight (c) 190 ° C. to 260 ° C. Carboxylic acid amide wax 0.1
-10 parts by weight

[0006]

[Chemical 3]

(Wherein R ₁ and R ₅ are alkyl groups or substituted alkyl groups having 10 to 30 carbon atoms, and R ₁ and R ₅ may be the same or different. R ₂ , R ₃ and R 5 ₄ is an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon residue or a phenylene group, which may be the same or different, and is a polyphenylene ether resin composition.

The polyphenylene ether resin used in the present invention is represented by the following general formula (3),

[0009]

[Chemical 4]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, or hydrogen, and R ₅ and R ₆ are not hydrogen at the same time) as a repeating unit, and the structural unit has the general formula (3 Homopolymers or copolymers of [a] and [b] can be used. Typical examples of homopolymers of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl1,4-phenylene) ether, and poly (2 , 6-diethyl-1,4-phenylene) ether,
Poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-
1,4-phenylene) ether, poly (2-methyl-6)
-N-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-)
1,4-phenylene) ether, poly (2-methyl-6)
-Hydroxyethyl-1,4-phenylene) ether,
Homopolymers such as poly (2-methyl-6-chloroethyl-1,4-phenylene) ether may be mentioned.

The polyphenylene ether copolymer is 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-
It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure such as a copolymer with cresol.

Further, in the polyphenylene ether resin of the present invention, various other phenylene ether units which have been proposed to be present in the polyphenylene ether resin may be used unless they are contrary to the gist of the present invention. It may be included as a partial structure. As an example of what is proposed to coexist in a small amount, Japanese Patent Application No. 63-1
2- (dialkylaminomethyl) -6 described in JP-A-2698 and JP-A-63-301222.
-Methylphenylene ether unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like.

Also included are those in which a small amount of diphenoquinone or the like is bound to the main chain of the polyphenylene ether resin.
Furthermore, for example, JP-A-2-276823, JP-A-63-108059 and JP-A-59-59724.
It also includes polyphenylene ether modified with a compound having a carbon-carbon double bond, which is described in Japanese Patent Laid-Open Publication No. 2003-242242.

The polyphenylene ether resin used in the present invention has a number average molecular weight of 1,000 to 10 as a molecular weight.
It is 10,000. Its preferred range is about 6,000.
~ 60,000. The number average molecular weight in the present invention is a polystyrene equivalent number average molecular weight determined by gel permeation chromatography using a calibration curve of standard polystyrene.

In the component (a) of the present invention, the cyclized terminal group represented by the following general formula (2) is averaged to 0.0 per 100 of the phenylene ether units constituting the resin.
Contains one or more and has a number average molecular weight of 1,000 to 100,
A polyphenylene ether resin in the range of 000 can be used.

[0016]

[Chemical 5]

This polyphenylene ether resin can be manufactured as follows. That is, the general formula (4)

[0018]

[Chemical 6]

(In the formula, R _{1 to} R ₅ are the same as defined in the formula (2), R ₁₀ and R ₁₁ are independently hydrogen,
It represents an alkyl group or a substituted alkyl group, but is not hydrogen at the same time. ) A polyphenylene ether resin having a terminal group represented by the following general formula (5)

[0020]

[Chemical 7]

(In the formula, R ₆ and R ₉ are the same as those defined in the formula (2)) in the absence of a compound having a carbon-carbon double bond and a radical polymerization initiator. It can be produced by heating at a temperature not lower than the glass transition temperature of the polyphenylene ether resin. Specific examples of the compound represented by the general formula (5) include styrene, α-methylstyrene, chlorostyrene, methylstyrene, stilbene, cinnamic acid alcohol benzalacetone, ethyl cinnamate, cinnamic acid nitrile, and 4-vinyl. Pyridine 2-vinyl-3,5-diamino- (s) -triazine and the like can be mentioned.

The styrene resin used as the component (b) is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer. . What is a styrene compound?
General formula (6)

[0023]

[Chemical 8]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5). Means a compound. Specific examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like. The compounds copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile;
Examples thereof include acid anhydrides such as maleic anhydride, which are used together with styrene compounds. Examples of the rubbery polymer that can coexist during the polymerization include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, a partially hydrogenated product thereof, and an ethylene-propylene copolymer rubber.

The method for producing the styrene resin of the present invention is not limited, and any of bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization well known to those skilled in the art may be used. The softening point used for the component (c) of the present invention is 190.
The method for producing the carboxylic acid amide wax having a specific structure of from 0 to 260 ° C. is not particularly limited, but it can be produced by allowing a dibasic acid to exist when reacting the carboxylic acid and the diamine. The softening point can be adjusted by changing the types of carboxylic acid, diamine and dibasic acid.

Specific examples of the carboxylic acid include palmitic acid, stearic acid, behenic acid, montanic acid, hydroxystearic acid and the like. Specific examples of the diamine include methylenediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, paraxylylenediamine, tolylenediamine, phenylenediamine, isophoronediamine and the like. Can be mentioned.

Specific examples of the dibasic acid include malonic acid, succinic acid, adipic acid, pimelic acid, azelaic acid and sebacic acid. The carboxylic acid amide wax of the present invention is required to have four amide bond structures in one molecule, and the effect of improving the molding processability of the polyphenylene ether resin is the diamide that has been used conventionally. Different from the compound.

The softening point of the carboxylic acid amide wax of the present invention is preferably 190 ° C to 260 ° C. Those having a softening point of 190 ° C. or lower volatilize during processing and reduce heat resistance. At 260 ° C. or higher, it does not melt sufficiently during processing, and the effect of improving moldability is lost. Specific examples of the carboxylic acid amide wax include N, N'-bis (2-stearoamidoethyl) -sebacamide, N, N
Examples include ′ -bis (2-stearoamidoethyl) azeraicamide and N, N′-bis (stearoamido-m-xylylene) sebacamide.

The component (c) is preferably added in an amount of 0.1 to 10 parts by weight. When it is less than 0.1 parts by weight, the effect of improving the moldability is small, and when it exceeds 10 parts by weight, the impact resistance is high. The mechanical strength such as properties is reduced. In the composition of the present invention, other additives such as a plasticizer, a stabilizer, an ultraviolet absorber, a flame retardant, a coloring agent, a release agent and a fibrous reinforcing agent such as glass fiber and carbon fiber, and further glass beads. , Calcium carbonate,
Fillers such as talc can be added. As the stabilizer, phosphite esters, hindered phenols,
The alkanolamines, acid amides, dithiocarbamic acid metal salts, inorganic sulfides, and metal oxides can be used alone or in combination. Examples of the ultraviolet absorber include benzotriazoles, salicylates, benzophenones and the like.

If necessary, other rubbery polymer such as styrene-butadiene block copolymer or hydrogenated product thereof may be added to the composition of the present invention. A hydrogenated product of a styrene-butadiene block copolymer is a block copolymer composed of at least one styrene polymer block and at least one olefin elastomer block.

The styrenic polymer block referred to in the present invention is specifically represented by the general formula (6)

[0032]

[Chemical 9]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5) Is a polymer or copolymer block derived from The olefin elastomer block referred to in the present invention includes monoolefins such as ethylene, propylene, 1-butene and isobutylene, conjugated diolefins such as butadiene, isoprene and 1,3-pentadiene, 1,4-hexadiene and norbornene derivatives. A polymer block having a form in which one or more olefin compounds selected from non-conjugated diolefins are polymerized or copolymerized, and the unsaturation degree of the block is 20% or less. Therefore, when the above diolefins are used as the constituent monomers of the olefin elastomer block, the degree of unsaturation of the block portion is 2
Measures to reduce the degree of unsaturation, such as hydrogenation, must be taken to the extent that it does not exceed 0%. Further, a styrene compound may be randomly copolymerized with the olefin elastomer block.

Any method may be used for mixing the respective components constituting the present invention. For example, an extruder, a heating roll, a Banbury mixer, a kneader or the like may be used.

[0035]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
The components used in the examples and comparative examples are as follows. Component (a): polyphenylene ether resin a-1; poly (2,6-dimethyl-1,4-phenylene) ether a-2 having an intrinsic viscosity of 0.50 (in chloroform at 30 ° C.) a-2; phenylene ether unit Poly (2,6-dimethyl-1,4-phenylene) having an intrinsic viscosity of 0.50 (at 30 ° C. in chloroform) having 0.25 terminal groups represented by the following formula (7) per 100 )ether

[0036]

[Chemical 10]

Component (b): Styrenic resin b-1; Rubber-reinforced polystyrene containing 9% by weight of polybutadiene b-2; 90% of 1,2-vinyl bonds contains 9% by weight of hydrogenated polybutadiene. Rubber-reinforced polystyrene (c) component c-1; N, N'-bis (2-stearoamidoethyl)
Sebacamide (softening point 255 ° C)

[0038]

[Chemical 11]

C-2; N, N'-bis (2-stearoamidoethyl) azelaicamide (softening point 235 ° C.)

[0040]

[Chemical 12]

C-3; N, N'-bis (stearoamide-m-xylylene) sebacamide (softening point 196 ° C.)

[0042]

[Chemical 13]

C-4; N, N'-ethylenebisstearamide (softening point 142 ° C.)

[0044]

[Chemical 14]

C-5; N, N'-diheptanoyl-p-
Phenylenediamide (softening point 210 ℃)

[0046]

[Chemical 15]

[0047]

Example 1 50 parts by weight of the polyphenylene ether shown in a-1 above and the rubber-reinforced polystyrene 5 shown in b-1 above
0 part by weight, 1.0 part by weight of carboxylic acid amide represented by c-1 were melt-kneaded at 300 ° C. in a twin-screw extruder with a screw diameter of 30 mm (PCM-30 manufactured by Ikegai Tekko KK), and pelletized through a water tank. did. The pellets were molded at 300 ° C. by an injection molding machine (IS-80EPN manufactured by Toshiba Machine Co., Ltd.) to prepare test pieces. And the resulting pellets,
Using the test piece, the characteristics of the material were evaluated by the following test methods, and the results are shown in Table 1.

[0048]

Example 2 Example 1 was repeated except that the c-1 component was changed to the c-2 component.

[0049]

Example 3 Example 1 was repeated except that the c-1 component was changed to the c-3 component.

[0050]

Example 4 Example 1 was repeated except that the component b-1 was changed to the component b-2 and the addition amount of the component c-1 was changed from 1.0 part by weight to 2.0 parts by weight.

[0051]

Comparative Example 1 The procedure of Example 1 was repeated except that the c-1 component was not added.

[0052]

Comparative Example 2 The procedure of Example 1 was repeated except that the c-1 component was changed to the c-4 component.

[0053]

Comparative Example 3 The procedure of Example 1 was repeated except that the c-1 component was changed to the c-5 component.

[0054]

Comparative Example 4 The procedure of Example 4 was repeated except that the c-1 component was changed to the c-4 component.

[0055]

Example 6 65 parts by weight of the polyphenylene ether shown in a-2 above and the rubber-reinforced polystyrene 3 shown in b-2 above
2 parts by weight of carboxylic acid amide shown as 5 parts by weight of c-1 was pelletized and molded in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

[0056]

Comparative Example 5 The procedure of Example 6 was repeated except that the c-1 component was not added.

[0057]

Comparative Example 6 The procedure of Example 6 was repeated except that the c-1 component was changed to the c-4 component.

[0058]

Comparative Example 7 The procedure of Example 6 was repeated except that the c-1 component was changed to the c-5 component. The test method is as follows. Heat distortion temperature: Weighted 1 according to ASTM D-648
It was measured at 8.6 kg / cm ² .

Melt flow rate: JIS K-721
According to 0, pellets were used and the measurement was performed at 250 ° C. under a load of 10 kg.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

EFFECTS OF THE INVENTION The carboxylic acid amide type wax having a specific softening point and structure of the present invention has excellent moldability while maintaining heat resistance.

Claims (2)

[Claims] 1. A (a) polyphenylene ether resin 10
To 100 parts by weight (b) Styrenic resin 0 to 90 parts by weight (c) Carboxylic amide wax 0.1 represented by the general formula (1) having a softening point of 190 to 260 ° C.
A polyphenylene ether resin composition comprising 10 to 10 parts by weight. [Chemical 1] (In the formula, R ₁ and R ₅ are alkyl groups having 10 to 30 carbon atoms or substituted alkyl groups, and R ₁ and R ₅ may be the same or different. R ₂ , R ₃ and R ₄ are carbon atoms. An alkylene group of formula 1 to 10, an alicyclic hydrocarbon residue or a phenylene group, which may be the same or different) 2. A polyphenylene ether resin having a cyclized terminal group represented by the following general formula (2) on average of 0.1 to 100 phenylene ether units constituting the resin.
Contains 01 or more and has a number average molecular weight of 1,000 to 10
The polyphenylene ether resin composition according to claim 1, which is in the range of 10,000. [Chemical 2] (In the formula, R _{1 to} R ₅ are each independently hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group, or a substituted aryl group, and R _{6 to} R ₉ are each independently hydrogen, an alkyl group, or a substituted aryl group. Alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, alkoxy group, N-lactam group, carboxylic acid group, carboxylic acid anhydride group, carboxylic acid ester group, carboxylic acid amide group, nitrile group, acyloxy group Or R ₆ and R ₇ , and R ₈ and R ₉ may be independently bonded to each other to form a ring having a spiro cyclic structure.)