JPH0328267A - 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.

CONSTITUTION: The objective compsn. is obtd. by compounding 100 pts.wt. polyarylene sulfide resin (A), 0.01-10 pts.wt. org. bisphosphite compd. (B) of formula I [R₁ and R₂ are each a (substd.) alkyl, a (substd.) aryl and an alkoxy] (e.g. compd. of formulas II and III, etc.), and 0-400 pts.wt. inorg. filler (e.g. glass fibers, CaCO₃, etc.). The above polyarylene sulfide 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 composite sole in which discoloration of certain shaped articles is significantly improved.

[Conventional technology and its issues]

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

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 hue of the resulting molded product may be discolored overall compared to the hue of the pellet before molding, or the surface of the molded product may have black streaks or mottled spots. Many unfavorable phenomena are observed in appearance, such as discoloration and discoloration when used at high temperatures after molding (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 evaporative gas or decomposition gas to be generated during the cutting process, so that 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 composition,
In particular, we have made extensive studies to suppress discoloration of molded products during processing of polyphenylene sulfide resin compositions and to obtain compositions that do not generate decomposition gas. the result,
A composition containing an organic bisphosphite compound having two phosphorus atoms in the molecule, represented by the following formula (1), has good thermal stability and can be used for extrusion of polyarylene sulfide resin, or for decomposition gas at a certain temperature. In addition, it was discovered that almost no evaporative gas is generated, there is no risk of ignition, and there is no impediment to physical properties or workability such as moldability, and it has the effect of reducing discoloration, etc., which is more noticeable than conventional methods. Ta. Furthermore, the present inventors have discovered that the above-mentioned properties can be further improved by adding a specific silane compound to the composition, thereby completing the present invention.

That is, the present invention comprises (^) 100 parts by weight of polyarylene sulfide resin, and (B) 0.0 parts by weight of an organic bisphosphite compound represented by the following formula (1). Ol to 10 parts by weight (wherein R and R are groups 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. ) (C) A polyarylene sulfide resin composition containing 0 to 400 parts by weight of an inorganic filler.

Furthermore, the present invention provides the above (A). (B) and (C) In addition to component a, one or more silane compounds selected from (b) aminoalkoxysilane, epoxyalkoxysilane, mercabutalkoxysilane, and vinylalkoxysilane are added. This is a polyarylene sulfide resin composite sole containing .01 to 5 parts by weight.

The base resin as the component (^) in the composition of the present invention is polyarylene sulfide resin (PAS), and is composed of the main repeating unit +^r-S-}- (where 8r is an arylene group). It is something that

Examples of the arylene group include (X is an alkyl group, preferably a C, to C6 alkyl group, or a phenyl group, and n is an integer of 1 to 4.) p. p'-diphenylene sulfone group, p, p''-diphenylene ether group, p. p'-diphenylene carbonyl group, etc. can be used.

In this case, it is preferable to use a polymer using the same repeating unit, that is, a homopolymer, among the arylene sulfide groups that are formed from the above-mentioned arylene group, but from the viewpoint of processability of the composite, different repeating units may be used. In some cases, cobolimers containing .

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

Furthermore, 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, a string containing a p-phenylene sulfide group and a m-phenylene sulfide group is used. A combination is particularly 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, components whose repeating units are contained in blocks (for example, Japanese Patent Laid-Open No. 61-1989-1) rather than random repeating units
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 in the present invention as component (A) III, polymers obtained by oxidative crosslinking or thermal crosslinking can also be used, but preferred are 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 57 seconds is IXIO to 5X10'bois, preferably 50 to 5X10'voise, particularly preferably 100 to 5X
Linear polymers in the lO' voids range are suitable.

If the number of voids is less than 10, the fluidity is too good and melt processing is difficult, and even if a shaped product is obtained, the mechanical strength is undesirably low. 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 added as the a component (B) is effective as long as it has the structure shown in the above formula (1).

(1) In the formula, R. , R. are selected from alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, and alkoxy groups, and each may be the same or different.

Among them, R. , R2 is preferably an alkyl group, substituted alkyl group, or alkoxy group having 5 or more carbon atoms, or an aryl group or a substituted aryl group from the viewpoint of stability during processing.

Particularly preferred is the case where R,, R, is an alkyl group or alkoxy group having 10 or more carbon atoms, or at least one is an aryl group or a substituted aryl group. Specifically, Structure A shown in Tables 1 to 3 (Note 1) of Examples described later,
B. Particularly preferred examples include substances such as C and D.

The amount of the component (B) expressed by the formula (1) used in the present invention is 100% of the polyarylene sulfide resin.
The amount is 0.01 to 10 parts by weight, preferably 0.1 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, a certain amount of inorganic filler ([') used in the present invention is:
Although it is not necessarily essential, it is preferable to include it in order to obtain a shaped product with excellent performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warping), and electrical properties. Depending on the purpose, this can be fibrous, non-W1 fibrous (powder, granular,
A plate-shaped filler is used.

Fibrous fillers include glass fiber, asbestos fiber,
Carbon fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum,
Examples include inorganic fibrous materials such as fibrous materials of metals such as titanium, copper, and brass. 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, powdery fillers include carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, and oxidized Metal oxides such as iron, titanium oxide, zinc oxide and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride, Examples include 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 the inorganic filler used is O to 4 per 100 parts by weight of the 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 perform certain shaping operations, and problems will also arise in the mechanical strength of the shaped product.

Next, as component (D) of the composition of the present invention, the above (A).
(B). (C) The silane compound preferably blended in combination with a certain amount is I type or two or more types of alkoxysilanes selected from aminoalkoxysilane, eboxyalkoxysilane, mercaptoalkoxysilane, and vinylalkoxysilane. It is.

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-aminopropyltriethoxysilane, T-aminopropyltriethoxysilane, -aminobrobyltrimethoxysilane, T-a-minopropylmethyldiethoxysilane, T-aminobrobylmethyldimethoxysilane, N-β<aminoethyl>-T-aminopropyltriethoxysilane, N-β( Aminoethyl
-r-aminopropyltrimethoxysilane, N-β(aminoethyl)-T-aminopropylmethyldiethoxysilane, N-β(aminoethyl)-T-aminobrovylmethyldimethoxysilane, N-7enyl-T -aminopropyltriethoxysilane, N-phenyl-T-aminopropyltrimethoxysilane, and the like.

Any silane compound having one or more epoxy groups and two or three alkoxy groups in one molecule is effective as the epoxy alkoxy silane.
For example, T-glycidoxypropyltrimethoxysilane,
Examples include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and T-glycidoxybrobyltriethoxysilane.

Any silane compound having one or more mercapto groups and two or three alkoxy groups in one molecule is effective as the mercaptoalkoxysilane, such as r-mercabutopropyltrimethoxysilane, Examples include T-mercabutobrobyltriethoxysilane.

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, and the like.

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 ([l) a certain amount is not only effective in improving shape processability and mechanical properties, but also when used in combination with (B) a certain amount, discoloration due to a certain forming process and the ability of a shaped product to be formed under high temperature. Is it even more effective against discoloration over time? was recognized as being able to demonstrate

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, boriad, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, and Examples include ether sulfone, polyetherimide, polyether ketone, and fluororesin. 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 preparing synthetic resin compositions. That is, the necessary amount can be mixed, kneaded using a single or twin screw extruder, and extruded to make pellets for a certain shape, and a part of the necessary amount can be mixed as a masterbatch or shaped. It is also possible to crush some 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 Table 3 were added in the amounts shown in Tables 1 to 3, and premixed for 5 minutes using a Henschel mixer. Furthermore, commercially available glass fibers (diameter 13 μm, length 3+ nm) and calcium carbonate were added in the amounts 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. I made a beret.

Next, with an injection molding machine, the cylinder temperature was 320°C, the mold temperature was 150°C, the thickness was 3 mm, the size was 500117I
A 70 mm flat test piece was shaped and the hue of the shaped product was measured using a color difference meter manufactured by Nippon Denshoku Kogyo ■.

The degree of black streaks or mottled discoloration occurring on the surface of certain shaped products 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 cut using an injection molding machine at a cylinder temperature of 320°C and a mold temperature of 150°C in accordance with STM D-638, and the strength and elongation were measured. Table 1 shows the results.
- Shown in Table 3.

Tables 1 to 3 (Note 1) F: C1. H210 P (Note 2) G: T-aminobutylene triethoxysilane H: T-glycidoxybrobyltrimethoxysilane 5 I: T-mercaptobrobyltrimethoxysilane J: Vinyltrimethoxysilane [invention Effect] As is clear from the above description and examples, the polyarylene sulfide resin composition of the present invention has significantly improved discoloration, high whiteness, and streak-like appearance compared to conventional polyarylene sulfide resin compositions. Or, a molded product with a good surface condition with less occurrence of mottled discoloration can be obtained.Also, it has excellent heat resistance, and almost no evaporation gas or decomposition gas is generated during extrusion or molding, and there are almost no problems caused by these. It also has excellent moldability and mechanical properties.

Claims (1)

[Scope of Claims] 1 (A) 100 parts by weight of polyarylene sulfide resin, (B) 0.01 to 10 parts by weight of an organic bisphosphite compound represented by the following formula (1) ▲ Numerical formula, chemical formula, table, etc. Yes▼ (However, in the formula, R_1 and R_2 are groups 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.) (C) Inorganic A polyarylene sulfide resin composition containing 0 to 400 parts by weight of a filler. 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.