JPH08165422A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE: To obtain a polyphenylene ether resin composition, containing a styrenic elastomer, etc., modified with an acid (anhydride) in a PPE-based resin, excellent in impact resistance and low glossiness and useful as automotive parts, etc. CONSTITUTION: This composition is obtained by melt kneading (A) 100 pts.wt. (i) polyphenylene ether resin or the component (i) and (ii) polystyrene-based resin with (B) 3-50 pts.wt. styrenic elastomer modified with an acid or an acid anhydride (preferably maleic anhydride having 0.1-10wt.% content thereof) and (C) 0.01-5 pts.wt. polyvalent amine compound (e.g. hexamethylenediamine) and/or polyvalent epoxy compound (e.g. a bisphenol type epoxy compound except an epoxy-modified polyolefin). Furthermore, polymers, represented by the formula, specifically poly(2,6-dimethyl-1,4-phenylene) ether. etc., are preferably used as the component (i).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyphenylene ether (hereinafter sometimes referred to as PPE) resin composition. More specifically, the present invention relates to a PPE resin composition having excellent impact resistance and having little gloss on the surface of a molded product.

[0002]

2. Description of the Related Art Polyphenylene ether is widely known as a resin having excellent heat resistance, mechanical properties and electrical properties, and is usually a modified polyphenylene ether resin composed of a composition such as polystyrene and rubber modified polystyrene (HIPS). Widely used as. Due to its excellent mechanical properties, electrical properties, workability, etc., it is used in a wide range of applications such as automobile parts, office equipment, electric appliance parts, and interior furnishings. In these applications, not only excellent impact resistance is required, but also a molded article appearance with suppressed surface gloss is required in order to obtain an antiglare effect, a calm atmosphere and a high-class feeling.

Conventionally, in order to improve impact resistance, a method of controlling the shape of rubber particles in a rubber-modified polystyrene to be blended or increasing the amount of rubber to be blended has been carried out. However, these methods require adjustment at the polymerization stage of polystyrene, and it has been difficult to adjust the impact resistance and gloss of the PPE resin composition obtained based on such polystyrene. .

As another method for improving impact resistance, it has been proposed to blend various styrene elastomers (Japanese Patent Laid-Open No. 59-196350, Japanese Patent Laid-Open No. 5-140445). Kaihei 5-230362, etc.).

On the other hand, as a method for obtaining a low-gloss surface, there has been carried out a method in which the surface of the mold is manipulated by subjecting the surface of the mold to embossing or applying a matte coating to the molded product. . Further, a method of adding a substance exhibiting a matting effect to the resin composition has also been attempted. For example, in thermoplastic resin,
Low gloss is obtained by blending a specific rubbery copolymer or filler (JP-A-63-101456). Further, in Japanese Patent Laid-Open No. 5-179131 by the applicant, PPE
A compound having a carbon multiple bond and a specific group and a specific silane coupling agent are blended with the resin system to improve low gloss.

[0006]

The above-described processing of the die surface has a drawback that it is difficult to process the side surface portion in relation to the upward slope, which increases the manufacturing cost of the die. There are problems such as high cost and complicated process. On the other hand, when a filler is added to the resin composition, there are drawbacks that the effect of lowering glossiness is low and the impact resistance is low. When a rubber-like copolymer is blended, there is a drawback that heat resistance and rigidity are lowered and melt fluidity is deteriorated. Further, the degree of gloss easily varies depending on the molding conditions. Further, even when a rubber-modified styrene-based resin containing rubber particles is blended, there is a problem that the degree of gloss is likely to vary depending on the molding conditions.
Therefore, an object of the present invention is to provide a PPE resin composition which has excellent impact resistance, has a stable low gloss on the surface of a molded article, and has excellent mechanical and thermal characteristics.

[0007]

The present invention relates to (A) polyphenylene ether resin or 100 parts by weight of polystyrene resin and (B) styrene elastomer modified with an acid or an acid anhydride. 50 parts by weight, and (C) polyvalent amine compound and / or polyvalent epoxy compound (excluding epoxy-modified polyolefin) 0.01 to 5
And a resin composition.

In the present invention, known PPE resins can be used. The PPE resin is, for example, a compound represented by the general formula (Formula 1):

[0009]

Embedded image In the above formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or at least two carbon atoms between the halogen atom and the phenyl ring. A haloalkyl group or a haloalkoxy group having a monovalent substituent selected from those containing no tertiary α-carbon, and n is an integer representing the degree of polymerization), The polymer represented by the above general formula (Formula 1) may be one kind alone or a copolymer in which two or more kinds are combined. In a preferred embodiment, R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms, and R ₃ and R ₄ are hydrogen atoms or 1 to ₄ carbon atoms.
4 alkyl group. For example poly (2,6-dimethyl-1,
4-phenylene) ether, poly (2,6-diethyl-1,4
-Phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-
6-propyl-1,4-phenylene) ether, poly (2,6
-Dipropyl-1,4-phenylene) ether, poly (2
-Ethyl-6-propyl-1,4-phenylene) ether, and the like. As the PPE copolymer, a copolymer containing a part of alkyl tri-substituted phenol such as 2,3,6-trimethylphenol in the polyphenylene ether repeating unit can be mentioned. Further, it may be a copolymer obtained by grafting a styrene compound on these PPE. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing styrene-based compounds such as styrene, α-methylstyrene, vinyltoluene and chlorostyrene onto the above PPE.

In the present invention, the component (A) is the above-mentioned polyphenylene ether resin or polystyrene resin with it. Polystyrene resins are known per se and have the general formula (Formula 2):

[0011]

Embedded image (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z represents a substituent which is a halogen atom or an alkyl group having 1 to 4 carbon atoms, and x is an integer of 0 to 5. ) Must have at least 25% by weight or more of repeating structural units derived from the aromatic vinyl compound represented by the formula (1) in the polymer. Examples of such styrene polymers include styrene and its derivatives such as homopolymers and copolymers of p-methylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, chlorostyrene and bromostyrene. Further, 70 to 99% by weight of the above-mentioned aromatic vinyl compound and 1 to 1 of diene rubber
30% by weight of rubber modified polystyrene (HIPS)
Can be used. Examples of the diene rubber constituting HIPS include homopolymers of conjugated diene compounds such as butadiene, isoprene, and chloroprene, copolymers of conjugated diene compounds with unsaturated nitrile compounds or aromatic vinyl compounds, and natural rubber. It is possible to use one kind or two or more kinds. Especially polybutadiene,
Butadiene-styrene copolymer is preferred.

HIPS can be obtained by emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization or a combination thereof.

The mixing ratio of PS resin to PPE resin is 90 to PS resin to 10 to 100 parts by weight of PPE resin.
~ 0 parts by weight. Preferably, PPE resin 10 to 90
The PS resin is 90 to 10 parts by weight based on parts by weight.

As the styrene elastomer itself, known ones can be used. For example, a styrene-butadiene block copolymer having one or more polystyrene and polybutadiene segments, or a styrene-isoprene copolymer having one or more polystyrene and polyisoprene segments, respectively. The polymer, or the unsaturated portion thereof, is selectively hydrogenated. The content of polystyrene segment in these styrene elastomers is 1
5 to 60% by weight is preferable. When the content of the polystyrene segment is less than 15% by weight, the compatibility with the PPE resin composition is reduced and sufficient impact resistance cannot be obtained. on the other hand,
If it exceeds 60% by weight, flexibility as an elastomer is lost, and thus sufficient impact resistance cannot be obtained.

The styrene elastomer modified with an acid or an acid anhydride is a styrene elastomer modified with an acid or an acid anhydride. As the acid or acid anhydride that can be used, unsaturated carboxylic acid or its anhydride, for example, monocarboxylic acid such as acrylic acid and methacrylic acid, maleic acid, fumaric acid, itaconic acid,
Endo-bicyclo- [2.2.1] -5-heptene-
Dicarboxylic acids such as 2,3-dicarboxylic acid, maleic anhydride, itaconic anhydride, endo-bicyclo- [2.2.
1] -5-heptene-2,3-dicarboxylic acid anhydride (hymic acid anhydride) and other dicarboxylic acid anhydrides, and maleic anhydride is particularly preferable.

The modification of the styrene-based elastomer with such an acid or acid anhydride can be carried out by a known method, for example, by graft-polymerizing or random-copolymerizing the above-mentioned modifier compound with the above-mentioned resin.

In the case of graft polymerization, first, a styrene-based elastomer, a modifying acid or acid anhydride, and, if necessary, a catalyst are charged into an extruder, a twin-screw kneader or the like, and 150
Kneading is performed while melting at about 400 to 400 ° C, preferably about 200 to 350 ° C. At this time, the addition amount of the acid or the acid anhydride is not particularly limited, but in order to sufficiently exert the effects of the present invention, 0.1 to 20 parts by weight, particularly 100 parts by weight of the styrene-based elastomer, Is preferably about 0.5 to 10 parts by weight.

As a catalyst to be added, if necessary, during the melt-kneading, a conventional radical polymerization catalyst can be used. For example, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, acetyl peroxide. , Tertiary butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, 2,5-dimethyl-
Peroxides such as 2,5-ditertiarybutylperoxyhexyne, diazo compounds such as azobisisobutyronitrile, and the like are preferable. The addition amount of the catalyst is preferably about 0.01 to 3 parts by weight with respect to 100 parts by weight of the styrene elastomer.

The content of the acid or acid anhydride in the modified styrenic elastomer is not particularly limited, but is 0.01 to 1
It is preferably within the range of 0% by weight.

As the modified styrene elastomer, a styrene elastomer modified with maleic anhydride is particularly preferable. The content of maleic anhydride in the modified styrene elastomer is preferably 0.1 to 10% by weight,
2 to 5% by weight is more preferable. If the content of maleic anhydride is less than 0.1% by weight, sufficient low gloss cannot be obtained. On the other hand, if it exceeds 10% by weight, the properties as an elastomer are impaired and sufficient impact resistance cannot be obtained. The method of graft-modifying a styrene elastomer with maleic anhydride is a known method, for example, JP-A-61-76518, JP-A-62-250018, and JP-A-62-
It can be satisfactorily performed by the method described in Japanese Patent No. 79211, etc.

The amount of the above component (B) is 100 parts of the component (A).
With respect to parts by weight, the upper limit is 50 parts by weight, preferably 30 parts by weight, while the lower limit is 1 part by weight, preferably 3 parts by weight. When the amount of the component (B) is less than the above range, sufficient low glossiness cannot be obtained, while when it is more than the above range, fluidity and rigidity are deteriorated, which is not preferable.

Next, the component (C) of the present invention will be described. As the polyvalent epoxy compound used in the present invention,
A compound having two or more epoxy groups in the molecule, for example, a bisphenol type epoxy compound obtained by reacting bisphenol A and epicrylhydrin at various ratios, or a novolak resin and epicrylhydrin Novolak type epoxy compounds, polyglycidyl esters obtained from polycarboxylic acid and epicryhydrin, alicyclic compounds, for example, alicyclic epoxy compounds obtained from dicyclopentane, aliphatic compounds having an alcoholic hydroxyl group (eg butane) Diol, hexanediol, glycerin, etc.) and glycidyl ethers obtained from epichlorohydrin, epoxidized polybutadiene, and an epoxy group compound-containing copolymer composed of an unsaturated monomer having an epoxy group and another unsaturated monomer ( However, epoxy modified Except olefin), and the like.

The polyvalent amine compound used in the present invention includes compounds having two or more amine groups in the molecule. For example, polymethylenediamine, polyetherdiamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, aliphatic polyvalent amines such as N-aminoethylethanolamine, metaphenylenediamine, xylenediamine, 4,4′-diaminodiphenylether, 4 , Aromatic polyvalent amines such as 4'-diaminodiphenylamine, alicyclic polyvalent amines such as 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, melamine,
Heterocyclic polyamines such as benzoguanamine.

With respect to the compounding amount of the polyvalent amine compound or the polyvalent epoxy compound, the upper limit is preferably 5 parts by weight, more preferably 3 parts by weight, while the lower limit is 0.
01 parts by weight, more preferably 0.05 parts by weight. If it is less than the above lower limit, sufficient low glossiness cannot be obtained, and if it exceeds the above upper limit, impact resistance is deteriorated and appearance is unfavorably caused.

In the resin composition of the present invention, other polymer components may be further copolymerized or blended. Other polymer components that can be copolymerized or blended include, for example, polyesters, polyamides,
Examples thereof include polycarbonate, polysulfide, polyacrylate, polysulfone, polyether ketone, polyacrylonitrile, ABS, AS and polyolefin.

In the resin composition of the present invention, as long as the physical properties are not impaired, when the resin is mixed according to the purpose,
During molding, other polymers, various rubbers, conventional additives such as pigments, dyes, fillers (glass fiber, carbon fiber, carbon black, silica, titanium oxide, etc.), heat-resistant agents, oxidative deterioration inhibitors, weathering agents, Lubricants, mold release agents, crystal nucleating agents, plasticizers, antistatic agents, flame retardants and the like can be added.

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be satisfactorily used. However, the melt-kneading method is generally preferable. The use of small amounts of solvent is possible, but generally not required. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously.

The reason why the PPE resin composition containing the styrenic elastomer modified with maleic anhydride and the polyvalent amine compound or the polyepoxy compound of the present invention has excellent impact resistance and low gloss is that it is modified. It is considered that the styrene-based elastomer thus produced is crosslinked by the polyvalent amine compound or the polyvalent epoxy compound in the composition.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

The following compounds were used in the examples. Ingredient (A) PPE: Intrinsic viscosity (chloroform, 25 ° C) 0.46 dl /
g of poly (2,6-dimethyl-1,4-phenylene) ether, manufactured by GE Plastics Co., Ltd. HIPS: high-impact polystyrene (trademark: Topolex 870-ST, manufactured by Mitsui Toatsu Chemicals, Inc.) component ( B) MAH-g-SEBS: maleic anhydride modified hydrogenated styrene-butadiene copolymer (trademark: Kraton FG-1901,
Shell Chemical Co., Ltd.), maleic anhydride content 0.
5% by weight SEBS (for comparison): hydrogenated styrene-butadiene copolymer (trademark: Kraton G-1651, manufactured by Shell Chemical Co., Ltd.) Component (C) hexamethylenediamine) 1,6-hexanediol diglycidyl ether.

Examples 1 to 4 and Comparative Examples 1 to 2 The amounts (parts by weight) of the respective components shown in Table 1 were melt-kneaded at a barrel set temperature of 280 ° C. using a twin-screw extruder (screw diameter of 30 mm). And extruded to form pellets. Carbon black was added to all resin compositions for coloring.
3% by weight has been added. By injection molding from the obtained pellets, a 150 mm square plate having a thickness of 3 mm is formed,
The 60 ° gloss was measured according to JIS K-7105.
Further, various test pieces were molded from the above pellets and subjected to the following tests. (1) Izod impact strength: Measured according to ASTM D256, 1/8 inch thick notched Izod impact strength (2) Tensile strength: Measured according to ASTM D638 (3) Tensile breaking elongation: Measured according to ASTM D638 (4) Thermal deformation temperature : According to ASTM D648
Table 1 shows the measurement results under a load of 18.6 kg / cm ² .

[0032]

[Table 1] As described above, the PPE resin compositions of Examples have both impact resistance and low gloss.

[0033]

According to the present invention, a PPE resin composition having excellent impact resistance and low gloss can be provided. Therefore, the resin composition of the present invention can be used in a wide variety of fields and is industrially useful.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08L 25/18 LEK 51/00

Claims (3)

[Claims] 1. A polyphenylene ether resin (A) or 100 parts by weight of this and a polystyrene resin,
(B) Styrene-based elastomer modified with acid or acid anhydride 3 to 50 parts by weight, and (C) polyvalent amine compound and / or polyvalent epoxy compound (excluding epoxy-modified polyolefin) 0.01 to 5 parts by weight A resin composition comprising: 2. The component (B) acid or acid anhydride is maleic anhydride, and the content thereof is 0.1 to 10% by weight.
The resin composition according to claim 1, which is 3. A resin composition obtained by melt-kneading the components (A), (B) and (C) of claim 1.