JP2945041B2 - Molding resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition having excellent heat resistance, chemical resistance, and mechanical properties.
Among automotive parts, etc., it is suitably used particularly in fields requiring heat resistance, such as tubes, hoses, pipes, films, sheets, gears, cams, bearings, bearings, slides, packing, gaskets, casters, joints, and connectors. , Fasteners, wire covering materials, optical fiber covering materials, SMT parts, etc.

[Prior art] Polyphenylene sulfide resin is known as a resin having excellent heat resistance, chemical resistance, and flame retardancy, but has a major drawback that it is very brittle when used alone. At present, the use is restricted.

On the other hand, polyamide resin has excellent properties such as excellent moldability and very toughness, and is therefore used for a wide range of applications, but has drawbacks such as dimensional change due to water absorption and reduced rigidity. doing. Therefore, in order to compensate for the above-mentioned drawbacks and obtain an excellent molding material having high practicality, some compositions comprising a polyphenylene sulfide resin and a polyamide resin have been proposed. (For example, JP
-69255, JP-A-59-1155462, JP-A-1-
However, in these compositions, the wettability of the polyphenylene sulfide resin and the polyamide resin is still insufficient, and the mechanical properties when used as a molded product are reduced to a level that is practically satisfactory. Had not reached.

[Problems to be Solved by the Invention] The present invention is to improve the moldability and toughness by compounding a polyamide resin without losing the excellent properties of polyphenylene sulfide resin.
Among the remarkable mechanical properties that occur when blending resins with completely different properties, such as polyphenylene sulfide resin and polyamide resin, the reduction in weld property, which is a major problem especially when trying to use it as a molded product, It is to solve the problem of improvement.

[Means for Solving the Invention] The present inventors have conducted a study on blending a polyamide resin with a polyphenylene sulfide resin in order to obtain a resin composition having excellent mechanical properties, particularly physical properties of a weld portion. A. Polyphenylene sulfide resin, B. Polyamide resin, C. Resin composition consisting of polyphenylene ether resin grafted with an acid anhydride and bonded with a molecular unit having an acid anhydride group or a structure derived therefrom in its molecule And the following formula: 1 ≦ (A) / {(A) + (B)} ≦ 99, 0.1 ≦ (C) / {(A) + (B)} ≦ 50 (However, the numbers represent% by weight. The resin composition characterized by satisfying
In particular, they have found that the properties of the weld portion are excellent, and have completed the present invention.

The polyphenyl sulfide resin used in the present invention has a general formula Is a polymer containing at least 70 mol%, preferably at least 90 mol% of a structural unit represented by the following formula:
And JP-B-45-3368, JP-B-52-12240, and the like. Sodium derived from sodium sulfide as the synthesis starting material remains in the polymer, and the sodium content is preferably 800 ppm or less, particularly preferably 400 ppm or less. Sodium content
If it exceeds 800 ppm, the mechanical properties of the obtained composition will be reduced.

The melt viscosity of the polyphenylene sulfide resin is preferably 100 to 20,000 poise (measuring temperature 320 ° C., shear rate 10
³ / sec), and more preferably 1,000 to 10,000 poise.

The polyamide resin used in the present invention, nylon,
4, nylon, 6, nylon, 8, nylon 9, nylon 10, nylon 11, nylon 12, nylon 46, nylon
Aliphatic polyamide resins such as 66, nylon 610, nylon 612, and nylon 1212, nylon 4T (T: terephthalic acid), nylon 4I (I: isophthalic acid), nylon 6T, nylon 6I, nylon 12T, nylon 12I, etc. Aromatic polyamide resins and copolymers thereof. The number average molecular weight of the polyamide resin is preferably 500 to 100,000, and more preferably 10,000 to 50,000.

The compounding ratio of the polyphenylene sulfide resin and the polyamide resin can be arbitrarily changed within the range of 1:99 to 99: 1 depending on the use. Preferably it is in the range of 10:90 to 90:10.

The polyphenylene ether resin to which the molecular unit having an acid anhydride group or a structure derived from the acid anhydride group used in the present invention is bonded is represented by a general formula (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are substituents selected from the group consisting of hydrogen, an aliphatic or aromatic alkyl group, and a halogen atom, and n represents a number average molecular weight of the polymer of about 500-500,0
Is a compound in which a molecular unit having an acid anhydride group or a structure derived from the acid anhydride group in the molecule is bonded to a polymer represented by the following formula: for example, 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), poly (2-ethyl-6-propyl-1,4-phenylene ether), poly (2,6-diallyl-)
1,4-phenylene ether), poly (2,6-dichloro-1,
4-phenylene ether), poly (2,6-dibromo-1,4
-Phenylene ether), poly (2-chloro-6-bromo-1,4-phenylene ether), poly (2,6-difluoro-1,4-phenylene ether), poly (2,8,6-trimethyl-1) , 4-phenylene ether), poly (2,3,5,6-tetrabromo-1,4-phenylene ether), etc., or copolymers thereof, with an acid anhydride group or a structure derived therefrom. Compounds in which the molecular units contained therein are bonded.

As a method of bonding a molecular unit having an acid anhydride group or a structure derived from the acid anhydride group to the polyphenylene ether resin in the molecule, any means known to those skilled in the art may be used. Alternatively, a polyphenylene ether resin having a phenolic -OH group at both ends is treated with an acid anhydride group such as trimellitic anhydride chloride in the presence of a basic substance such as amines, pyrimidines and pyridines. A method of reacting a molecular unit having the same, or a method of grafting a molecular unit having an acid anhydride group or a structure derived therefrom in a polyphenylene ether resin in the presence or absence of a radical generator, etc. Is raised.

As the radical generator, any compound left to those skilled in the art may be used. For example, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butyl peroxide) Oxy) 3,3,5
-Trimethylcyclohexane, 2,5-dimethyl-di (t
-Butylperoxy) hexane and the like can be used. As the molecular unit having an acid anhydride group grafted to the polyphenylene ether resin or a structure derived from the acid anhydride group in the molecule, α, β-unsaturated carboxylic acid or a derivative thereof is preferable. For example, maleic acid, maleic anhydride , Succinic acid, succinic anhydride, hymic acid, hymic anhydride, itaconic acid, itaconic anhydride, citraconic anhydride, aconitic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester,
Metal salts of maleic acid monoethyl ester, fumaric acid monoethyl ester, vinyl fumaric acid, fumaric acid monoethyl ester metal salt, maleimide and the like, among which the molecular unit having an acid anhydride group in the molecule is more preferable. Particularly preferred is maleic anhydride.

The amount of grafting of a molecular unit having an acid anhydride group or a structure derived therefrom in the molecule to the polyphenylene ether resin of the present invention is preferably in the range of 0.01 to 20 mol% based on the amount of the monomer constituting the polyphenylene ether resin. In particular, the range of 0.05 to 10 mol% is preferable. If the graft amount exceeds 20 mol%, undesired results such as coloring, reduction in molecular weight, and gelation of the compounded resin are caused. If the composition is less than 0.01 mol%, the effect of the modification is hardly observed when the composition is used. The graft reaction of a molecule having an acid anhydride group or a structure derived therefrom in the molecule thereof onto the polyphenylene ether resin can be performed by a conventionally known method, in the presence of a solvent, or in the absence of a solvent using an extruder or the like. The reaction can be performed in the presence or absence of a radical generator.

The compounding amount of the polyphenylene ether resin (C) in which a molecular unit having an acid anhydride group or a structure derived from them in the molecule is bonded to the polyphenylene sulfide resin (A) or the polyamide resin (B), (The numbers represent% by weight.) It is.

If the content is less than 0.1% by weight, the effect of the modification is hardly observed when the composition is used. If the content is more than 50% by weight, undesired results such as a decrease in the chemical resistance and moldability of the composition and coloring of the molded product. Invite.

Various additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, a dye, a pigment, a plasticizer, a lubricant, and a flame retardant, which are added to a normal thermoplastic resin, if necessary, to the resin composition of the present invention. The addition of various reinforcing agents such as glass filler, mineral filler and the like is not particularly limited.

The preparation of the resin composition of the present invention can be achieved by a conventionally known technique such as a Brabender, a kneader, a bumper mixer, and an extruder.

[Example] Production Example 1 [Synthesis of polyphenylene ether grafted with acid anhydride group (admixture)] Poly (2,6-dimethyl-1,4-phenylene ether)
[Asahi Kasei Kogyo Co., Ltd.] 100 parts by weight, maleic anhydride,
3 parts by weight, 1 part by weight of Perhexa 25B [manufactured by NOF CORPORATION], 30 mmφ twin screw extruder [PCM-30 manufactured by Ikegai Iron Works Co., Ltd .: L /
D = 17], and the mixture was mixed at a temperature of 300 to 320 ° C. to obtain a pelletized target product. The obtained polymer was dissolved in toluene-
Repeated re-precipitation with methanol, vacuum drying,
When a graft material of maleic anhydride was determined by titration with sodium methylate, 0.7 mol% of maleic anhydride was grafted.

Example 1 Nylon 66 [Leona 1300: manufactured by Asahi Kasei Corporation] 70
Parts by weight, polyphenylene sulfide resin [Topren T
-4: manufactured by Topren Co., Ltd.] 30 parts by weight, synthesized in Production Example 1
5 parts by weight of [Admixture] was mixed with a 30 mmφ twin screw extruder [PCM-30]
Ikegai Iron Works Ltd .: L / D = 17] at a temperature of 290-310 ° C
The composition was mixed and further pelletized to obtain a composition. The pair obtained
Injection molding machine [PS
-40E manufactured by Nissei Plastics Industry Co., Ltd.]
It was prepared and the following physical properties were measured.

Weld part thin-walled tensile properties It has a shape with a length of 127 mm (a in the figure), a width of 12.7 mm (b in the figure), and a thickness of 0.8 mm as shown in FIG. Molded pieces were made using the mold as formed. This molded piece was subjected to a tensile test according to the tensile test method of ASTM-D-638, and the tensile strength and the tensile elongation were measured. In the figure, 2 is a sprue, 3 is a runner,
Reference numeral 4 denotes a test piece.

Tensile properties (1/8 inch): ASTM-D638 Bending properties (1/8 inch): ASTM-D790 Izod impact strength: ASTM-D256 Examples 2 to 6, Comparative Examples 1 to 12 The compositions shown in Table 1 were implemented. Mixing was performed in the same manner as in Example 1, and the physical properties were measured.

Table 2 also shows the results of Examples 1 to 6 and Comparative Examples 1 to 12.

The composition containing the admixture of the present invention has extremely good properties in the weld portion, and also has excellent tensile properties, bending properties and Izod impact strength. On the other hand, in the composition containing no admixture, the physical properties of the weld portion were remarkably reduced, and the tensile properties, bending properties, and Izod impact strength were also reduced.

[Effects of the Invention] As described above, the resin composition of the present invention has excellent physical properties of a weld portion, and also has excellent mechanical properties, heat resistance,
Since it has chemical resistance, it is used not only for electric / electronic parts and automobile parts, but also for a wide range of applications.

[Brief description of the drawings]

FIG. 1 is a plan view of a mold for producing a test piece according to an embodiment of the present invention. 1 ... weld part, 2 ... sprue, 3 ... runner,
4 Test piece.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 81/00-81/02 C08L 77/00 C08L 71/08-71/12

Claims (1)

(57) [Claims] 1. A. polyphenylene sulfide resin, B. polyamide resin, C. polyphenylene ether resin graft-modified with an acid anhydride and bonded to a molecular unit having an acid anhydride group or a structure derived therefrom in the molecule. A resin composition comprising the following formula: 1 ≦ (A) / {(A) + (B)} ≦ 99, 0.1 ≦ (C) / {(A) + (B)} ≦ 50 (where, Wherein the numerals represent% by weight).