JPH0328268A - Poly arylene sulfide resin compound - Google Patents

Abstract

PURPOSE: To obtain a resin compsn. which provides a molded article with remarkably improved discoloration by compounding a polyarylene sulfide resin with an org. bisphosphite compd. or an org. bisphosphonite compd.

CONSTITUTION: The objective compsn. is obtd. by compounding 100 pts. wt. polyarylene sulfide resin (A), 0.01-10 pts. wt. org. bisphosphite compd. or org. bisphosphonite compd. (B) of formula I or formula II [R₁-R₄ are each a (substd.) alkyl, a (substd.) aryl and an alkoxy; x is a divalent (substd.) alkylene and (substd.) arylene] (e.g. compd. of formulas III and IV, etc.), and 0-400 pts. wt. inorg. filler (e.g. glass fibers, CaCO₃, etc.). This resin compsn. provides a molded article with remarkably improved discoloration and high whiteness in comparison with the conventional one and with a surface condition with less generation of stripe-like or spotted discoloration can be obtd. In addition, excellent heat resistance and little generation of vaporized gas or decomposed gas during extrusion and molding, are exhibited and hindrance caused by them hardly occurs and molding processability and mechanical physical properties are excellent.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyarylene sulfide resin compositions. More specifically, the present invention relates to a polyarylene sulfide resin bottom with significantly improved discoloration of a shaped article.

[Conventional technology and its issues]

In recent years, electric/electronic equipment parts materials, automobile equipment parts materials,
Thermoplastic resin compositions that have excellent mechanical properties, high heat resistance, chemical resistance, and flame retardancy are increasingly required for chemical parts materials.

Polyarylene sulfide resin, typified by polyphenylene sulfide resin, is one of the resins that meet this demand, and demand is increasing due in part to its good physical properties relative to cost.

However, when this resin is processed by injection molding, etc., the color of the resulting molded product may change overall compared to the hue of the pellet before molding, or there may be black streaks or mottled discoloration on the surface of the molded product. There are many undesirable phenomena in terms of appearance, such as the problem of the occurrence of oxidation, and the problem of discoloration when used at high temperatures after cutting (hereinafter abbreviated as discoloration, etc.).

In order to solve this problem, a method of adding organic monophosphite was developed as a technique to prevent discoloration (Japanese Patent Laid-Open No. 47-17
No. 35) has been proposed.

However, as a result of additional testing by the inventors, it was found that this method has various problems. That is, the heat resistance of the additive is poor, and there is a tendency for evaporation gas or decomposition gas to be generated during certain processing, and it cannot be said that the workability, physical properties, and appearance are fully satisfactory.

[Means to solve the problem]

The present inventors have developed a polyarylene sulfide resin composite sole,
In particular, we have made extensive studies to suppress the occurrence of discoloration of shaped products during processing of polyphenylene sulfide resin compositions and to obtain compositions that do not generate decomposition gas. As a result, a composition containing an organic bisphosphite compound or an organic bisphosphonite compound having two phosphorus atoms in the molecule, represented by the following formula (1) or (2), has good thermal stability. When extruding polyarylene sulfide resin, almost no decomposition gas or evaporative gas is generated at a certain temperature, there is no risk of ignition, and there is no problem with physical properties or workability such as formability. It has been found that this method has a more significant effect in reducing discoloration than conventional methods. Furthermore, the present inventors have discovered that the above-mentioned properties can be further improved by adding a specific silane compound to the composition, and have completed the present invention.

That is, the present invention includes (A) 100 parts by weight of polyarylene sulfide resin and (B) 0.01 to 10 weight parts of an organic bisphosphite compound or organic bisphosphonite compound represented by the following formula (1) or (2). (wherein R,, R2, R., R. is a group selected from an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkoxy group, and each may be the same or different. .X represents a divalent alkylene group, a substituted alkylene group, an arylene group, or a substituted arylene group.

) (C) A polyarylene sulfide resin composition containing 0 to 400 parts by weight of an inorganic filler.

Furthermore, the present invention is as described above (^). In addition to a certain amount of (B) and (C), one or more silane compounds selected from (D) aminoalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, and vinylalkoxysilane are added in an amount of 0.01 to This is a polyarylene sulfide resin composite sole containing 5 parts by weight.

The base resin (^) in the assembled sole of the present invention is a polyarylene sulfide resin (PAS), which is composed of the main repeating unit +Ar-S-}- (where Ar is an arylene group). It is something.

Examples of the arylene group include (Y is an alkyl group, preferably a C, to C6 alkyl group, or a phenyl group, and n is an integer of 1 to 4.) I'll'''Phenylene sulfone group p. p' −
Diphenylene ether group p. A p'-diphenylenecarbonyl group, etc. can be used.

In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, it is preferable to use a polymer using the same repeating unit, that is, a homopolymer, but from the viewpoint of processability of the composition, it is preferable to use a polymer containing different repeating units. Cocobo reimers may be preferred in some cases.

As the homopolymer, a substantially linear one having a p-phenylene sulfide group as a repeating unit and using a p-phenylene group as an arylene group is particularly preferably used.

In addition, as the copolymer, combinations of two or more different types of arylene sulfide groups consisting of the above-mentioned arylene groups can be used, but among them, combinations containing p-phenylene sulfide groups and m-phenylene sulfide groups are particularly preferred. Preferably used. Among these, p-phenylene sulfide group is 50 mol% or more, preferably 70 mol% or more.
From the viewpoint of physical properties such as heat resistance, formability, and mechanical properties, it is preferable that the content is mol % or more.

In this case, the repeating unit of the bokun is included in a block shape (for example, JP-A-61
The material described in Japanese Patent Publication No. 14228) has almost the same processability, but has excellent heat resistance and mechanical properties, and can be preferably used.

As the polyarylene sulfide resin used as the (A) M component used in the present invention, polymers obtained by oxidative crosslinking or thermal crosslinking can be used, but it is preferable to use polyarylene sulfide resins obtained by condensation polymerization from bifunctional monomers. It is a polymer with a linear molecular structure.

Among them, the melt viscosity measured under the conditions of a temperature of 310°C and a shear rate of 5/sec is 1 x 10 to 5 x 10' voids, preferably 50 to 5 x 10' voids, particularly preferably 100 to 5 x
Linear polymers in the 10' void range are suitable.

If it is less than 10 poise, the fluidity will be too good and melt processing will be difficult, and even if a shaped article can be obtained, the mechanical strength will be low, which is undesirable. Moreover, those having more than 5×10′ voids have poor fluidity and are difficult to melt process.

In the present invention, any organic bisphosphite compound or organic bisphosphonite compound added as part (8) is effective as long as it has the structure shown in the above formula (1) or (2). It is.

In the formula (1) or (2), R1 to R4 are selected from an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkoxy group, and may be the same or different.

Among them, R and to R4 are preferably alkyl groups having 5 or more carbon atoms, substituted alkyl groups, aryl groups, or substituted aryl groups from the viewpoint of stability during processing, gas generation, etc.

It is particularly preferable that R and ~R4 are all alkyl groups or alkoxy groups having IO or more carbon atoms, or at least 1
This is the case of an aryl group or a substituted aryl group. Specifically, structures A. Examples include substances such as B, C, and D.

Moreover, X is a divalent alkylene group, a substituted alkylene group, an arylene group, or a substituted arylene group.

The amount of the precept (B) represented by the formula (1) or (2) used in the present invention is 0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight, per 100 parts by weight of the polyarylene sulfide resin. It is 1 to 5 parts by weight.

If the amount is too small, the intended effect cannot be obtained, and if it is too large, problems such as deterioration of physical properties and generation of gas occur, which is not preferable.

Next, the inorganic filler as component (C) used in the present invention has properties such as mechanical strength, heat resistance, dimensional stability (resistance to deformation, warpage), electrical properties, etc., although they are not necessarily essential. In order to obtain a shaped product with excellent properties, it is preferable to blend
Depending on the purpose, fibrous or non-fibrous (powder-like, plate-like) fillers are used for this purpose.

Fibrous fillers include glass fiber, asbestos fiber,
Carbon fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride #a! 1. Inorganic fibrous materials such as boron ta fibers, potassium titanate fibers, and metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass can be mentioned. Particularly typical fibrous fillers are glass fibers or carbon fibers. Note that high melting point organic fibrous substances such as polyamide, fluororesin, and acrylic resin can also be used.

On the other hand, silicates such as carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, phosphorus, talc, clay, diatomaceous earth, and wollastonite are used as powdery fillers. , metal oxides such as iron oxide, titanium oxide, zinc oxide, and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, and other silicon carbide, silicon nitride, and nitride. Examples include boron and various metal powders.

Further, examples of the plate-shaped filler include Myriki, glass flakes, and various metal foils.

These inorganic fillers can be used alone or in combination of two or more. The combined use of a fibrous filler, particularly glass fiber or carbon fiber, and a granular and/or plate-like filler is a particularly preferable combination from the viewpoint of combining mechanical strength, dimensional accuracy, electrical properties, and the like.

A particularly preferred combination is an average fiber length of 30 to 500μ.
It is a combination of glass fiber of m and inorganic powdery granular material with an aspect ratio of 5 or less.

When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. Examples of this include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be used after surface treatment or convergence treatment, or may be added at the same time when preparing the material.

(C) The amount of inorganic filler used as a filler is 0 to 4 per 100 parts by weight of polyarylene sulfide resin (A).
00 parts by weight, preferably 10 to 250 parts by weight. If it is too small, the mechanical strength will be poor, and if it is too large, it will be difficult to form the shape, and there will also be problems with the mechanical strength of the shaped product.

Next, as the component (0) of the composition of the present invention, the above (A).
(B), (C) The silane compound that is preferably blended in combination with component a is one or two selected from aminoalkoxysilane, eboxyalkoxysilane, mercabutalkoxysilane, and vinylalkoxysilane.
It is more than one kind of alkoxysilane.

As the aminoalkoxysilane, any silane compound having one or more amino groups and two or three alkoxy groups in one molecule is effective; for example, T-aminobrobyltriethoysilane , r-aminopropyltrimethoxysilane, T-aminopropylmethyldiethoxysilane, T-aminopropylmethyldimethoxysilane, N-β(aminoethyl)-T-aminobrobyltriethoxysilane, N-β(aminopropyltrimethoxysilane) ethyl)
1-aminopropyltrimethoxysilane, N-β(aminoethyl)-T-aminopropylmethyldiethoxysilane, N-β(aminoethyl)-γ-aminobrobylmethyldimethoxysilane, N-phenyl-r- Examples include aminobrobyltriethoxysilane, N-7enyl-T-aminobrobyltrimethoxysilane, and the like.

As the epoxyalkoxysilane, any silane compound having one or more epoxy groups and two or three alkoxy groups in one molecule is effective.
For example, γ-glycidoxypropyltrimethoxysilane,
Examples include β-(3,4-epoxycycylhexyl)dityltrimethoxysilane, γ-glycidoxibipyltriethoxysilane, and the like.

As the mercaptoalkoxysilane, any silane compound having one or more mercapto groups and two or three alkoxy groups in one molecule is effective, such as T-mercaptobrobyltrimethoxysilane. , T-mercabutobrobyltriethoxysilane, and the like.

As the vinyl alkoxysilane, any silane compound having one or more vinyl groups and two or three alkoxy groups in one molecule is effective, such as vinyl} IJ ethoxysilane, vinyl trimethoxy Examples include silane, vinyltris (β-methoxyethoxy) silane, etc.

The amount of the alkoxysilane used in the present invention is 5 parts by weight or less, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the polyarylene sulfide resin. If it is too small, the intended effect will be small, and if it is too large, the mechanical properties will deteriorate, which is undesirable.

The combination of (D) Bokmin is not only effective in improving the shape processability and mechanical properties, but also the combination with (B) Bokmin can reduce discoloration due to certain forming processes, and reduce the resistance of shaped products to high temperatures. It was also found that it was even more effective against discoloration over time.

Further, as the base resin of the present invention, it is also possible to use a small amount of other thermoplastic resins in a range that does not interfere with the purpose. The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures. For example, aromatic polyesters made of aromatic dicarboxylic acids and diols or oxycarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate, polyamides, polycarbonates, ABS, polyphenylene oxides, polyalkyl acrylates, polyacetals, polysulfones, and polyethersulfones. , polyetherimide, polyetherketone, fluororesin, etc. Moreover, two or more types of these thermoplastic resins can also be used in combination.

Furthermore, the composition of the present invention contains known substances that are generally added to thermoplastic resins and thermosetting resins, such as stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, mold release agents, and hardening agents. Flame retardants, flame retardant aids, coloring agents such as dyes and pigments, lubricants, nucleating agents, etc. can also be added in combination as appropriate depending on the required performance.

The polyarylene sulfide resin composition of the present invention can be prepared using equipment and methods generally used for manufacturing synthetic resin compositions. That is, a necessary amount can be mixed, kneaded using a single-screw or twin-screw extruder, and extruded to form a pellet for molding, and a necessary portion can be mixed and shaped as a masterbatch. It is also possible to pulverize part or all of the polyarylene sulfide resin, mix it, and melt-extrude it to improve the dispersion and mixing of each part.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Examples 1 to 29 and Comparative Examples 1 to 6 Table 1 to
The additives shown in Tables 1 to 3 were added in the amounts shown in Tables 1 to 3, and premixed for 5 minutes using a Henschel mixer. Further, depending on the case, commercially available glass fibers (diameter 13 μm, length 3 mm>) and calcium carbonate are added in the amount shown in the table, mixed for 2 minutes in a blender, and then passed through an extruder with a cylinder temperature of 310°C to form a polyphenylene sulfide resin composition. pellets were made.

Next, using an injection molding machine, the cylinder temperature was 320°C, the mold temperature was 150°C, the thickness was 3 mm, and the size was 50 mm x 70 mm.
Nippon Denshoku Industries ■
It was measured using a color difference meter.

In addition, the degree of black streaks or mottled discoloration occurring on the surface of the shaped product was also observed. In addition, the molten resin was free-flowed during injection molding, and the amount of gas generated from the molten resin was evaluated. Furthermore, a tensile test piece was formed using an injection molding machine at a cylinder temperature of 320°C and a mold temperature of 150°C in accordance with ASTM D-638, and the strength and elongation were measured. Table 1 shows the results.
~3.

Tables 1 to 3 (Note 1) F = (CIDH2.ro→coPR R=CI2~CIS Alkyl group (Note 2) G: T-aminopropyl 1T ethoxysilane H: T-
Glycidoxypyltrimethoxysilane I: T-mercabutopropyltrimethoxysilane J: Vinyltrimethoxysilane [Effects of the Invention] As is clear from the above description and examples, the polyarylene sulfide resin composition of the present invention Compared to conventional polyarylene sulfide resin compositions, discoloration and the like are significantly improved, and a molded article with a high degree of whiteness and a good surface condition with less occurrence of sliver-like or mottled discoloration can be obtained. Furthermore, it has excellent heat resistance, hardly any evaporative gas or decomposition gas is generated during extrusion or shaping, there are almost no problems caused by these gases, and it has excellent shaping processability and mechanical properties.

Voluntary writing of procedural amendments) January 26, 2016 Day

Claims (1)

[Scope of Claims] 1 (A) 100 parts by weight of polyarylene sulfide resin and (B) 0.01 to 0.01 to an organic bisphosphonite compound or organic bisphosphonite compound represented by the following formula (1) or (2). 10 parts by weight ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R_1, R_2, R_3, R_4 are alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups and alkoxy groups, each of which may be the same or different. X represents a divalent alkylene group, substituted alkylene group, arylene group, or substituted arylene group.) (C) Inorganic filler 0 A polyarylene sulfide resin composition containing ~400 parts by weight. 2 In addition to (A), (B), and (C) of claim 1, (D
) At least one alkoxysilane selected from aminoalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, and vinylalkoxysilane.
．． A polyarylene sulfide resin composition containing 01 to 5 parts by weight.