JPH03103468A - Polyphenylene ether-based resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having improved compatibility of both resins and excellent impact resistance, comprising a polyphenylene ether-based resin (blend), ABS-based resin and oxazolinyl group-containing acrylonitrile- aromatic vinyl-based copolymer. CONSTITUTION:A composition comprising (A) 10-90 pts.wt., preferably 20-80 pts.wt. polyphenylene ether-based (PPE for short) or blend of PPE and polystyrene resin (PS for short), preferably modified in such a way that at least part of PPE or PS contains at least one of COOH, acid anhydride group and epoxy group, (B) 90-10 pts.wt., preferably 80-20 pts.wt. ABS-based resin and (C) 1-30 pts.wt., preferably 2-20 pts.wt. based on 100 pts.wt. total amounts of the components A and B of an oxazolinyl group-containing acrylonitrile-aromatic vinyl-based copolymer (oxazolinyl group-containing ABS resin).

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a polyphenylene ether (hereinafter referred to as PPE) resin silk composition, and more specifically, to a polyphenylene ether (hereinafter referred to as PPE) resin silk composition. This invention relates to resin compositions.

(Prior Art) PPE or a resin composition made of PPE and a polybrene resin is widely used because of its excellent mechanical properties and electrical properties.

However, this resin composition is known to have poor solvent resistance. Therefore, it was proposed to blend this with ABS resin. However, since PPE and A[3S have poor compatibility as they are, various efforts have been made. For example, ■'a of the 7-nitrile nitrile group in ABS resin.
A method using ABS resin with a lower degree of
0046M), ■ A method using multiple ABS resins with different concentrations of acrylonitrile groups (Japanese Patent Publication No. 63-7580
JP-A-60-11549 and the like have been proposed.

(Problem to be solved by the invention) However, although the above method (■) improves compatibility,
Since the number of acrylonitrile groups is reduced, the excellent properties originally possessed by ABS resins, such as sub-solvent properties and heat resistance, are lost, making it impossible to achieve the original purpose. In addition, in the method (2), different acrylonitrile groups I
Since ABS with I1 degree is used, the process becomes complicated,
This is not a practical method.

Therefore, we have developed a PPE resin composition that improves the compatibility between PPE and ABS resin and has excellent solvent resistance and secondary heat resistance without impairing the originally excellent properties of 8BS resin. The purpose is to provide something.

(Means for Solving the Problems) As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that PPE or PPE and polystyrene-based resins contain acrylonitrile-aromatic vinyl containing an oxylizolinyl group. We have discovered that adding a copolymer improves the compatibility between PPE and ABS, and have reached the present invention.

That is, the PPE resin composition of the present invention comprises (A) 10 to 90 parts by weight of a polyphenylene ether resin or a polystyrene resin, (B) 90 to 10 parts by weight of an AB S resin, and (C ) It is characterized by containing 1 to 30 parts by weight of an oxazolinyl group-containing acrylonitrile-aromatic vinyl copolymer based on a total of 100 parts by weight of (A) and (B).

As the PPE resin used as component (8) in the present invention, known ones can be used, for example, the general formula: (wherein R1, R2, R3 and R4 each independently represent a hydrogen atom, a halogen atom, an a monovalent substituent selected from groups, alkoxy groups, haloalkyl groups having at least two carbon atoms between the halogen atom and the vinyl ring, and haloalkoxy groups that do not contain a tertiary alpha carbon. , where q is an integer representing the degree of polymerization〉 A general term for polymers represented by In a preferred specific example, R1
and R2 is an alkyl group having 1 to 4 carbon atoms, and R
3 and R4 are hydrogen atoms or alkyl groups 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-medyl-6-ethyl-1,4)
-phenylene) ether, poly(2-methyl-6-propyl-1.4-7enylene) ether, poly(2,6-
dibropyl-1,4-phenylene〉ether, poly(2
-ethyl=6-propyl-1,4phenylene>ether, and the like. Examples of the PPE copolymer include copolymers containing a portion of alkyl trisubstituted phenol, such as 2,3.6-trimethylphenol, in the polyphenylene ether repeating unit. Alternatively, a copolymer in which a styrene compound is grafted onto these PPEs may be used. Styrenic Compound Graph 1 Uniform polyphenylene ether is a copolymer obtained by graft polymerizing a styrene compound such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, etc. to the above-mentioned PPE.

In the present invention, component (A) is the above-mentioned PPE resin or PPE resin and polystyrene (hereinafter referred to as PS).
It is a mixture with 〉-based resin. The polystyrene resin used here is known per se,
General formula (in the formula, R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is a halogen atom or a C 1 to 4 alkyl group)
(representing a substituent that is an alkyl group of Must. Examples of such styrene-based polymers include homopolymers of styrene or its derivatives, as well as polybutadiene, polyisoprene,
Styrenic polymers mixed with or modified with natural or synthetic elastomeric materials such as butyl rubber, EPDM, ethylene-propylene copolymer, natural rubber, shrimp chlorohydrin, and also styrene-containing copolymers, e.g. Examples include nitrile-acrylonitrile copolymer (S8N), styrene-butadiene copolymer, styrene-maleic anhydride copolymer, and styrene-acrylonitrile-butadiene copolymer (ABS). Preferred styrenic polymers for the present invention are homopolysbrene and rubber reinforced polystyrene.

It is desirable that the mixing ratio of the polystyrene resin to the polyphenylene ether resin be within a range that does not impair the excellent properties of the polyphenylene ether resin. Preferably, it is a ratio.

In the present invention, at least a portion of component (8) PPE or PS is modified to have at least one of an epoxy group, a carboxyl group, and an acid anhydride group in the molecule. It is preferable to be there.

Epoxidation, carboxylation, or acid anhydride conversion of the PPE can be carried out by known methods.

Regarding epoxidation, for example, JP-A-63-12552
It is described in Publication No. 5. The terminally epoxidized polyphenylene ether can be obtained by bringing polyphenylene ether and a substance having an epoxy group into contact under heating. The compound having an epoxy group is preferably an epoxy compound having a halogen group at one end or an epoxy compound having an epoxy group at both ends. Specifically, preferred epoxidized products at one end include shrimp chlorohydrin, 2-methylepichlorohydrin, etc., and preferred epoxidized products at both ends include 2,2-bis(4-glycidylphenyl ether) propane, epoxy resin, etc. be. From the viewpoint of suppressing blocking of polyphenylene ethers, moon-terminated epoxidized products are particularly preferred.

Carboxylation and acid anhydride conversion are described, for example, in Japanese Patent Publication No. 1983-500456.
Terminal carboxylated or acid anhydride PPE is obtained by reacting an acid chloride having a carboxyl group or an acid hydride group, such as trimellitic anhydride chloride, with a polyphenylene ether.

Next, modification of PS, that is, epoxidation, carboxylation, or acid anhydride conversion, is carried out using styrene alone or styrene alone or in the presence of a radical polymerization initiator or chain transfer agent having, for example, an epoxy group, a carboxyl group, or an acid anhydride group. It can be obtained by polymerizing a radically polymerizable monomer copolymerizable with.

Examples of such radically polymerizable monomers include p-methylstyrene, α-mebrustyrene, p-methoxystyrene, acrylonitrile, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Also,
Those polymerized in the presence of a rubbery polymer are more preferably used.

Furthermore, the following method can also be used to modify PPE, a mixture of PPE and PS, or a portion other than only the ends of PS. That is, a compound having an unsaturated bond and an epoxy group, a carboxyl group, or an acid anhydride group in a branch, such as maleic anhydride, maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, etc., is used in PPE.
This is a method of melt-kneading a mixture of PPE and PS or PS in the presence or absence of a radical polymerization initiator.

These modifications do not require that all of the PPE or PS be modified;
For example, it may be contained in an amount of 70% by weight or less based on the total amount of precepts (A).

Next, the ABS resin of Bokubun (B) used in the present invention consists of vinyl cyanide monomer (1), aromatic vinyl monomer (2) in the presence of diene rubber (1). and, if necessary, other copolymerizable monomers (2), using a known polymerization method, for example, in the presence of (a), A graft copolymer obtained by graft copolymerization by continuously supplying a mixture of {2} and a polymerization initiator, or in the presence of (a),
A product obtained by graft copolymerization of (C) and optionally (2), and a product obtained by copolymerizing (1), <C>, and optionally (2) in the absence of (A). It is a combination with.

Examples of the diene rubber (a) used in the present invention include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, etc. Alternatively, two or more types can be used in combination. In the present invention, polybutadiene rubber and/or styrene-butadiene copolymer rubber is preferably used.

Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.

Examples of the aromatic vinyl monomer (c) include styrene, α-methylstyrene, p-mebrustyrene, and pt-butylstyrene, among which styrene and/or
Alternatively, α-methylstyrene is preferably used.

Other copolymerizable monomers (such as acrylic acid,
α, β monounsaturated carboxylic acids such as methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic 1-t-
α, β monounsaturated carboxylic acid esters such as Bubl, cyclohexyl methacrylate; α, β monounsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride: N-phenylmaleimide, N-methylmaleimide, N Examples include imide compounds of α,β monounsaturated dicarboxylic acids such as -t-butylmaleimide.

There is no particular restriction on the composition or ratio of the above precepts in the ABS resin, but from the viewpoint of improving the moldability and impact resistance of the resulting PPE resin composition, ABS resin 10
Preferably, 5 to 85 parts by weight of the diene rubber (1) is used per 0 parts by weight. Similarly, 5 to 50 parts by weight, particularly preferably 7 to 45 parts by weight, of vinyl cyanide (2) is preferred.Aromatic For group vinyl (c), 10-90I
It is preferably Jt parts, more preferably 13 to 83 parts by weight, and particularly preferably 17 to 77 parts by weight.

Further, in the PPE resin composition of the present invention, the content of diene rubber (A) is preferably in the range of 1 to 60% by weight, more preferably 3 to 55% by weight, particularly preferably 5% by weight. ~50% by weight.

Furthermore, when the weight of the diene rubber in the PPE resin composition of the present invention is 15% by weight or more, the impact resistance of the resin composition is dramatically improved.

There are no particular restrictions on the manufacturing method of the above-mentioned ABS resin, including bulk polymerization, solution polymerization, bulk suspension polymerization, fl! Generally known methods such as turbid polymerization and emulsion polymerization are used. It is also possible to obtain the above-mentioned ABS resin silk by blending separately copolymerized resins.

The blending ratio of the above components (A) and (B) is (A)
(B) 90 to 10 parts by weight per 10 to 90 parts by weight, preferably (A) to 20 to 80 parts by weight (
B) It is 80 to 20 parts. When (A) exceeds 90 parts by weight, the formability becomes poor, and (
If B) exceeds 90 parts, the heat resistance will decrease.

Next, component (C), which is a feature of the present invention, will be described. Component (C) is (i) an oxazolinyl group-containing unsaturated monopolymer, (ii) acrylonitrile J3, and (iii)
It is a copolymer of aromatic vinyl compounds.

Preferred unsaturated monomers (i) containing ox-V zolinyl groups include those represented by the general formula: C-12, where Z contains a polymerizable double bond. Preferred substituent groups Z are as follows.

0 is a butyl group.

Particularly preferred compounds are vinyloxazolines having the general formula in which R II is a hydrogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms, such as a methyl group, an i- and n-probyl group; R II has the above meaning and is preferably a hydrogen atom or a methyl group.

In addition, examples of the aromatic vinyl compound (iii) include styrene, α-methylstyrene, p-methylstyrene, p-t
-butylstyrene, etc., and styrene and α-methylstyrene are preferred.

The copolymer of component (C) includes, for example, an oxazolinyl group-containing acrylonitrile-styrene copolymer, an oxazolinyl group-containing ABS resin (containing butadiene), an oxazolinyl group-containing graft copolymer in which acrylonitrile, oxlyzoline, and polystyrene are grafted onto butadiene. Including merging etc.

In the oxazolinyl group-containing copolymer composed of the above copolymer components (i), (ii) and (iii),
The copolymer mother occupied by the oxazolinyl group-containing unsaturated monomer is preferably 0.001 to 14% by weight, more preferably 0.001 to 14% by weight. The range is 0.01% to 5%. Copolymerization amount is 0.0
01 @Amount% If there is no vortex, the impact strength of the assembly is low;
Moreover, if it exceeds 14% by weight, the copolymer tends to gel, and a molded article with good surface texture cannot be obtained.

There are no particular restrictions on the method for producing the copolymer of component (C), and commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. Copolymerization component m. (++ There are no particular restrictions on the preparation method for t and (iii), and they may be added all at once at the initial stage. In order to prevent the polymerization from occurring, part or all of the ingredients may be polymerized while being continuously or dividedly charged.

In addition, the above-mentioned copolymer components (iL(ii) and (ii)
It is also possible to copolymerize 0 to 70 parts by weight of other copolymerizable monomers with respect to the total of 100 parts by weight of i).

Other copolymerizable monostars include α,β monounsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, monot-butyl methacrylate, and cyclohexyl methacrylate.

Component (C) is used in an amount of 1 to 30 parts by weight, preferably 2 to 30 parts by weight, per 100 parts by weight of the above-mentioned components (A) and (B).
Add 20 parts by weight. If component (C) is less than 1 part by weight, the compatibility of (A) and (B) will not improve, resulting in poor appearance of the shaped product, and if it exceeds 30 parts by weight, thermal stability and moldability will decrease. .

The PPE resin composition of the present invention has the above-mentioned feature (8).
, (B) and (C), polystyrene (PS), styrene/acrylonitrile copolymer (SAND), polymethacrylate (PMMA),
Styrene/methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acrylonitrile copolymer, p-methyl Styrene/acrylic nitrile copolymer, styrene/N-7. Vinyl copolymers such as enylmaleimide copolymers, methacrylic acid-butadiene-styrene terpolymer (MBS) resins, AE
Thermoplastic resins such as S resin, AAS resin, polycarbonate, polyproamide (nylon-6), and polyhexamethylene adipamide (nylon-6,6) may be mixed as appropriate, or polyethylene, polypropylene, ethylene/propylene copolymer ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/5-ethylidene-2-norbornene copolymer, ethylene/propylene/1,4-hexadiene copolymer, By appropriately mixing polyolefin rubbers such as ethylene/vinyl acetate copolymer and ethylene/butyl acrylate copolymer, it is possible to adjust the physical properties and characteristics to more or less desired properties. In addition, depending on the purpose, pigments, dyes, glass fibers, reinforcing materials and fillers such as metal flakes, carbon fibers, heat stabilizers,
Antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers,
Antistatic agents, flame retardants, etc. can be added.

There are no particular limitations on the method for producing the resin composition of the present invention, and conventional methods can be used satisfactorily.

However, melt mixing methods are generally preferred. Any melt mixing method can be used provided it can handle the molten viscous mass. The method may be used batchwise or continuously.

In particular, extruders, Banbury mixers, rollers, twenty-one gooses, etc. can be mentioned as examples.

(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples.
The present invention is not limited to these.

In addition, the following compounds were used in the examples.

PPE-1: Poly-(2.6-dimethyl-1.4-phenylene)ether (unmodified) with an intrinsic viscosity of 0.46 dl/g measured at 30°C in chloroform.PPE-2 :PPE-1 100. PPE modified in an extruder at 300°C by adding all parts by weight of anhydrous maleic to the parts by weight PS: Rubber-reinforced polystyrene, trademark: HT-644 Mitsubishi Monsanto Seikaritsu L ABS-1: ABS resin, trademark ;Tufflex 610
1 ABS-2 manufactured by Mitsubishi Monsanto (I!1: ABS resin, trademark: CE-301, manufactured by Denki Kagaku Kogyo Co., Ltd.) and oxazolinyl group-containing AS: vinyloxazoline 5%, styrene 70% by weight, and acrylonitrile 25% by weight Copolymer with a number average molecular star of about 50,000, trademark: CX-RAS-1
005, Nippon Shokubai (l) Manufactured Examples 1 to 3 and Comparative Example 1
~2 Each component was mixed in the proportion shown in the table, and the temperature was set at 290°C.
It was extruded using a axial extruder UN (screw diameter 50 mm) to make pellets.

After drying this pellet, a test piece was molded using a Kende Arugata 1 (150 ton) set at a cylinder temperature of 280'C, and the Izod impact strength was measured.

The results are shown in the table.

The Izod impact strength is 178 inches Izod! according to AST}l D256. J impact strength (notched) is measured, heat deformation thermal polishing (HDT) is AST
Measured according to tl D64B.

Further, delamination was evaluated visually by folding a test piece with a thickness of 176 inches and rlJ1/2 inch.

Light bolting resistance was determined by immersing a hollow-shaped product attached to a bending jig that produces 1% strain in light bolting, and determining the state of υj bending after 12 hours. Items that did not break were marked with ○, and items that did crack were marked with X.

Component (A) PP[-1 PPE-2 PS Component (B): ABS-1 55 ABS-2 Component (C): Oki V zolinyl group-containing AS 5 40 Example 30 40 10 5555 5 5 Izod impact strength (Ko -cm/cm) 11D (°C) Layer peeling kerosene resistance comparative example 4040 (Effects of the invention) The PPE resin composition of the present invention is composed of PPE resin and ABS.
Since the compatibility of the resins is good, the impact resistance is high, and since it maintains the excellent properties of ABS resins, such as solvent resistance and heat resistance, its uses are wide and useful.

60 60

Claims (2)

[Claims] (1) (A) polyphenylene ether resin or this and 10 to 90 parts by weight of polystyrene resin, (B) 90 to 10 parts by weight of ABS resin, and (C) oxazolinyl group-containing acrylonitrile-aromatic vinyl copolymer. A polyphenylene ether resin composition comprising 1 to 30 parts by weight based on a total of 100 parts by weight of (A) and (B). (2) The polyphenylene ether resin according to claim 1, wherein at least a part of component (A) is modified to have at least one group selected from a carboxyl group, an acid anhydride group, and an epoxy group in the molecule. Composition.