JPH03197563A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. markedly improved in the impact resistance and brittleness by compounding a polyarylene sulfide resin with a specific copolyamide. CONSTITUTION:The title compsn. is prepd. by compounding: 99-75wt.% polyarylene sulfide resin [a polymer comprising repeating units of formula I (wherein R is H or 1-5C alkyl; and (n) is 0-4), pref. one comprising repeating units of formula II]; with 1-25wt.% copolyamide contg. a dimerized component as the comonomer [e.g. a polyamide obtd. from epsilon-caprolactam, hexamethylenediamine, and linolenic acid dimer, i.e., dimer acid (6/6.36 nylon)]. Thus the resin compsn. improved in the impact resistance and brittleness is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyarylene sulfide resin composition containing a specific copolyamide.

Specifically, the present invention relates to polyarylene sulfide resin compositions with improved impact resistance and brittleness.

[Prior art and its problems] Polyarylene sulfide resins, represented by polyphenylene sulfide resins, themselves have excellent heat resistance, and molding materials reinforced with reinforcing agents such as glass fibers are particularly useful for automobiles. It is being used in parts and electronics-related parts, especially in areas that require heat resistance, and demand as a useful engineering plastic is increasing.

However, unreinforced polyarylene sulfide resin is unsuitable as a molding material because it has insufficient mechanical properties such as tensile elongation at break and impact resistance.

Furthermore, even when reinforced with glass fiber etc., polyarylene sulfide resin itself is fragile, so
However, it has insufficient impact resistance, which limits its application to many uses despite its excellent performance.

Conventionally, in order to improve the brittleness and impact resistance of this polyarylene sulfide resin, compositions have been known in which an olefin copolymer consisting of an α-olefin and a glycidyl ester of a β-unsaturated acid is blended. , Japanese Unexamined Patent Publication No. 58-
154757 (non-reinforced composition) and 1 2 JP-A-59-152953 (glass fiber reinforced composition)
has been disclosed.

In addition, JP-A-59-113055 discloses a composition comprising a polyphenylene sulfide resin mixed with a polyamide-based or polyester-based thermoplastic elastomer.
Furthermore, JP-A-61-148268 discloses compositions in which polyphenylene sulfide resin is blended with ethylene-propylene-nonconjugated diene copolymer rubber.

However, in any of the compositions, the effect of improving copper impact resistance and brittleness, and the improvement of flexibility were insufficient.

In addition, when other resins are blended with the polyarylene sulfide resin, the viscosity may increase and moldability may be adversely affected.

Means for Solving Problem E] In view of the problems of the prior art as described above, the present inventors have improved the impact resistance and brittleness while maintaining the rigidity of polyarylene sulfide resin, and have improved flexibility. With the aim of obtaining a polyarylene sulfide resin that provides a polyarylene sulfide resin with excellent moldability, we have conducted intensive studies and found that by blending a specific amount of a specific copolyamide into a polyarylene sulfide resin, we have developed The inventors have discovered that the above object can be achieved without impairing the excellent heat resistance of the resin, and have arrived at the present invention.

That is, the gist of the present invention is as follows: a) 99 to 75% by weight of polyarylene sulfide resin
b) 1 to 25% by weight of a copolyamide containing a dimerized fatty acid component as a copolymerization component;

The present invention will be explained in detail below.

The polyarylene sulfide resin in the composition of the present invention is a polymer consisting of repeating monomers represented by the following structural formula.

(R represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, and n represents an integer of θ to 4.) 4 Among these, preferable polymers include polymers consisting of repeating units represented by -mXS, i.e. , polyphenylene sulfide (hereinafter referred to as PPS).

).

PPS is generally a polymer with a relatively small molecular weight obtained by the production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by the production method typified by JP Publication No. 52-12240. There are polymers with relatively high molecular weight, and the degree of polymerization of the above polymers can be increased by heating in an oxygen atmosphere after polymerization, or by adding a crosslinking agent such as peroxide and heating. In the present invention, it is possible to use PPS obtained by any method.
In terms of the toughness of S itself, an essentially linear polymer obtained by the production method typified by the above-mentioned Japanese Patent Publication No. 52-12240 may be more preferably used.

Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula, etc.

The melt viscosity of PPS used in the present invention is not particularly limited as long as it is possible to obtain molded products, but in terms of the toughness of PPS itself, it is 100 poise or more, but in terms of moldability, it is 10,000 poise. The following are more preferably used.

Further, the PPS used in the present invention can be added with ordinary additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, and coloring agents. For control purposes, ordinary peroxidants and JP-A-59-1
Crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A No. 31650, or JP-A-58-204045;
It is also possible to incorporate crosslinking inhibitors such as dialkyl acid dicarboxylate and aminotriazole described in JP-A-58-204046 and the like.

The copolyamide containing a dimerized fatty acid component as a copolymerization component in the composition of the present invention will be explained below.

The main component of the copolyamide as used in the present invention is a polyamide produced by polycondensation of three or more specific lactams, polymerizable ω-amino acids, or dibasic acids and diamines. Specifically, raw materials for these polyamides include lactams such as ε-caprolactam, enanthralactam, capryllactam, lauryllactam, α-pyrrolidone, and α-piperidone, 6-aminocaproic acid,
omega-amino acids such as 7-aminehebutanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, adipic acid, glutaric acid, pimelic acid, superric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecadionic acid,
Hexadecadioic acid, hexadecenedioic acid, eicosandioic acid, eicosadienedionic acid, diglycolic acid, 2,2.4-1-limethyladivic acid, xylylene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid acids, dibasic acids such as terephthalic acid, isophthalic acid, hexamethylene diamine, tetramethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2.2.4 (or 2.4.4 )-trimethyl Examples include diamines such as hekylymethylenediamine, bis-(4,4'-aminocyclohexyl)methane, and metagysylylenediamine.

Examples of such polyamide materials include nylon 4.6.7.8.11.12.6, 6.6.9.6.
10.6.11.6.12.6T, 6/6.6.6/
Examples include 12.6/6T.

The dimerized fatty acid component, which is a copolymerization component of the copolyamide, can be obtained by polymerizing fatty acids such as saturated, ethylenically unsaturated, acetylenically unsaturated, natural or synthetic basic fatty acids having 8 to 24 carbon atoms. It is a component formed from polymerized fatty acids.

Specific examples of such fatty acids include dimers of liquilenic acid and the like.

Commercially available polymerized fatty acids usually have dimerized fatty acid as the main component and also contain monomer acids and dimerized fatty acids as raw materials, but the content of dimerized fatty acids is 70% by weight or more. It is preferable that

The content of the dimerized fatty acid component in the copolyamide of the present invention is 0.1 to 45% by weight, preferably 0.5 to 40% by weight.
Weight%. If the content is too small, the effect of improving impact properties in the polyarylene sulfide resin composition will be insufficient. On the other hand, if the amount is too high, the melt viscosity becomes too low, making it difficult to form a composition with polyarylene sulfide resin.

As a method for producing the copolyamide of the present invention, for example, the above-mentioned main component polyamide raw material is polycondensed in the presence of a diamine having 2 to 22 carbon atoms and the above-mentioned dimerized fatty acid.

Examples of diamines having 2 to 22 carbon atoms include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine. methylene diamine, tridecamethylene diamine, tridecamethylene diamine, octadecamethylene diamine, 2.2.4 (or 2.4.4
)-Aliphatic diamines such as trimethylhexamethylene diamine, cyclohexane diamine, methylcyclohexane diamine, alicyclic diamines such as bis-(4,4-aminocyclohexyl)methane, aromatic diamines such as gysylylene diamine, etc. can be given.

The content of copolyamide containing dimerized fatty acid in the polyarylene sulfide resin composition is 1 to 25% by weight.
, preferably 3 to 20%. If the content is less than 1% by weight, no improvement in impact resistance or brittleness is observed. Furthermore, if the amount added exceeds 25% by weight, the inherent characteristics of polyarylene sulfide resin, such as rigidity and heat resistance, will be greatly impaired, which is not preferable.

In the present invention, inorganic fillers may be included in the compositions of the present invention up to about 65% by weight of the total composition, preferably in the range of about 30 to about 60% by weight of the total composition.

Inorganic fillers useful in the present invention can be selected from materials such as glass materials, calcium carbonate, calcium sulfate, talc, mica, and the like. Preferably, glass substances are used. The glass material may be selected from any commercially available product commonly used as a filler and reinforcing agent, such as glass fibers or glass peas, but the preferred material for the present invention is glass fiber.

Various other additives may be used in the polyarylene sulfide resin composition of the present invention in small amounts up to about 5% by weight of the total composition. These additives include materials such as flow enhancers (processability) agents, silanes and pigments. Compatible processing agents include solid ethylene copolymers (see U.S. Pat. No. 4,134,874), saturated fatty acid salts such as zinc stearate, and N,N-alkylene bis(alkanamides), 10 to 30 carbon atoms. Glycerides and phosphated glycerides of saturated fatty acids with
It can be selected and added from among alkanolamides and esters derived from saturated long-chain fatty acids and long-chain saturated aliphatic alcohols. General purpose fillers such as lithium carbonate are also suitable as processing agents. It is also possible to add a compatibilizer such as an epoxy resin.

The method for preparing the composition of the present invention is not particularly limited, but the polyarylene sulfide resin, the copolyamide, and optionally the reinforcing agent are mixed in a -screw or multi-screw extruder at a temperature higher than the melting point of the polyarylene sulfide resin. A typical method is to melt-knead and then pelletize. The melting and mixing temperature is preferably 280 to 340'C. If it is less than 280°C, the polyarylene sulfide resin will not be sufficiently melted, which is not preferable. If it exceeds 340°C, the thermal deterioration of the copolyamide will become significant, so it is not preferable. do not have.

[Examples] The present invention will be described in more detail with reference to Examples below, but the present invention is not limited by these Examples unless it departs from the gist thereof.

In the examples, a polyamide (abbreviated as 676.36 nylon) made from a dimer (dimer acid) of ε-caprolactam, hexamethylene diamine, and liquilenic acid was used as a copolyamide containing a merized fatty acid. Composition ratio is 6/6
．． 36 = 60/40 (weight ratio), and the content of dimer acid was 33.2% by weight.

Toshi Phillips PPS resin (product name M-288)
8) 95 parts by weight and 5 parts by weight of the above copolyamide were triblended, melt-kneaded in a twin-screw extruder set at 300°C, taken out in the form of a strand, and pelletized with a strand cutter. Next, the pellets were fed to an injection molding machine set at 300°C.
A test piece for mechanical property evaluation was molded at a mold temperature of 140 to 150°C.

A bending test was conducted in accordance with ASTM D-790, and the bending elastic modulus and bending displacement at break were measured. The displacement at break is the distance the crosshead moves until the bent piece breaks in the test method of ASTM D-790 Method I-A. In addition, Izot impact values of 1/2 inch and 1/8 inch (published by Notchi) were measured according to ASTM D256. The measurement results are shown in Table-1.

Examples 2 to 3, Comparative Examples 1 to 2 Melt mixing and injection were performed in the same manner as in Example 1, except that the amounts of PPS resin and copolyamide used in Example 1 were changed as shown in Table 1. Molding was carried out, and the bending elastic modulus, bending fracture displacement, and Izot impact value of the obtained test piece were measured. The results are shown in Table-1.

Comparative Example 3 The same procedure as in Example 1 was conducted except that nylon 6 was used instead of the copolyamide in Example 1. The results are shown in Table-1.

Reference Example A molded product was molded in the same manner as in Example 1 using only PPS resin M-2888 manufactured by Toshi-Philips, and the bending test and Izot impact test were carried out. The results are shown in Table-1.

Example 4 54 parts by weight of PPS resin in Example 1, copolymerized poly 1
3-4- 6 parts by weight of amide and glass fiber (Nippon Electric Glass Co., Ltd.)
40 parts by weight of T-717) was triblended, and the rest was melt-kneaded and injection molded in the same manner as in Example 1.
The bending elastic modulus, bending fracture displacement,
Izod impact value and heat distortion temperature (HDT) were measured. The results are shown in Table-2.

Comparative Example 4 60 parts by weight of the PPS resin in Example 1 and 40 parts by weight of the glass fiber in Example 4 were triblended, and the rest was carried out in the same manner as in Example 4. The results are shown in Table-2.

Note that HDT was measured according to ASTM-D-648.

Copolyamides containing dimerized fatty acids were added at 5% by weight (Example 1), 10% by weight (Example 2) and 20% by weight (
Example 3) The blended polyarylene sulfide resin composition has increased bending fracture displacement and Izot impact strength compared to the polyarylene sulfide resin that does not contain copolymerized polyamide (reference example), and has an effect of improving brittleness. Remarkably, on the other hand, the decrease in stiffness (1 old y elastic modulus) was slight.

A composition containing a smaller amount of copolyamide than the range of the present invention (Comparative Example 1) showed no improvement in brittleness, while a composition containing a larger amount of copolyamide (Comparative Example 2) showed no improvement in brittleness. Although the effect is great, the decrease in rigidity is significant.

Further, when a polyamide containing no dimerized fatty acid component was used (Comparative Example 3), no brittleness improving effect was observed.

Even when glass fiber is used as a reinforcing agent, the polyarylene sulfide resin composition containing 6% by weight of copolyamide (Example 4) is different from the polyarylene sulfide resin composition containing no copolyamide (Example 4). Compared to Comparative Example 4), the bending displacement at break and the isot impact strength were increased, and the effect of improving brittleness was remarkable, while the decrease in stiffness (flexural modulus) and HDT was slight.

[Effects of the Invention] According to the present invention, a polyarylene resin composition with significantly improved impact resistance and brittleness can be obtained, and is extremely useful in the fields of various automobile parts, mechanical parts, electrical and electronic parts, etc. We can provide materials.

Claims (1)

[Claims] (1) A polyarylene sulfide resin composition comprising a) 99 to 75% by weight of a polyarylene sulfide resin and b) 1 to 25% by weight of a copolyamide containing a dimerized fatty acid component as a copolymerization component.