JPH06248172A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve moldability, solvent resistance, oil resistance, and impact resistance by mixing a specific poly(phenylene ether) resin with a polyamide resin, a rubbery polymer, and a polymer of an itaconic acid derivative. CONSTITUTION:100 pts.wt. mixture of 30-80 wt.% poly(phenylene ether) resin hating a backbone comprising structural units represented by formula I (wherein R1 is a 1-3C alkyl and R2 and R3 each is H or a 1-3C alkyl) and 70-20wt.% polyamide resin is mixed with 3-30 pts.wt. rubbery polymer and 0.01-20 pts.wt. itaconic acid derivative polymer which has a backbone comprising structural units represented by formula II (wherein R4 and R5 both are oxygen, hydroxy, a 1-6C alkyl, or amino).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition. More specifically, the present invention is characterized by blending polyphenylene ether resin, polyamide resin, rubbery polymer, and polymer of unsaturated carboxylic acid, moldability, solvent resistance, oil resistance and impact resistance. The present invention relates to a thermoplastic resin composition having improved properties.

[0002]

2. Description of the Related Art Polyphenylene ether resins are excellent in thermal properties, mechanical properties, electrical properties, etc., but have a drawback that they are inferior in moldability due to their high melt processing temperature and low fluidity. Further, it has a strong resistance to inorganic chemicals such as acids and alkalis, but dissolves in organic solvents such as acetone, benzene, toluene, and halogenated hydrocarbons, causes swelling, and has solvent resistance, There is a strong demand for improvement in oil resistance.

JP-B-60-11966 proposes a method of melt-kneading a polyphenylene ether resin, a polyamide resin, and a specific unsaturated compound in order to improve solvent resistance and oil resistance. However, the composition obtained by this method is not always sufficient in impact resistance, and generally has a strong odor during kneading, resulting in very poor workability.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art, to provide good molding processability, solvent resistance and oil resistance, as well as excellent impact resistance. Is to provide a resin composition.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied various experiments for the purpose of improving / improving the drawbacks of polyphenylene ether resins and polyamide resins without impairing their excellent properties. As a result, by blending a polyphenylene ether resin, a polyamide resin, a rubbery polymer and a polymer having an itaconic acid component as a constituent component, it is possible to obtain a composition that solves the problems at once. With the knowledge obtained, further intensive study was conducted to complete the present invention.

That is, the present invention provides (a) a general formula,

[Chemical 3] (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and R
₃ is the same or different from each other, hydrogen atom or carbon number 1
To 3 lower alkyl groups. ) A polyphenylene ether-based resin having a structural unit represented by the main chain in the main chain, (b) a polyamide resin, and a total amount of both of 100 parts by weight,
(C) rubbery polymer, 3 to 30 parts by weight, and (d) general formula,

[Chemical 4] (Wherein R ₄ and R ₅ are the same oxygen, or the same or different from each other, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms or an amino group) in the main chain. Polymer of itaconic acid derivative having 0.01 to 20
A thermoplastic resin composition, which is a resin composition composed of parts by weight, wherein a weight composition ratio of (a) polyphenylene ether resin and (b) polyamide resin is 30/70 to 80/20.

The present invention will be described in more detail below. The (a) polyphenylene ether resin used in the resin composition of the present invention is a polymer having a structural unit represented by the above general formula 3 in the main chain, and may be a homopolymer or a copolymer. Good.

Specifically, poly (2,6-dimethyl-
1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-
Methyl-6-ethyl-1,4-phenylene) ether,
Examples thereof include poly (2-methyl-6-propyl-1,4-phenylene) ether, and especially poly (2,6-
Dimethyl-1,4-phenylene) ether is preferably used.

The (b) polyamide resin used in the present invention is not particularly limited as long as it has a —CONH— bond in the polymer main chain and can be melted by heating.
Specifically, nylon-4, nylon-6, nylon-
One or more selected from aliphatic nylons such as 6,6, nylon-610, nylon-11, and nylon-12, polyhexamethylenediamine terephthalamide, aromatic nylons obtained from metaxylene diamine and adipic acid. Polyamides of can be preferably used.

The mixing ratio of both components of the polyphenylene ether resin (PPE) and the polyamide resin (PA) is a weight ratio,
There is no limitation within the range of PPE / PA = 30/70 to 80/20, but the range of 35/65 to 65/35 is preferable. The composition containing the polyphenylene ether resin in an amount smaller than the above range loses the excellent properties such as thermal properties, mechanical properties, and electrical properties inherent to the polyphenylene ether resin. Further, a composition containing a polyphenylene ether resin in an amount larger than the above range is not preferable because the effect of improving solvent resistance and oil resistance is small.

The rubbery polymer (c) used in the present invention is a rubbery polymer having rubber elasticity at room temperature obtained from a conjugated diene compound alone or a combination of at least one diene compound and an olefin and a vinyl compound. is there.

Specific examples of the rubbery polymer include polybutadiene, polyisoprene, polychloroprene, polychlorobutadiene, ethylene-propylene-diene terpolymer, styrene-butadiene copolymer (random copolymer, block copolymer). (Including all copolymers, graft copolymers, etc.), or hydrogenated products thereof, isobutylene-butadiene copolymer, acrylonitrile-butadiene copolymer,
Butyl acrylate-acrylonitrile copolymer, styrene-isoprene copolymer, or hydrogenated product thereof, styrene-butadiene-styrene teleblock copolymer,
Alternatively, hydrogenated products thereof, styrene-isoprene-styrene tereblock copolymers, or hydrogenated products thereof, methylmethacrylate-butadiene copolymers, butylmethacrylate-butadiene copolymers and the like can be mentioned.

The amount of the rubbery polymer added in the present invention is 3 to 100 parts by weight of the composition comprising (a) a polyphenylene ether resin and (b) a polyamide resin.
30 parts by weight, preferably 5 to 15 parts by weight. When the amount is 3 parts by weight or less, the impact resistance is insufficiently improved, and when the amount is 30 parts by weight or more, the dispersibility of the rubbery polymer becomes poor, resulting in a molded article. The appearance characteristics such as smoothness and mechanical properties tend to decrease.

The polymer of the itaconic acid derivative (d) used in the present invention is a polymer of the itaconic acid derivative having the structural unit represented by the above general formula 4 in the main chain. (D)
The polymer of the itaconic acid derivative is specifically a homopolymer selected from the group consisting of itaconic acid, monoesters and diesters of itaconic acid, itaconic anhydride, monoamides and diamides of itaconic acid, It is a copolymer composed of two or more kinds selected from the above group. In particular, a homopolymer of itaconic acid has a great effect of improving impact resistance and can be preferably used.

The polymer of the itaconic acid derivative (d) is obtained mainly by radical polymerization of the itaconic acid derivative monomer, and is not particularly limited as long as it has a degree of polymerization of 10 or more. Polymers can be used. The addition amount of the polymer of the itaconic acid derivative (d) in the present invention is as follows: (a) polyphenylene ether resin and (b)
It is in the range of 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the composition comprising the polyamide resin.
10 to 10 parts by weight. If the amount added is less than 0.01 parts by weight, the impact resistance is not sufficiently improved, and if it exceeds 20 parts by weight, the appearance properties such as fluidity and smoothness of the molded product deteriorate.

The resin composition of the present invention includes other thermoplastic resins such as PC, PBT, PET, PE, PP, maleic acid modified PP, POM, PMMA, MS, MBS, A.
S, AAS, AES, AMBS, PS, HIPS, styrene-maleic acid copolymer resin (Dylark manufactured by Arco Chemical Co., USA), polyphenylene sulfide, polyether ether ketone, polysulfone and the like can be blended.

If desired, various known additives may be added to the resin composition of the present invention. For example, a reinforcing material, a filler, a stabilizer, an ultraviolet absorber, an antistatic agent, a lubricant, a release agent, a dye, a pigment and the like can be mentioned. Further, it is preferable for the purpose of the present invention to use an appropriate amount of a known organic peroxide such as benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile or a diazo compound as a radical generator.

Examples of the above-mentioned filler and reinforcing agent are glass fiber, glass beads, glass flake, glass fiber cloth, glass fiber mat, graphite, carbon fiber, carbon fiber cloth, carbon fiber mat, carbon black, carbon flake. Selected from metal fibers and flakes made from aluminum, stainless steel, brass and copper, metal powder, organic fibers, acicular titanate titanate, mica, talc, clay, (acicular) titanium oxide, wollastonite, calcium carbonate You may mix | blend the one or more types of strengthening agents mentioned above. In order to increase the rigidity and strength and further improve the appearance and smoothness of the molded product, the diameter of the fiber may be reduced. As a glass fiber having a small fiber diameter, E-FMW- manufactured by Nippon Inorganic Co., Ltd.
800 (average fiber diameter 0.8 μm) and E-FMW-170
0 (average fiber diameter of 0.6 μm) can be exemplified.

The surface of the above-mentioned reinforcing agent is a known surface treatment agent such as vinylalkylsilane, methacryloalkylsilane, epoxyalkylsilane, aminoalkylsilane,
The surface treatment may be performed with a titanate coupling agent such as mercaptoalkylsilane, chloroalkylsilane, isopropyltriisostearoyl titanate, or a zircoaluminate coupling agent. Further, as a sizing agent for fibers, a known sizing agent such as an epoxy-based, urethane-based, polyester-based or styrene-based sizing agent may be used.

In the resin composition of the present invention, if necessary,
As a flame retardant, triphenyl phosphate, tricresyl phosphate, a polycondensate thereof, or a known phosphorus compound such as red phosphorus can be added. Further, a halogen compound such as decabromodiphenyl ether, brominated polystyrene, low molecular weight brominated polycarbonate, or brominated epoxy compound can be added as a flame retardant. Flame retardant aids such as antimony trioxide, antimony tetraoxide, zirconium oxide can also be used in combination with the halogen compound.

The resin composition of the present invention can be obtained by heating and melt-kneading, but the temperature and time for melt-kneading are not particularly limited. An extruder, a Banbury mixer, a kneader or the like is used for kneading, and the extruder is preferably used from the viewpoint of operability. In carrying out this blending operation, the blending order of each raw material is not particularly limited. For example, a method of melting and kneading all the ingredients together.
A method in which (b) a polyamide resin and (d) a polymer of itaconic acid derivative are melt-kneaded in advance, and then (a) a polyphenylene ether resin and (c) a rubbery polymer are additionally added and melt-kneaded, preferably ( a) a method in which a polyphenylene ether resin and (d) a polymer of itaconic acid derivative are melt-kneaded in advance, and then (c) a rubbery polymer and (b) a polyamide resin are additionally added and melt-kneaded, (a) polyphenylene ether A method in which the resin, (c) the rubbery polymer and (d) the itaconic acid derivative polymer are melt-kneaded in advance and (b) the polyamide resin is additionally added and melt-kneaded can be employed.

The effects of the present invention will be specifically described in detail below with reference to Examples and Comparative Examples. Note that the following examples are for specific description, and do not limit the embodiments of the present invention or the scope of the invention.

[0023]

【Example】

Example 1 4.0 kg of poly (2,6-dimethyl-1,4-phenylene) ether (PPE) powder having an intrinsic viscosity of 0.45 dl / g (in chloroform at 30 ° C.) and styrene-butadiene-styrene. Type block copolymer (SEB
S) (Clayton G1651 manufactured by Shell Chemical Co., Ltd.) and 640 g of itaconic acid polymer (polymerization degree 100)
After mixed with g, they were melt-kneaded at 290 ° C. using a twin-screw extruder and extruded into pellets. The above pellet 3.0k
g and 2.6 kg of polyamide (Nylon-6, Amylan CM1097, manufactured by Toray Industries, Inc.) were mixed, and the pellets obtained by melt-kneading at 290 ° C. using a twin-screw extruder were used.
After drying under reduced pressure at 105 ° C. for 20 hours, various test pieces were molded by injection molding. Various physical property values measured using this test piece are shown in Table 2. Further, there was no odor during kneading, and workability was very good. Example 2 In Example 1, the itaconic acid polymer was used in an amount of 120.
pelletized in place of g, and 3.0 kg of the above pellets,
Except that 2.5 kg of polyamide was mixed and pelletized
The same procedure as in Example 1 was performed. The various physical properties obtained are shown in Table 2.

Example 3 In Example 1, the itaconic acid polymer was used in an amount of 400.
pelletized in place of g, and 3.0 kg of the above pellets,
Except that 2.4 kg of polyamide was mixed and pelletized.
The same procedure as in Example 1 was performed. The various physical properties obtained are shown in Table 2.

Example 4 In Example 1, the degree of polymerization of the itaconic acid polymer was 200.
Example 1 was repeated except that the amount of the pellets was changed to 64 g, the amount of the pellets was changed to 64 g, and 3.0 kg of the above pellets and 2.6 kg of polyamide were mixed and pelletized.
The various physical properties obtained are shown in Table 2.

Example 5 In Example 1, the polymerization degree of the itaconic acid polymer was changed to 10 and the amount used was 32 g to pelletize, 3.0 kg of the above pellets and 2.6 kg of polyamide were mixed,
The same procedure as in Example 1 was carried out except that pelletization was performed. The various physical properties obtained are shown in Table 2.

Example 6 In Example 1, 3.2 kg of PPE, a diethyl itaconate polymer (degree of polymerization: 300), and a usage amount of 32 g were mixed, melt-kneaded using a twin-screw extruder, and extruded into pellets. . 3.0 kg of the above pellets, 640 g of styrene-isoprene block copolymer hydrogenated product, and polyamide (Nylon-6,6, Amylan CM3 manufactured by Toray Industries, Inc.)
007) 3.1 kg were mixed, and the pellets obtained by melt-kneading with a twin-screw extruder were dried under reduced pressure at 105 ° C. for 20 hours, and various test pieces were molded by injection molding. Various physical property values measured using this test piece are shown in Table 2.

Example 7 In Example 6, the amount of PPE used was 4.8 kg, the diethyl polymer of itaconic acid was a diamide polymer of itaconic acid (polymerization degree 400), the amount of 40 g was used, and the styrene-isoprene block copolymer was added. Styrene-isoprene block-
Example 6 was repeated except that the amount of the styrene copolymer hydrogenated product used was 960 g and the amount of polyamide used was 2.1 kg. The various physical properties obtained are shown in Table 2.

Comparative Example 1 In Example 1, pelletization was carried out without using the itaconic acid polymer, and 3.0 kg of the above pellets and 2.
Example 1 was repeated except that 6 kg was mixed and pelletized. The various physical properties obtained are shown in Table 2.

Comparative Example 2 In Example 1, pelletized without SEBS,
The same procedure as in Example 1 was performed except that 3.0 kg of the above pellets and 3.0 kg of polyamide were mixed and pelletized. The various physical properties obtained are shown in Table 2.

Comparative Example 3 In Example 1, the amount of the itaconic acid polymer used was 60 g.
In addition, the amount of SEBS used was changed to 1.2 kg and pelletized, and 3.0 kg of the above pellets and 8.5 k of polyamide were used.
The same procedure as in Example 1 was performed except that g was mixed and pelletized. The various physical properties obtained are shown in Table 2.

Comparative Example 4 In Example 1, the itaconic acid polymer was used in an amount of 2.4.
Pellet instead of kg, 3.0 kg of the above pellet
And 1.7 kg of polyamide were mixed and pelletized, and the same procedure as in Example 1 was performed. However, this composition was impractical because of poor fluidity and appearance of molded articles.

[0033]

EFFECTS OF THE INVENTION By adopting the constitution of the present invention, it has excellent moldability, solvent resistance and oil resistance, and further,
A polyphenylene ether resin composition exhibiting excellent impact resistance can be obtained. In addition, there is no odor during kneading and workability is very good.

[0034]

Table 1 PPE polymer Rubber polymer Polyamide Example 1 50 0.2 (n = 100) 8 50 Example 2 50 1.5 ↑ 8 50 Example 3 50 50 5.0 ↑ 8 50 Example 4 50 0.8 (n = 200) 8 50 Example 5 50 0.4 (n = 10) 8 50 Example 6 40 0.3 (n = 300) 6 60 Example 7 60 0.5 (n = 400) 12 40 Comparative Example 1 50 0 8 50 Comparative Example 2 50 0.4 (n = 100) 0 50 Comparative Example 3 20 0.4 ↑ 8 80 Comparative Example 4 50 30 ↑ 8 50 The number of parts in the table is based on weight. Is represented.

[0035]

[Table 2] Tensile yield Tensile yield DTUL IZOD Yield strength Elongation (* 1) Impact strength (unit) (MPa) (%) (° C) (J / m) Example 1 56 82 187 214 Example 2 59 100 188 320 Example 3 59 66 187 269 Example 4 59 86 188 298 Example 5 60 89 89 187 290 Example 6 59 100 188 209 Example 7 60 90 90 189 225 Comparative Example 1 29 2 188 13 13 Comparative Example 2 587 188 18 Comparative Example 3 54 35 169 173 (* 1) DTUL: Low load (0.45 MPa)

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[Procedure amendment]

[Submission date] October 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and R
₃ differs same species or with one another, a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. Polyphenylene ether resins having a structural unit represented by the main chain), (b) a polyamide resin, 100 parts by weight of the total amount of both,
(C) rubber polymer 3 to 30 parts by weight, and (d) the formula of 2,

[Chemical 2] (Wherein, R _4, R _5, the same one oxygen or different same species or from each other, a hydroxyl group, having 1 to 6 carbon atoms
Is an alkoxy group or an amino group. ) Polymer of an itaconic acid derivative having a structural unit represented by
A resin composition comprising 20 parts by weight, (a) a thermoplastic resin composition ratio by weight of polyphenylene ether resins and (b) the polyamide resin is characterized by a 30 / 70-80 / 20 Composition.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Chitokuichi 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Sanryo Gas Chemical Co., Ltd. Plastics Center (72) Inventor Yoshio Fukaya 5-chome, Higashi-Hachiman, Hiratsuka-shi, Kanagawa No. 6-2 Sanryo Gas Chemical Co., Ltd. Plastics Center

Claims (3)

[Claims] 1. (a) General formula: (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and R
₃ is the same or different from each other, hydrogen atom or carbon number 1
To 3 lower alkyl groups. ) A polyphenylene ether-based resin having a structural unit represented by the main chain in the main chain, (b) a polyamide resin, and a total amount of both of 100 parts by weight,
(C) rubbery polymer, 3 to 30 parts by weight, and (d) general formula: (Wherein R ₄ and R ₅ are the same oxygen, or the same or different from each other, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms or an amino group) in the main chain. Polymer of itaconic acid derivative having 0.01 to 20
A thermoplastic resin composition, which is a resin composition composed of parts by weight, wherein a weight composition ratio of (a) polyphenylene ether resin and (b) polyamide resin is 30/70 to 80/20. 2. The polymer of (a) itaconic acid derivative is a homopolymer of itaconic acid.
The thermoplastic resin composition described. 3. A polyphenylene ether resin (a),
The thermoplastic resin according to claim 1, wherein (c) the rubber-like polymer and (d) the polymer of the itaconic acid derivative are melt-kneaded in advance, and then (b) a polyamide resin is additionally added and melt-kneaded. A method for producing a composition.