JPH08176433A - Low-gloss polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE: To obtain a polyphenylene ether resin composition which can give a molding having excellent impact resistance, a low-gloss surface, and excellent thermal and mechanical properties. CONSTITUTION: This composition comprises 100 pts.wt. poly-phenylene ether resin or both this resin and a polystyrene resin, 1-30 pts.wt. polystyrene modified with an epoxy compound, and 1-30 pts.wt. polyolefin modified with an acid or its anhydride.

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 polystyrene or rubber-modified polystyrene (H
It is widely used as a modified polyphenylene ether resin composed of a composition such as IPS). 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. Among such various uses,
For automobile interior parts, home appliances parts, interior furnishings, etc.,
In order to obtain an anti-glare effect and to obtain a calm atmosphere and a high-class feeling, it is necessary to obtain a material for obtaining a molded article having a low-gloss appearance with the surface gloss suppressed (that is, matte). Became.

Conventionally, in order to obtain a low-gloss surface, a method of manipulating the surface of the mold by subjecting the surface of the mold to texturing or applying a matte coating to the molded product has been used. Further, a method of adding a substance exhibiting a matting effect to the resin composition has also been attempted. For example, a thermoplastic resin is blended with a specific rubbery copolymer or filler (Japanese Patent Laid-Open No. 63-101456) to provide low gloss. In addition,
In Japanese Patent Laid-Open No. 61-89240, a PPE resin is blended with a rubber-modified styrene resin containing rubber particles having a specific particle diameter to reduce gloss. Further, in Japanese Patent Laid-Open No. 5-179131 by the present applicant, a compound having a carbon multiple bond and a specific group and a specific silane coupling agent are blended with a PPE resin to improve low gloss. .

[0004]

The processing of the surface of the mold has the drawback that the manufacturing cost of the mold is high and that the processing of the side surface is difficult due to the draft angle. There is also a problem that the process becomes complicated. 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 having excellent impact resistance, stable low gloss on the surface of a molded article, and excellent mechanical and thermal characteristics.

[0005]

DISCLOSURE OF THE INVENTION The present invention comprises 100 parts by weight of (A) polyphenylene ether resin or polystyrene resin and (B) 1 to 30 parts by weight of polystyrene resin modified with a compound having an epoxy group. (C) A resin composition comprising 1 to 30 parts by weight of a polyolefin resin modified with an acid or an acid anhydride.

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):

[0007]

Embedded image (In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and at least 2 between the halogen atom and the phenyl ring.
A haloalkyl group having 1 carbon atoms or a haloalkoxy group, which represents a monovalent substituent selected from those not containing a tertiary α-carbon, and n is an integer representing the degree of polymerization) It is a general term, and may be a single type of the polymer represented by the above general formula (Formula 1) or a copolymer in which two or more types are combined. In a preferred embodiment R ₁
And R ₂ is an alkyl group having 1 to 4 carbon atoms, and R ₃
And R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 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 above polyphenylene ether repeating unit can be mentioned. Further, it may be a copolymer obtained by grafting a styrene compound on these PPE. The styrene compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing styrene compounds such as styrene, α-methylstyrene, vinyltoluene and chlorostyrene to the above PPE.

Polystyrene resins are known per se and have the general formula (Formula 2):

[0009]

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 p is an integer of 0 to 5. )
The repeating structural unit derived from the aromatic vinyl compound represented by the above formula must be contained in the polymer at least 25% by weight or more. 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, rubber-modified polystyrene (HIPS) composed of 70 to 99% by weight of the above-mentioned aromatic vinyl compound and 1 to 30% by weight of diene rubber 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. Particularly, polybutadiene and butadiene-styrene copolymer are preferable.

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

The mixing ratio of the PS resin to the PPE resin is 90 to 0 parts by weight with respect to 10 to 100 parts by weight of the PPE resin. Preferably, PPE resin 1
The PS resin is 90 to 10 parts by weight with respect to 0 to 90 parts by weight.

The polystyrene resin composition modified with a compound having an epoxy group (B) used in the present invention is the above PS resin modified with a compound having an epoxy group.

Examples of the compound having an epoxy group as a modifier include unsaturated epoxy compounds such as glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether and glycidyl ether of hydroxyalkyl (meth) acrylate. Glycidyl methacrylate is preferred.

The modification of the polystyrene resin with such an epoxy group-containing compound is carried out by a known method, for example, by graft-polymerizing the above-mentioned modifier compound onto the above-mentioned resin, if necessary in the presence of a radical polymerization catalyst. be able to.

The amount of the epoxy group-containing compound with respect to the polystyrene resin is not particularly limited, but in order to exert the effect of the present invention, it is 0.05 to 20% by weight, particularly 0.2.
-15% by weight is preferred.

The upper limit of the amount of component (B) is preferably 30 parts by weight, particularly 15 parts by weight, per 100 parts by weight of component (A). On the other hand, the lower limit is preferably 1 part by weight, especially 3 parts by weight. If it exceeds the above range, heat resistance and mechanical strength are lowered, while if it is less than the above range, the effect of the present invention is not sufficiently exhibited.

The (C) acid- or acid-anhydride-modified polyolefin (hereinafter sometimes referred to as PO) resin composition used in the present invention is a polyolefin resin obtained by polymerizing an α-olefin monomer as a main component. A resin obtained by graft-polymerizing an acid or an acid anhydride, preferably an α, β-unsaturated (di) carboxylic acid or an anhydride thereof, or a monomer of an olefin whose main component is an α-olefin, and an acid or an acid anhydride. And preferably α, β-unsaturated (di) carboxylic acid or an anhydride thereof is copolymerized.

Examples of α-olefins include ethylene,
Propylene, 1-butene, 1-hexane, 3-methyl-
1-butene, 3-methyl-1-pentene, 4-methyl-
1-pentene, 3,3-dimethyl-1-butene, 4,4
-Dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1
-Hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3
-Cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2,2
2,1] -heptane and the like can be mentioned. Among these, preferable examples are ethylene, propylene, and 1.
-Butene, 1-hexene, 3-methyl-1-butene, 3
-Methyl-1-pentene, 4-methyl-1-pentene,
Examples thereof include 3-methyl-1-hexene, and particularly ethylene, propylene, 1-butene, 3-methyl-1.
-Butene and 4-methyl-1-pentene are preferred. These α-olefins may be used alone or in combination of two or more. These α-olefins may be one kind,
Moreover, you may use 2 or more types. When two or more α-olefins are used, the olefins may be randomly distributed in the copolymer resin or may be distributed in blocks.

Further, unsaturated monomers copolymerizable with the above-mentioned copolymers are formed into vinyl esters such as vinyl acetate and vinyl propionate, and acrylic acid such as methyl acrylate, ethyl acrylate and vinyl acrylate. Esters and methacrylic acid esters may be copolymerized.

The acid or acid anhydride that can be used for modifying the PO resin is an unsaturated carboxylic acid or an anhydride thereof, for example, a monocarboxylic acid such as acrylic acid or methacrylic acid, maleic acid, fumaric acid or itacone. Acids, dicarboxylic acids such as endo-bicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid, maleic anhydride, itaconic anhydride, endo-bicyclo- [2.2.1] -5 Examples thereof include dicarboxylic acid anhydrides such as heptene-2,3-dicarboxylic acid anhydride (hymic acid anhydride), and dicarboxylic acid and its anhydride are particularly preferable.

In the case of graft polymerization, first, a PO-based copolymer, a modifying acid or acid anhydride, and, if necessary, a catalyst are charged into an extruder, a twin-screw kneader, or the like, and the mixture is heated to 150 to 400.
The mixture is kneaded while melting at about C, preferably about 200 to 350C. At this time, the addition amount of the acid or the acid anhydride is not particularly limited, but in order to sufficiently exert the effect of the present invention, it is 0.1 to 20 with respect to 100 parts by weight of the PPE resin or the PS resin. It 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 PPE resin or the PS resin.

The content of the acid or acid anhydride in the modified PO resin is not particularly limited, but is preferably in the range of 0.01 to 10% by weight. Specifically, when modified with maleic anhydride or hymic acid anhydride, the content of maleic anhydride or hymic acid anhydride in the modified resin is preferably 0.1 to 10% by weight, more preferably 0.2. 10 to 10% by weight. If the content of the acid or acid anhydride is out of the above range, the desired effect cannot be obtained.

The upper limit of the amount of component (C) is preferably 30 parts by weight, particularly 15 parts by weight, relative to 100 parts by weight of component (A). On the other hand, the lower limit is preferably 1 part by weight, especially 3 parts by weight. If it exceeds the above range, heat resistance and mechanical strength are lowered, while if it is less than the above range, the effect of the present invention is not sufficiently exhibited.

Modified PS Resin and Modified PO
The ratio of the system resin is 1: 9 to 9: 1, and particularly 8: 2 to 2:
8 is preferable. If the amount is out of the above range, the compatibility of the polyolefin-based resin is lowered, surface peeling occurs, and sufficient impact resistance cannot be obtained.

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 of the resin composition 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 resin composition of the present invention has an excellent low gloss is that the modified PPE resin and / or the modified PS resin and the modified PO resin in the resin composition react and gel. It is considered that the PO-based resin and the PPE-based resin or the PS-based resin are compatibilized by modification so that they have excellent impact resistance.

[0030]

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 /
Poly (2,6-dimethyl-1,4-phenylene) ether of g, manufactured by Nippon GE Plastics PS: Polystyrene (CR-3500, manufactured by Dainippon Ink and Chemicals, Inc.) Component (B) Modified PS: Glycidyl methacrylate Modified polystyrene (trademark: Marproof CP-1005S, manufactured by NOF CORPORATION), glycidyl methacrylate content 5% by weight SEBS (for comparison): Hydrogenated butadiene-styrene copolymer (trademark: Kraton G1650, manufactured by Shell Chemical Co., Ltd.) Component (C) Modified PO1: Maleic anhydride modified ethylene-ethyl acrylate copolymer (trademark; GB-301, manufactured by Nippon Unicar Co., Ltd.), maleic anhydride content 0.5% by weight Modified PO2: Maleic anhydride modified ethylene- Proprene copolymer (trademark: MP-061, manufactured by Mitsui Petrochemical Industry Co., Ltd.)

Examples 1 and 2 and Comparative Examples 1 and 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. A 150 mm square plate with a thickness of 3 mm is formed from the obtained pellets by injection molding.
The 60 ° gloss was measured according to SK-7105. Further, various test pieces were molded from the above pellets and subjected to the following tests.

Izod impact strength: ASTM D256
1/8 inch thick Notched Izod impact strength is measured according to: Tensile strength: Measured according to ASTM D638 Tensile breaking elongation: Measured according to ASTM D638 Bending strength: Measured according to ASTM D638 Bending elastic modulus: Heat distortion temperature (HDT) : Measured at a load of 18.6 kg / cm ² according to ASTM D648 Melt index (MI): Measured at a temperature of 250 ° C. and a load of 10 kg according to ASTM D1238

[0034]

[Table 1] The resin compositions of the examples have low gloss and excellent impact resistance.

[0035]

Industrial Applicability According to the present invention, it is possible to provide a PPE resin composition which is excellent in impact resistance, has a low gloss surface of a molded article, and is excellent in mechanical and thermal characteristics. Therefore, the resin composition of the present invention can be used in a wide variety of fields and is industrially useful.

Claims (3)

[Claims] 1. A polyphenylene ether resin or 100 parts by weight of a polystyrene resin and a polystyrene resin, 1 to 30 parts by weight of a polystyrene resin modified with a compound having an epoxy group, and an acid or an acid (C). A resin composition comprising 1 to 30 parts by weight of a polyolefin resin modified with an anhydride. 2. The ratio of components (B) and (C) is from 1: 9.
The resin composition according to claim 1, which is in the range of 9: 1. 3. The resin composition according to claim 1, wherein the compound having an epoxy group is glycidyl acrylate or glycidyl methacrylate, and the acid or acid anhydride is maleic acid or maleic anhydride.