JP3041927B2 - Resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition, and more particularly to a resin composition comprising a polyphenylene ether resin and a polyolefin resin as main resin components, in particular, improved impact resistance. It relates to a resin composition.

[Conventional technology]

Polyphenylene ether resin is a useful resin with excellent mechanical and electrical properties and high heat resistance, but it has the drawbacks of poor moldability and solvent resistance, so the use of polyphenylene ether resin itself is within its scope. Is severely restricted.

On the other hand, polyolefin resins, especially crystalline polyolefin resins, are not only excellent in moldability and solvent resistance, but also have features such as low specific gravity and low cost. Widely used. However, such a polyolefin resin also has a drawback of low heat resistance, which is a major obstacle to further expanding the use of the polyolefin resin.

Under such circumstances, it is industrially valuable to blend a polyphenylene ether resin and a polyolefin resin, each having excellent characteristics, to produce a resin composition having the advantages of both. And a resin composition comprising a polyphenylene ether resin (JP-B-42-7069, JP-A-2-115248, etc.) have been proposed.

However, in general, polyphenylene ether resin and polyolefin resin have low affinity with each other, and there is a disadvantage that sufficient compatibilization cannot be achieved by mere blending.

Examples of the resin composition in which such inconvenience has been improved include a resin composition containing an acid-modified polyolefin resin and a polyphenylene ether resin (Japanese Patent Laid-Open No. 60-120748); a resin composition comprising a modified olefin resin and a modified polyphenylene ether resin. (JP-A-63-128056) and the like have been proposed.

[Problems to be solved by the invention]

However, even with these conventionally proposed resin compositions, the degree of compatibilization is not sufficient, and solvent resistance,
Although properties such as moldability are improved, mechanical properties such as impact resistance are unsatisfactory.

The aim of the present invention is to provide a resin composition having excellent mechanical properties, especially impact strength, comprising a polyphenylene ether resin having characteristics of heat resistance and a polyolefin resin having characteristics of solvent resistance and economy as main constituent resin components. Is to provide.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, when a specific organic compound is blended with a polyphenylene ether resin and a polyolefin resin, a resin composition having a high degree of compatibility can be obtained. To complete the present invention.

That is, the present invention relates to (A) a polyphenylene ether resin, (B) a polyolefin resin, and (D) a general formula (R ₁ O) _m R (COOR ₂ ) _{n wherein} R is a linear or branched chain. R ₁ is a hydrogen atom or an alkyl group, an aryl group, an acyl group or a carbonyldioxy group containing 1 to 10 carbon atoms.
R ₂ represents a hydrogen atom or an alkyl or aryl group containing 1 to 20 carbon atoms, m is equal to 1 or 2, n is 2 or more, and (OR ₁ ) is α with respect to the carbonyl group. And at least two carbonyl groups are separated by 2 to 6 carbon atoms], and the weight of (A) and (B) Expressed as a ratio, (A) :( B) = 99: 1 to 1:99, and the amount of (D) per 100 parts by weight of the total amount of (A) and (B) is 0.1 to 30 parts by weight. The present invention relates to a resin composition.

The polyphenylene ether resin (A) in the present invention has a general formula Is a polymer comprising a repeating unit represented by R ₁ , R ₂ , R ₃ and R ₄ in the formula are the same or different from each other selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbonoxy group and a substituted hydrocarbonoxy group. Represents different groups. Examples of the substituent in the substituted hydrocarbon group and the substituted hydrocarbon oxy group include a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, an amide group, an ether group, a sulfide group,
Examples thereof include thermally stable groups such as a sulfone group.

Specific examples of such polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), and 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), poly (2,6-butyl-1,4-
Phenylene ether), poly (2,6-dipropenyl-1,4
-Phenylene ether), poly (2,6-dilauryl-1,4
-Phenylene ether), poly (2,6-diphenyl-1,4
-Phenylene ether), poly (2,6-dimethoxy-1,4
-Phenylene ether), poly (2,6-diethoxy-1,4
-Phenylene ether), poly (2-methoxy-6-eoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy-1,4-phenylene ether), poly (2-methyl-6- Phenyl-1,4-phenylene ether, poly (2-methyl-1,4-phenylene ether), poly (2-ethoxy-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether) ), Poly (3-methyl-6-t-butyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2,5-dibromo-1,4 -Phenylene ether), poly (2,6-dibenzyl-1,4-phenylene ether) and various copolymers containing plural kinds of repeating units constituting these polymers.
Some copolymers include 2,3,6-trimethylphenol, 2,3,5,
Polysubstituted phenols such as 6-tetramethylphenol and 2,6
-Including copolymers with dimethylphenol. In the present invention, the polyphenylene ether resin includes those obtained by graft-modifying the above-mentioned polyphenylene ether resin with a styrene monomer such as styrene or α-methylstyrene. Among these polyphenylene ether resins, preferred polyphenylene ether resins are poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. .

The molecular weight of the polyphenylene ether resin that can be used in the present invention is not generally defined because its preferred range varies depending on the purpose, but it is generally expressed in terms of intrinsic viscosity measured in chloroform at 30 ° C. 0.1 to 0.7
dl / g, more preferably 0.2 to 0.6 dl / g.

Methods for producing such polyphenylene ether resins are known, for example, US Pat. Nos. 3,306,874 and 3,306,875,
No. 3,257,357, and JP-B-52-17880, JP-A-50-51197, and JP-A-1-304119.

The polyolefin resin (B) in the present invention is ethylene, propylene, butene-1, pentene-1, hexene-1,
3-methylbutene-1,4-methylpentene-1, octene
Α-olefins such as 1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1; and olefins such as cyclic olefins described in JP-A-2-115248. It is a homopolymer or a copolymer.

Copolymers obtained by copolymerizing olefins and a small amount of another unsaturated monomer, and modified products of the copolymers and the above-mentioned olefins, alone or copolymerized by oxidation, halogenation, sulfonation, etc. It shall be included in the polyolefin resin.

Examples of other unsaturated monomers copolymerizable with olefins include acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic anhydride, arylmaleimide, and alkylmaleic acid. Unsaturated organic acids such as imides or derivatives thereof; vinyl esters such as vinyl acetate and vinyl butyrate: aromatic vinyl compounds such as styrene and methyl styrene; vinyl silanes such as vinyl trimethylmethoxysilane and γ-methacryloyloxypropyl trimethoxysilane; Cyclopentadiene, 4-ethylidene-2-norbornene, 4-methyl-1,
Examples include non-conjugated dienes such as 4-hexadiene and 5-methyl-1,4-hexadiene. Of these, ethylene,
Copolymers or homopolymers containing a majority weight of propylene, butene-1,3-methylbutene-1,4-methylpentene-1 are preferred. Crystallinity of propylene homopolymer, propylene-ethylene block or random copolymer, etc. Propylene polymers are more preferred.

The molecular weight of the polyolefin resin cannot be specified unconditionally because its preferred range varies depending on the purpose, but it is generally expressed in terms of melt flow rate (MFR) measured at a temperature of 230 ° C and a load of 2.16 kg / cm ^2. 0.01
400400 g / 10 min, preferably 0.15 to 60 g / 10 min.

The polyolefin resin can be produced by a conventionally known method such as polymerization or modification. Also,
Commercial products are also widely available and can be used by appropriately selecting from them.

In the present invention, when a resin composition having higher impact strength is desired, it is desirable to incorporate the elastomer (C) into the composition.

Examples of such elastomers include natural rubber, polybutadiene rubber, polyisoprene rubber, butyl rubber, ethylene-propylene copolymer rubber, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, hydrogenated and non-hydrogenated rubbers. Styrene-conjugated diene block copolymer rubber, polyester rubber, acrylic rubber,
Examples thereof include silicone rubber and the like and modified products thereof.

Among them, preferred elastomers are ethylene-propylene copolymer rubbers including terpolymers obtained by copolymerizing diene compounds and graft copolymers obtained by graft copolymerizing unsaturated monomers such as styrene; And styrene-conjugated diene-based block copolymer rubbers such as styrene-isoprene diblock copolymers and styrene-butadiene block copolymers containing hydrogenated products such as partially hydrogenated products.

In the present invention, the aliphatic polycarboxylic acid derivative (D) which is a central component in the present invention, which is thought to function as a compatibilizer between the polyphenylene ether resin and the polyolefin resin, is represented by the general formula (R ₁ O) _m R (COOR ₂ ) _{and n} is an aliphatic polycarboxylic acid represented by _n , a salt thereof, or an ester thereof. Here, R is a linear or branched saturated hydrocarbon group containing 2 to 20 carbon atoms, R ₁ is a hydrogen atom or an alkyl or aryl group containing 1 to 10 carbon atoms, An acyl group or a carbonyldioxy group, each R ₂ is a hydrogen atom or 1 to 20
Represents an alkyl group or an aryl group containing carbon atoms, m is equal to 1 or 2, n is 2 or more,
(OR ₁ ) is in the α or β position to the carbonyl group, and at least two carbonyl groups are separated by 2 to 6 carbon atoms.

Specific examples of such aliphatic polycarboxylic acid derivatives (D) include oxycarboxylic acids exemplified by citric acid, malic acid, tartaric acid, agaric acid, etc .; calcium citrate, calcium malate, potassium citrate, potassium malate, etc. And oxycarboxylates exemplified by acetyl citrate, stearyl citrate, distearyl citrate, acetyl malate, stearyl malate and the like. Of these, oxycarboxylic acids are preferred, and citric acid and malic acid are more preferred.

In some cases, the aliphatic polycarboxylic acid derivative (D) of the present invention is more preferably used together with an alkenyl aromatic hydrocarbon such as styrene or α-methylstyrene.

Further, it is no problem to use a conventionally known modifier such as disclosed in the above-mentioned JP-A-63-128056 together with the aliphatic polycarboxylic acid derivative (D) of the present invention.

The resin composition of the present invention can be produced by a general method used for thermoplastic resin blends, such as melt kneading and solution mixing. Regarding the mixing order of all the components, when all the components are simultaneously and simultaneously mixed, both or one of the polyphenylene ether resin (A) and the polyolefin resin (B) is separately mixed with the aliphatic polycarboxylic acid derivative (D) in advance. For example, various cases can be adopted, such as mixing with other components after changing to a denatured product.

As a method for producing the resin composition of the present invention, melt kneading is preferable, and the kneading order is such that at least a part of the polycarboxylic acid derivative (D), at least a part of the polyphenylene ether resin (A) and at least a part of the polyolefin resin (B) are simultaneously mixed. A mode of kneading is preferred. Here, as the method of melt kneading, various conventionally known methods can be adopted.
That is, the above-mentioned components are mixed by a known mixing means used for mixing resins or liquid or solid additives such as a Henschel mixer, a super mixer, a ribbon blender, a V blender, etc., to form a uniform mixture. After that, a method of kneading the mixture using a kneading means such as a Banbury mixer, a plast mill, a Brabender plastograph, a single-screw or twin-screw extruder, and the like can be given as examples.

During kneading, the temperature is selected in the range of 150 to 400 ° C, preferably 200 to 350 ° C. In some cases, it is preferable to perform kneading in the presence of a radical generator in order to obtain a more uniform resin composition.

Examples of such radical generators include halogenated imides such as N-bromosuccinimide; benzoyl peroxide;
Dicumyl peroxyside, di-t-butylperoxyside, cumene hydroperoxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,1,3
Organic peroxides such as -bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate; persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile, 1, And diazo compounds such as 1'-azobis (cyclohexanecarbonitrile).

When such a radical generator is used, its amount is generally 10 parts by weight or less, preferably 0.001 part by weight, based on 100 parts by weight of the total of the polyphenylene ether resin (A), the polyolefin resin (B) and the elastomer (C). To 5 parts by weight.

The composition of the polyphenylene ether resin (A) and the polyolefin resin (B) in the resin composition of the present invention is selected depending on the purpose such as heat resistance and fluidity required for the composition. (A): (B) = 99: 1 to 1:99 in terms of the weight ratio of (B), preferably 5:95 to
80:20.

The resin composition of the present invention can contain the above-mentioned elastomer (C) if desired. Here, the proportion is usually 70% by weight or less, preferably 1 to 50% by weight, based on the total amount of the polyphenylene ether resin (A), the polyolefin resin (B) and the elastomer (C).

In the present invention, (D) per 100 parts by weight of the total amount of (A) and (B) (or the total amount of (A), (B) and (C) when using optional component (C)) Amount of 0.1 ~
It is 30 parts by weight, preferably 0.2 to 20 parts by weight.

The resin composition of the present invention may contain a wide range of substances other than the above substances, if desired. Examples of such other substances which are preferably included for specific purposes include binders, other resins, flame retardants, stabilizers, plasticizers,
Examples include lubricants, pigments, reinforcing fibers, and fillers.

Examples of the binder include diamines, dicarboxylic acids, diepoxy compounds, diols and the like described in JP-A-63-128056.
And dioxanes such as diphenylmethane diisocyanate and hexamethylene diisocyanate; and bisoxazolines such as 2,2'-bis (2-oxazoline).

Examples of other resins include polyamides such as nylon-6, nylon-66, and nylon-12; polyamide imides; polyacrylates such as polymethyl methacrylate; and polyhalogenation such as polyvinyl chloride and polyvinylidene chloride. Vinyls and the like.

Examples of flame retardants include triphenyl phosphate, tricresyl phosphate, phosphates obtained from a mixture of isopropylphenol and phenol, and mixtures of difunctional phenols such as benzohydroquinone or bisphenol A with other alcohols or phenols. Phosphate esters exemplified by the obtained phosphate and the like; brominated compounds exemplified by decabromobiphenyl, pentabromotoluene, decabromodiphenyl ether, hexabromobenzene, brominated polystyrene, brominated epoxy resin; melamine, melamine triyl Nitrogen-containing compounds such as socinurate; and inorganic substances such as red phosphorus, antimony trioxide, and boron oxide.

Specific examples of the reinforcing fibers include inorganic fibers such as glass fiber, potassium titanate fiber, rock wool, and carbon fiber; organic fibers such as aromatic polyamide fiber and polybenzimidazole fiber; and metal fibers such as brass fiber and aluminum zinc fiber. Are enumerated.

Specific examples of the filler include glass beads, milled glass fiber, asbestos, wollastonite, mica, talc, clay, calcium carbonate, magnesium hydroxide,
Inorganic fillers such as silica and diatomaceous earth; metal fillers such as aluminum flake and zinc flake; organic fillers such as polyimide powder.

In addition, specific examples of the stabilizer include sterically hindered phenols, organic phosphites, oxalic acid diamides, and sterically hindered amines. Specific examples of the pigment include titanium oxide,
Examples thereof include zinc sulfide and the like, and specific examples of the lubricant include polyethylene wax, paraffin and the like.

The mixing ratio of the above-mentioned other substances can be arbitrarily selected according to the purpose. However, if a general guideline for using them is given, polyphenylene ether resin (A), polyolefin resin (B) and elastomer For the total amount of class (C), 100 parts by weight,
00 parts by weight or less; the flame retardant is 30 parts by weight or less, preferably 1 to 20 parts by weight; the stabilizer is 20 parts by weight or less, preferably 0.001 to 10 parts by weight; Parts by weight, preferably 0.1 to 80 parts by weight;

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the examples.

Note that the tensile elongation and Izod impact strength (with notch) in the examples are ASTM D638 and ASTM D256 for test pieces (thickness 3.2 mm) prepared by injection molding, respectively.
It is the value measured at 23 ° C according to
T) is a value measured under the condition of a load of 4.6 kg / cm ² according to ASTM D648.

The intrinsic viscosity of the polyphenylene ether resin is a value measured at 30 ° C. in chloroform using an Ubbelohde viscometer.

Examples 1 to 8 and Comparative Examples 1 and 2 30 parts by weight of poly (2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.40 dl / g, polypropylene having an MFR of 0.4 g / 10 minutes [Sumitomo Chemical Industry Co., Ltd .: Sumitomo Noblen D5
01] 70 parts by weight, 2 parts by weight of styrene and 1,3-bis (t
1 part by weight of a radical generator composition in which -butylperoxyisopropyl) benzene was dispersed at a concentration of 8% by weight in polypropylene, and the elastomers and aliphatic polycarboxylic acid derivatives shown in Table 1 as shown in Table 1 The obtained parts by weight were mixed using a super mixer.

The obtained mixture is supplied from the upstream to a first supply port, a first kneading section,
Continuous supply to the first supply port of a 50 mm twin-screw kneading extruder [TEM-50 manufactured by Toshiba Machine Co., Ltd.] equipped with a second supply port, a second kneading section, a vent port and a cylinder head in this order. While kneading at a barrel temperature of 260 ° C., the resin composition of the present invention was obtained.

Table 1 shows the tensile elongation and Izod impact strength of the resin composition.

The HDT of the resin composition in Example 1 was as high as 148 ° C.

Reference Example 1 The poly (2,6-dimethyl-1,4-phenylene ether), DL-malic acid, styrene and radical generator composition in Example 1 were respectively 100 parts by weight, 1 part by weight, 2 parts by weight and 1 part by weight. The parts by weight were mixed using a super mixer, and the obtained mixture was extruded using the twin-screw kneading extruder in Example 1 at a barrel temperature of 300 ° C. The extruded strand was pelletized to obtain a pellet of the composition.
This is designated as a pre-kneaded material M-1.

Reference Example 2 The procedure of Reference Example 1 was repeated, except that DL-malic acid in Reference Example 1 was replaced with citric acid, to obtain pellets of the composition. This is designated as a pre-kneaded material M-2.

Reference Example 3 100 parts by weight, 1 part by weight, 2 parts by weight, and 1 part by weight of each of the polypropylene, DL-malic acid, styrene and the radical generator composition in Example 1 were mixed using a super mixer to obtain a mixture. The mixture was extruded using the twin-screw extruder in Example 1 at a barrel temperature of 230 ° C. The extruded strand was pelletized to obtain a pellet of the composition. This is designated as Prekneaded Material M-3.

Reference Example 4 The procedure of Reference Example 3 was repeated, except that DL-malic acid in Reference Example 3 was replaced with maleic anhydride to obtain pellets of the composition. This is designated as Prekneaded Material M-4.

Example 9 16 parts by weight of the pre-kneaded material M-1 obtained in the above reference example,
64 parts by weight of the pre-kneaded material M-3, 20 parts by weight of ethylene-propylene rubber (manufactured by Sumitomo Chemical Co., Ltd .: Esplen E111P) and 1 part by weight of hexamethylenediamine were mixed, and the resulting mixture was used in Example 1. It was extruded at a barrel temperature of 260 ° C. using a twin-screw extruder. The extruded strand was pelletized to obtain a resin composition of the present invention.

The tensile elongation and Izod impact strength of the composition were 160% and 28 kg · cm / cm, respectively.

Example 10 Except that the pre-kneaded material M-1 was changed to the pre-kneaded material M-2, the same operation as in Example 9 was carried out to obtain resin composition pellets.

The tensile elongation and Izod impact strength of the resin composition were 145% and 25 kg · cm / cm, respectively.

Example 11 The procedure of Example 9 was repeated, except that the pre-kneaded material M-3 was replaced with the pre-kneaded material M-4, to obtain pellets of the resin composition.

The tensile elongation and Izod impact strength of the resin composition were 170% and 29 kg · cm / cm, respectively.

〔The invention's effect〕

As described above, according to the present invention, mechanical properties, particularly impact strength, of a polyphenylene ether resin having heat resistance and a polyolefin resin having solvent resistance, economy and the like as main constituent resin components. And a resin composition excellent in the above.

Continuation of the front page (56) References JP-A-63-113058 (JP, A) JP-A-2-163158 (JP, A) JP-A-61-502195 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) C08L 71 / 12,23 / 00,21 / 00 C08K 5/20

Claims (4)

(57) [Claims] 1. A polyphenylene ether resin, (B) a polyolefin resin, and (D) a compound represented by the general formula (R ₁ O) _m R (COOR ₂ ) _{n wherein} R is a linear or branched 2 to 20 R ₁ is a hydrogen atom or an alkyl group, an aryl group, an acyl group or a carbonyldioxy group containing 1 to 10 carbon atoms.
R ₂ represents a hydrogen atom or an alkyl or aryl group containing 1 to 20 carbon atoms, m is equal to 1 or 2, n is 2 or more, and (OR ₁ ) is α with respect to the carbonyl group. And at least two carbonyl groups are separated by 2 to 6 carbon atoms], and the weight of (A) and (B) Expressed as a ratio, (A) :( B) = 99: 1 to 1:99, and the amount of (D) per 100 parts by weight of the total amount of (A) and (B) is 0.1 to 30 parts by weight. Resin composition. (A) a polyphenylene ether resin,
(B) a polyolefin resin, (C) an elastomer and (D) a general formula (R ₁ O) _m R (COOR ₂ ) _{n wherein} R is a linear or branched 2 to 20 carbon atoms Wherein R ₁ is a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, an aryl group, an acyl group or a carbonyldioxy group;
R ₂ represents a hydrogen atom or an alkyl or aryl group containing 1 to 20 carbon atoms, m is equal to 1 or 2, n is 2 or more, and (OR ₁ ) is α with respect to the carbonyl group. And at least two carbonyl groups are separated by 2 to 6 carbon atoms], and the weight of (A) and (B) Expressed as a ratio, (A) :( B) = 99: 1 to 1:99, and the amount of (C) based on the total amount of (A), (B) and (C) is 70% by weight or less. Wherein the amount of (D) is 0.1 to 30 parts by weight per 100 parts by weight of the total of (A), (B) and (C). 3. The resin composition according to claim 1, wherein the aliphatic polycarboxylic acid derivative is an oxycarboxylic acid. 4. The resin composition according to claim 1, wherein the aliphatic polycarboxylic acid derivative is malic acid or citric acid.