JPH07188547A - Thermoplastic resin composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition by adding a polyamide resin, a rubber polymer, a diester of an unsaturated dicarboxylic acid and an acid to a polyphenylene ether resin, thus shows good moldability, solvent resistance and oil resistance as well as excellent shock resistance. CONSTITUTION:The resin composition comprises (A) 30 to 80 pts.wt. of a polyphenylene ether resin having recurring units of the formula (R1 is a 1 to 3C alkyl; R2, R3 are H, a 1 to 3 C alkyl), preferably poly(2,6-dimethyl-1,4- phenylene) ether, (B) 70 to 20 pts.wt. of a polyamide resin, preferably nylon 6, where the total of (A)+(B) is adjusted to 100 pts.wt., (C) 3 to 30 pts.wt., 100 pts.wt. of (A)+(B), of a rubber polymer such as polybutadiene. (D) 0.05 to 15 pts.wt. of a diester of an unsaturated dicarboxylic acid, preferably dimethyl itaconate or a polymer of a diester of dicarboxylic acid, preferably) polymer of di-t-butyl fumarate, and (E) 0.05 to 2 pts.wt. of an acid, preferably p-toluenesulfonic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyphenylene ether resin composition. More specifically, the present invention is characterized in that a polyphenylene ether resin is blended with a polyamide resin, a rubbery polymer, and a specific unsaturated carboxylic acid ester, or these polymers, and an acid and water. The present invention relates to a thermoplastic resin composition having improved moldability, solvent resistance, oil resistance and impact resistance.

[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.

In Japanese Patent Publication No. 60-11966, in order to improve solvent resistance and oil resistance, a polyphenylene ether resin, a polyamide resin and an unsaturated compound having a specific functional group such as an acid anhydride group are melt-kneaded. The method of doing is proposed. However, since the disclosed method melt-kneads the above-mentioned three components at the same time, the resulting composition is not always sufficient in terms of impact resistance, and also has a strong odor during kneading, resulting in poor workability. Further, regarding the unsaturated carboxylic acid ester, the impact improving effect is not substantially exhibited when used alone.

JP-A-61-204262 proposes a resin composition comprising a maleic anhydride modified polyphenylene ether resin, a polyamide resin and an elastomer block copolymer. However, maleic anhydride used to modify the polyphenylene ether resin is unstable in an open system and undergoes a chemical change due to atmospheric moisture,
There is a case where the physical properties of the resin composition obtained by using it deteriorate.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art, to provide good moldability, solvent resistance, oil resistance, and excellent impact resistance. Is to provide a thermoplastic resin composition. Another object of the present invention is to provide a method for producing a thermoplastic resin that does not generate an odor during kneading and does not cause a reduction in workability.

The present inventors have conducted various experimental studies with the aim of improving and improving the drawbacks of polyphenylene ether resin without impairing the excellent properties possessed by polyphenylene ether resin. , A polyamide resin, a rubbery polymer and a specific unsaturated carboxylic acid ester, or these polymers, and by finding that the problem can be solved all at once by blending an acid and water, The present invention has been completed through intensive studies.

[0007]

The present invention will be specifically described 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 general formula 1 in the main chain, and may be a homopolymer or a copolymer. It may be.

[0008]

[Chemical 1] (In the formula, R1 is a lower alkyl group having 1 to 3 carbon atoms, R2,
R3 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. )

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 66,
One or more polyamides selected from the group consisting of aliphatic nylons such as nylon 610, nylon 11 and nylon 12, polyhexamethylene diamine terephthalamide, aromatic nylons obtained from metaxylene diamine and adipic acid are preferred. Can be used for

The weight mixing ratio of both components of the polyphenylene ether resin (PPE) and the polyamide resin (PA) is PP.
There is no limitation within the range of E / 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 homopolymer of a conjugated diene compound or a polymer obtained by combining at least one of a diene compound and an olefin and a vinyl compound, and has rubber elasticity at room temperature. It is a rubbery polymer.

Specifically, polybutadiene, polyisoprene, polychloroprene, polychlorobutadiene, ethylene-propylene-diene terpolymer, styrene-butadiene copolymer (random copolymer, block copolymer, graft copolymer (Including all polymers, 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 tereblock copolymer, or hydrogenated product thereof, styrene-isoprene-styrene tereblock copolymer, or hydrogenated product thereof, methylmethacrylate-butadiene copolymer, butylmethacrylate-butadiene copolymer and the like. To be

The addition amount of the rubbery polymer in the present invention is
The amount is 3 to 30 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the composition containing the (a) polyphenylene ether resin and the (b) polyamide resin. If it is 3 parts by weight or less, the impact resistance is insufficiently improved, and if it is 30 parts by weight or more, the dispersibility of the rubbery polymer becomes poor and the appearance properties such as smoothness of the molded product and the mechanical properties are deteriorated. Show a trend.

The diester of unsaturated dicarboxylic acid (d) used in the present invention is a diester of a dicarboxylic acid having an ethylenic double bond with two alkyl groups having 1 to 8 carbon atoms. May be the same or different from each other. The unsaturated dicarboxylic acid diester polymer is a polymer obtained by polymerizing the unsaturated dicarboxylic acid diester. (D) Specific examples of diesters of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid and their methyl, ethyl, isopropyl, butyl or t-butyl diesters. Particularly, dimethyl itaconate is preferably used. Specific examples of the unsaturated dicarboxylic acid diester polymer include maleic acid, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid and their methyl, ethyl, isopropyl, butyl or t-butyl diesters obtained by polymerization. The polymer having an appropriate degree of polymerization is exemplified, and a di-t-butyl fumarate polymer is particularly preferably used.

The addition amount of the (d) diester of unsaturated dicarboxylic acid or the polymer of unsaturated dicarboxylic acid diester in the present invention is in the range of 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight. Parts by weight. If the amount added is less than 0.05 parts by weight, the impact resistance cannot be sufficiently improved, and if it exceeds 15 parts by weight, the appearance properties such as fluidity and smoothness of the molded product deteriorate.

The acid (e) used in the present invention is not particularly limited as long as it is a general inorganic or organic acid, and specifically, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfurous acid, oxalic acid, nitrous acid. , Acetic acid, phthalic acid, benzoic acid, acrylic acid, p-toluenesulfonic acid, formic acid, carbonic acid, hypochlorous acid, boric acid, etc., and p-toluenesulfonic acid is particularly preferably used. The addition amount of the (e) acid in the present invention is as follows.
It is in the range of 0.05 to 2 parts by weight, preferably 0.1 to
It is 1.5 parts by weight. If the addition amount is less than 0.05 parts by weight, improvement of impact resistance is insufficient, and if it exceeds 2 parts by weight, appearance defects and discoloration of the molded product occur, which is not preferable.

The amount of water (f) used in the production of the resin composition of the present invention is in the range of 0.05 to 2 parts by weight, preferably 0.2 to 1 part by weight. Addition amount is 0.
If it is less than 05 parts by weight, the effect of improving the impact resistance of the resin composition will be insufficient, and if it exceeds 2 parts by weight, surging will occur during extrusion of the resin composition and a poor appearance will occur in the molded product, which is preferable. Absent.

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

The resin composition of the present invention may contain various known additives, if desired. 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 flakes, 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 One or more strengthening agents may be added. 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 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.

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 heat-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 the production of the resin composition of the present invention, a preferable method is to use (a) a polyphenylene ether resin and (d) a diester of an unsaturated dicarboxylic acid or a polymer of an unsaturated dicarboxylic acid diester, (e) an acid and (f) water. After mixing and previously melt-kneading, (b) a polyamide resin and (c) a rubbery polymer are additionally added and melt-kneaded, and (a) a polyphenylene ether resin and (d) a diester of an unsaturated dicarboxylic acid or Polymer of unsaturated dicarboxylic acid diester, (e) acid,
In this method, (f) water and (c) a rubbery polymer are mixed in advance and melt-kneaded, and then (b) a polyamide resin is additionally added and melt-kneaded.

[0025]

EXAMPLES Hereinafter, the effects of the present invention will be described specifically and in detail by showing Examples and Comparative Examples. In addition,
The following examples are for specific description, and do not limit the embodiments of the present invention or the scope of the invention. Example 1 Intrinsic viscosity of 30 ° C. in chloroform, 0.45 dl / g
Mitsubishi Gas Chemical Co., Ltd. poly (2,6-dimethyl-
50 parts by weight of 1,4-phenylene) ether (PPE) powder, a rubbery polymer styrene-butadiene-styrene block copolymer hydrogenated product 8 manufactured by Asahi Chemical Industry Co., Ltd. 8
Parts by weight, 1.5 parts by weight of dimethyl itaconate (acid ester), 0.5 parts by weight of p-toluenesulfonic acid as an acid, and 1 part by weight of water were mixed with a mixer and then heated to 290 ° C. using a twin-screw extruder. Melt-kneaded and extruded to obtain pellets. Next, 60 parts by weight of the pellets and 50 parts by weight of polyamide 6 (PA) manufactured by Mitsubishi Kasei Co., Ltd. were mixed by a mixer, melt-kneaded at 290 ° C. using a twin-screw extruder, and extruded to obtain pellets. . There was no odor during melt-kneading, and workability was good. The obtained pellets 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. In addition, DTUL is under a load of 0.45 MPa,
The Izod strength was measured at 23 ° C.

Example 2 The amount of dimethyl itaconate used was changed to the amount shown in Table 1 and pelletized and molded in the same manner as in Example 1. Various physical property values measured using this test piece are shown in Table 2. There was no odor during melt-kneading, and workability was good.

Example 3 Pellet was molded in the same manner as in Example 1 except that the amount of p-toluenesulfonic acid used was changed to the amount shown in Table 1. Various physical property values measured using this test piece are shown in Table 2. There was no odor during melt-kneading, and workability was good.

Example 4 Mixing and pelletizing were carried out in the same manner as in Example 1 except that 0.5 part by weight of phosphoric acid was used instead of p-toluenesulfonic acid. Various physical property values measured using this test piece are shown in Table 2.

Examples 5 to 6 Diethyl itaconate was replaced with diethyl itaconate, 5 parts by weight were used in Example 5 and 10 parts by weight were used in Example 6, and mixed and blended according to the formulation shown in Table 1. Pelletized and molded as in Example 1. Various physical property values measured using this test piece are shown in Table 2.

Examples 7 to 8 Dimethyl itaconate was replaced by dibutyl itaconate, the amount of p-toluenesulfonic acid used was changed in Example 7, and the amount of water used in Example 8 was changed. The contents were mixed, pelletized and molded in the same manner as in Example 1. Various physical property values measured using this test piece are shown in Table 2.

Examples 9 to 10 are dimethyl itaconate, and in Example 9, a dimethyl itaconate polymer (a homopolymer having a number average molecular weight of about 19000).
In Example 10, instead of the fumaric acid-di-tert-butyl polymer (a homopolymer having a degree of polymerization of about 50), the contents of mixing shown in Table 1 were mixed and pelletized in the same manner as in Example 1,
Molded. Various physical property values measured using this test piece are shown in Table 2.

Example 11 Using dimethyl itaconate which was placed in a flask and left for 21 days without a lid, pelletizing was performed in the same manner as in Example 1. Table 2 shows various physical property values measured using this test piece.
It was shown to. There was almost no deterioration in physical properties as compared with Example 1. There was no odor during melt-kneading, and workability was good.

Comparative Example 1 In place of dimethyl itaconic acid, 1.5 parts by weight of maleic anhydride left in a flask for 21 days was used, and p-toluenesulfonic acid and water were not used. The contents of the mixture were mixed, pelletized and molded in the same manner as in Example 1. Various physical property values measured using this test piece are shown in Table 2. The obtained composition had a weak Izod impact strength, and the appearance of the molded product was poor.

Comparative Example 2 Dimethyl itaconate was used, p-toluenesulfonic acid and water were not used, and the contents of mixing shown in Table 1 were mixed, pelletized and molded in the same manner as in Example 1. Various physical property values measured using this test piece are shown in Table 2. This composition has Iz
Since the od impact strength was weak and the appearance of the molded product was poor, it was not practical.

Comparative Examples 3 to 8 The amounts of dimethyl itaconate, p-toluenesulfonic acid, and water used were changed to those shown in Table 1 and mixed and pelletized in the same manner as in Example 1. And then molded. Various physical property values measured using this test piece are shown in Table 2. In Comparative Example 8, foaming occurred during the first extrusion and became unstable, and the appearance of the molded product was poor, so that it was not practical.

Comparative Example 9 A styrene-butadiene-styrene block copolymer hydrogenated product was mixed and pelletized in the same manner as in Example 1 except that the amount of hydrogenated product used was changed to 1 part by weight. I went. Various physical property values measured using this test piece are shown in Table 2.

[0037]

By adopting the constitution of the present invention, it is possible to obtain a resin composition having good molding processability, solvent resistance and oil resistance, and exhibiting excellent impact resistance. Further, no odor is generated in the manufacturing process, and workability is not deteriorated.

[0038]

Table 1 Example PPE rubbery acid acid acid water PA / comparative example polymer Ter, etc. Example 1 50 8 1.5 0.5 0.5 1.0 50 Example 2 50 8 0.2 0.2 0.5 1.0 50 Example 3 50 8 1.5 1.5 1.0 50 50 Example 4 50 8 1.5 0.5 0.5 1.0 50 Example 5 50 8 8 5.0 0.75 1.5 50 Example 6 50 8 10.0 0.75 1.5 50 Example 7 50 8 1.5 0.1 1.0 50 Example 8 50 8 1.5 1.5 0.5 0.1 50 Example 9 50 8 3.0 0 0.75 1.5 50 Example 10 50 8 3.0 0.75 1.5 50 Example 11 50 8 1.5 0.5 0.5 1.0 50 Comparative Example 1 50 8 * 1.5 0 0 50 Comparative Example 2 50 8 1.5 0 0 50 Comparative Example 3 50 8 0.03 0.5 1.0 50 Comparative Example 4 50 8 18.0 0.75 .5 50 Comparative Example 5 50 8 1.5 0.03 1.0 50 Comparative Example 6 50 8 1.5 0.5 0.5 0.03 50 Comparative Example 7 50 8 1.5 2.5 2.5 1.0 50 Comparative Example 8 50 8 1.5 0.5 0.5 2.5 50 Comparative Example 9 50 1 1.5 0.5 1.0 50 *: Maleic anhydride In addition, the number of parts in the table is expressed on a weight basis.

[0039]

Table 2 Example Tensile yield strength Break elongation DTUL Izod strength / Comparative example (MPa) (%) (° C) (J / m) Example 1 54 102 188 237 Example 2 56 92 187 135 Example 3 55 65 172 228 Example 4 59 100 186 221 Example 5 53 84 176 185 Example 6 51 66 66 169 141 Example 7 56 56 89 185 184 Example 8 58 67 184 203 203 Example 9 57 104 189 569 169 Example 10 69 183 215 Example 11 56 89 185 209 Comparative Example 1 41 7 175 78 Comparative Example 2 36 3 178 14 Comparative Example 3 39 2 170 15 Comparative Example 4 51 57 57 170 85 Comparative Example 5 44 6 168 17 Comparative Example 6 48 21 171 39 Comparative Example 7 40 12 181 102 Comparative Example 8 (Molded product Measurements can not) Comparative Example for good 9 58 15 183 67

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Shinya Miya, 5-6-2 Higashi-Hachiman, Hiratsuka City, Kanagawa Sanryo Gas Chemical Co., Ltd. Plastics Center (72) Noriaki Honda, Higashi-Hachiman, Hiratsuka City, Kanagawa Prefecture Chome 6-2 Sanryo Gas Chemical Co., Ltd. Plastics Center

Claims (3)

[Claims] 1. (a) Polyphenylene ether resin 30 to
80 parts by weight, (b) 70 to 20 parts by weight of polyamide resin,
Total 1 of polyphenylene ether resin and polyamide resin
(C) 3 to 30 parts by weight of a rubbery polymer, (d) 0.05 to 15 parts by weight of a diester of an unsaturated dicarboxylic acid or a polymer of an unsaturated dicarboxylic acid diester, and (e) an acid with respect to 00 parts by weight. A thermoplastic resin composition comprising 0.05 to 2 parts by weight. 2. (a) Polyphenylene ether resin 30 to
80 parts by weight, 100 parts by weight of the total of the polyphenylene ether resin and the polyamide resin (c) the rubbery polymer 3
˜30 parts by weight, (d) unsaturated dicarboxylic acid diester or unsaturated dicarboxylic acid diester polymer 0.05
˜15 parts by weight, (e) 0.05 to 2 parts by weight of acid and (f) 0.05 to 2 parts by weight of water are melt-kneaded in advance, and 70 to 20 parts by weight of (b) polyamide resin is additionally added. A method for producing a thermoplastic resin composition, which comprises melt-kneading. 3. (a) Polyphenylene ether resin 30 to
80 parts by weight, 0.05 to 15 parts by weight of (d) a diester of an unsaturated dicarboxylic acid or a polymer of an unsaturated dicarboxylic acid diester, and (e) an acid of 0.1 part by weight per 100 parts by weight of a polyphenylene ether resin and a polyamide resin. 05-2
Parts by weight and (f) 0.05 to 2 parts by weight of water are melt-kneaded in advance, and then (b) 70 to 20 parts by weight of polyamide resin and (c) 3 to 30 parts by weight of rubber polymer are additionally added and melted. A method for producing a thermoplastic resin composition, which comprises kneading.