KR100527220B1 - Polyarylene sulfide resin composition - Google Patents

Abstract

The present invention is excellent in molding processability, and in particular, it is possible to form a mold having excellent mechanical properties of the molded article without corrosion or contamination of metal parts such as a mold during molding, and (A) 100 parts by weight of polyarylene sulfide resin. It relates to a polyarylene sulfide resin composition containing (B) 0.05 to 3 parts by weight of zinc oxide whisker.

Description

Polyarylene sulfide resin composition {POLYARYLENE SULFIDE RESIN COMPOSITION}

The present invention relates to an improved polyarylene sulfide resin composition. More specifically, the present invention relates to a polyarylene sulfide resin composition which is excellent in molding processability, in particular, does not corrode and contaminate metal parts such as a mold during molding, and is excellent in mechanical properties of molded articles.

Polyarylene sulfide (hereinafter referred to as PAS) resin represented by polyphenylene sulfide (hereinafter, abbreviated as PPS) resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame resistance. It is widely used in electronic device component materials, automotive device component materials, and chemical device component materials.

However, this resin has a sulfur atom in its molecular structure and its raw material contains alkali metals such as sulfur, chlorine and sodium, so that by-products containing a large amount of sulfur, chlorine, and alkali metals are produced during resin synthesis. Has the disadvantage of corroding and contaminating metal materials such as molds during molding, and also causes corrosion and contamination of metals or plating or deposited metals inserted into components when used as molded part materials. There is a problem.

As a means to solve this problem, it has been proposed to deionize the polymerized PAS resin with an acid, hot water, an organic solvent, and the like, and to reduce these impurities to 500 ppm or less, and even 200 ppm or less. Although they are quite effective, PAS resins and their compositions have a very high molding process temperature of at least 280 ° C. or higher, so even after these impurities are removed and purified, they still generate a corrosive gas during molding process, so that they do not have sufficient corrosion resistance to metals. .

As a technique for solving this problem, a proposal has conventionally been made in which a supplement for harmful substances is added to the resin to suppress corrosiveness and impurities. For example, lithium carbonate (Japanese Patent Publication No. 79-162752), hydrotalcite (Japanese Patent Publication No. 86-275353), zinc carbonate, zinc hydroxide (Japanese Patent Publication No. 90-105857) ), Zinc borate (Japanese Patent Laid-Open No. 94-306288), and the like. However, according to the inventor's follow-up investigation, although some kinds of additives are recognized to have some effect on the corrosion protection of metals, they are still not enough, and even a small amount of compounding causes problems such as deterioration of mechanical properties. Admitted. In addition, although Japanese Patent Application Laid-Open No. 92-164961 has an example of adding specific zinc oxide, it is hard to say that mechanical properties are still sufficient, and further improvement is desired.

In view of these problems, the present invention improves the corrosion and contamination of metals during molding of PAS resin compositions and their use, and improves tensile strength and elongation, impact strength and toughness even when a relatively large amount of corrosion inhibitor is used. It is an object of the present invention to provide a PAS resin composition having no adverse effect on mechanical properties such as corrosion resistance and having excellent corrosion resistance and mechanical properties.

Summary of the Invention

The present inventors have intensively studied to achieve the above object, and as a result, by blending a specific zinc oxide in the PAS resin, the corrosion and contamination to the metal is remarkably improved, and at the same time, the adverse effect on the mechanical properties of the corrosion inhibitor is The present invention has been completed by discovering that both of these properties are solved by maintaining excellent mechanical properties.

That is, the present invention,

(A) 100 parts by weight of polyarylene sulfide resin,

(B) 0.05 to 3 parts by weight of zinc oxide whisker

It is a polyarylene sulfide resin composition which mix | blended with a basic structural component and melt-kneaded.

That is, this invention is a polyarylene sulfide resin composition containing 100 weight part of said (A) and 0.05-3 weight part of (B).

Hereinafter, the components of the present invention will be described in detail.

PAS resin as (A) component in the composition of this invention consists mainly of-(Ar-S)-(where Ar is an arylene group) as a repeating unit. As an arylene group, p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p'- diphenylene sulfone group, p, p'- biphenylene group, p ', p', for example -Diphenylene ether group, p, p'- diphenylene carbonyl group, naphthalene group, etc. can be used. In this case, in the arylene sulfide group comprised with the said arylene group, the copolymer using a heterogeneous repeating unit may be preferable at the point of the processability of a composition other than the polymer using the same repeating unit, ie, a homopolymer.

As a homopolymer, what uses a p-phenylene group as an arylene group and makes a p-phenylene sulfide group a repeating unit is especially used preferably. In addition, as a copolymer, although the 2 or more types of combination different from the arylene sulfide group which consists of the said arylene group can be used, the combination containing p-phenylene sulfide group and m-phenylene sulfide group is especially especially used preferably. . Among these, containing 70 mol% or more, preferably 80 mol% or more of p-phenylene sulfide groups is suitable in terms of physical properties, such as heat resistance, moldability, and mechanical properties.

Moreover, among these PAS resins, although the high molecular weight polymer of the substantially linear structure obtained by condensation polymerization mainly from the monomer which mainly consists of a bifunctional halogen aromatic compound can be used preferably, it is the axis | shaft other than PAS resin of linear structure. A polymer in which a branched structure or a crosslinked structure is partially formed by using a small amount of a monomer such as a polyhaloaromatic compound having three or more halogen substituents at the time of polymerization may also be used. The polymer which heated at high temperature in presence, raise | melted melt viscosity by oxidative crosslinking or heat crosslinking, and improved moldability can also be used.

In addition, the PAS resin of (A) component consists mainly of the said linear PAS (310 degreeC, the viscosity in shear rate 1200sec <^-1> 10-300 Pa.s), and the one part (1-30 weight%, Preferably Is also preferred is a mixed system with branched or crosslinked PAS resin having 2 to 25% by weight of relatively high viscosity (300 to 3000 Pa · s, preferably 500 to 2000 Pa · s).

In addition, the PAS resin used in the present invention is subjected to deionization such as acid washing, hot water washing, organic solvent washing (or a combination thereof) after polymerization to remove by-product impurities and the like, thereby chlorine content and alkali metal content. Is preferably 500 ppm or less, preferably 300 ppm or less.

Next, the zinc oxide whisker used as the component (B) in the present invention has an average fiber diameter (short diameter) of 0.1 to 5 µm and an average fiber length (long diameter) of 2 to 100 µm in the needle section measured under a microscope. At the same time, the average aspect ratio is preferably 5 or more. Among commercially available products, there are zinc oxides having a three-dimensional tetrapod shape, and one of the compounds which is preferable as a whisker having the above-described shape, but is not limited thereto.

The compounding quantity of the said (B) component is 0.05-3 weight part with respect to 100 weight part of polyarylene sulfide resin, Preferably it is 0.1-1 weight part. 0.05 parts by weight is not sufficient for preventing corrosion and fouling of metals. Moreover, when it exceeds 3 weight part, the mechanical properties equivalent to the case where (B) component is not mix | blended will be no longer maintained.

In addition, it is preferable to treat the surface of the zinc oxide whisker of the component (B) with an epoxyalkoxysilane and / or an aminoalkoxysilane in terms of dispersibility and mechanical properties. As an epoxy alkoxysilane, any silane compound which has one or more epoxy groups in 1 molecule, and has two or three alkoxy groups is effective, For example, (gamma)-glycidoxy propyl trimethoxysilane and (gamma)-glycy Doxypropyl triethoxysilane etc. are mentioned. As aminoalkoxysilane, as long as it is a silane compound which has one or more amino groups in 1 molecule, and has two or three alkoxy groups, any may be effective, for example, (gamma) -aminopropyl trimethoxysilane and (gamma) -aminopropyl trie Oxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and the like.

As for the compounding quantity of these alkoxysilanes, 0.05-5 weight% is preferable with respect to the zinc oxide whisker of (B) component.

In the present invention, addition of phosphoric acid or hypophosphorous acid or salts thereof as (C) component can improve long-term moist heat resistance and is preferable.

(C) Phosphoric acid or hypophosphorous acid or salts used herein, for example, monophosphate, hypophosphorous acid, monobasic calcium phosphate, sodium monophosphate, calcium hypophosphite, hypophosphite, magnesium hypophosphite, sodium hypophosphite At least 1 type, or 2 or more types chosen from the salts of zinc, alkali metal, or alkaline-earth metal, such as these, are mentioned, Preferably it is calcium hypophosphite, magnesium hypophosphite, zinc hypophosphite. The compounding quantity of the said (C) component is 0.05-2 weight part with respect to 100 weight part of polyarylene sulfide resins (A), Preferably it is 0.1-1 weight part. When too small, the improvement effect on the target long-term heat-and-moisture resistance cannot be acquired, and when too small, there exists a problem, such as gas generation during shaping | molding, and is unpreferable.

By coexisting the component (C) with the component (B), long-term moisture and heat resistance can be improved by the interaction between the two components without unexpectedly impairing the effect of preventing corrosion and fouling of the metal of the component (B). It was confirmed. Although (C) component is effective even if it mix | blends in particular as it is, the method of mix | blending one part or all part in advance with the inorganic or organic filler which is (D) component mentioned later, and mix | blending it with another component is also effective. There is no restriction | limiting in particular about the method of sticking (C) component, For example, the solution containing the said compound may be sprayed and adhered to a filler, and in the case of glass fiber etc., it uses the roll coater and the said solution to fiber. It may be attached by applying. Moreover, it is also possible to process together with coupling agents, such as an epoxy resin, a urethane resin-based sizing agent, aminosilane, and an epoxysilane generally used as surface treating agents, such as glass fiber.

The inorganic or organic filler of the component (D) used in the present invention is not necessarily an essential component, but is preferably blended in order to obtain a molded article having excellent performances such as mechanical strength, heat resistance, dimensional stability (bending and deformation), and electrical properties. Depending on the purpose, fibrous, granular or plate fillers or mixtures thereof are used here.

Examples of the fibrous filler include glass fibers, asbestos fibers, carbon fibers, silica fibers, silica alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and the like. And inorganic fibrous materials such as metal fibrous materials such as aluminum, titanium, copper, and brass. In particular, representative fibrous fillers are glass fibers, carbon fibers, or potassium titanate fibers. In addition, high-melting organic fibrous substances such as aromatic polyamides, acrylic resins, and fluororesins can also be used.

On the other hand, as the granular filler, carbon black, graphite, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicate such as wollastonite, iron oxide, titanium oxide, alumina Oxides of metals such as, metal carbonates such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, other silicon oxides, silicon nitride, and various metal powders. Especially representative are carbon black, silica, glass beads or glass powder, calcium carbonate, talc and the like.

Moreover, a mica, glass powder, various metal foils etc. are mentioned as a plate-shaped filler.

These fillers can be used alone or in combination of two or more. The combination of fibrous fillers, in particular glass fibers or carbon fibers, with granular or plate-like fillers is a preferred combination because it combines mechanical strength, dimensional accuracy, electrical properties and the like.

In addition, when using these fillers, it is preferable to use it by surface treatment or sizing treatment with a sizing agent or a surface treating agent if necessary. Examples of this treatment agent are functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds and the like.

The compounding quantity of the said (D) component is 1 to 75 weight% with respect to the total composition, Preferably it is 3 to 70 weight%. In too many cases, the molding operation becomes difficult and a problem arises in the mechanical strength of the molded article.

In addition, as a molded article composition used in the present invention, known materials generally added to thermoplastic resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, flame retardants, dyes such as dyes and pigments, lubricants and crystallization accelerators, crystal nucleating agents and the like are also required performance. It can add suitably according to the.

The preparation of the resin composition of the present invention can be produced by equipment and methods generally used for the production of synthetic resin compositions. Generally, necessary components may be mixed, melt kneaded using a single screw or twin screw extruder, and extruded into pellets for molding. Moreover, it is also one of the preferable methods to melt-extrude a resin component and to add and mix | blend an inorganic component like glass fiber in the meantime.

The material pellets thus obtained can be molded using generally known thermoplastic resin molding methods such as injection molding, extrusion molding, vacuum molding and compression molding, but most preferably injection molding.

Hereinafter, the present invention will be described in detail with Examples and Comparative Examples, but the present invention is not limited thereto.

Examples 1-14 and Comparative Examples 1-10

As the component (A), a substantially linear polyphenylene sulfide resin (manufactured by Kureha Chemical Industry Co., Ltd., "Portron KPS", viscosity 50 Pa.s (310 占 폚, 1200 sec ^-1 ) 100 (B) component was added and mixed for 2 minutes with the Henschel mixer with respect to the weight part by addition, and (C) and (D) components were added in the quantity shown in Tables 1-2, and it was blended with a blender. The mixture was mixed for a second, and the mixture was kneaded with an extruder having a cylinder temperature of 310 ° C. to prepare pellets of the polyphenylene sulfide resin composition.The pellets were measured for corrosion resistance, mechanical properties, and long-term moisture resistance. To 2 are shown.

Example 15

The glass fiber of (D) component was apply | coated so that it may become the ratio shown in Table 2, and the (C) calcium hypophosphite solution melt | dissolved in the solvent, on the conditions same as the said Example except having used it in the state adhering enough previously. The composition was prepared and evaluated. The results are shown in Table 2.

In addition, the evaluation method is as follows.

[Corrosion resistance]

4 g of the pellets were placed in the bottom of a test tube having an internal diameter of 18 mm and a height of 160 mm, and a test piece (15 x 160 x 2 mm) of a mold material (SKD-11) mainly composed of iron, chromium, and carbon was suspended at a predetermined position. The top of the test tube was plugged, heated at 320 ° C. for 3 hours, and then the test piece was taken out and observed with a naked eye and a microscope to investigate the corrosion state, and the relative grades were rated according to the degree of the corrosion state as follows.

(Tensile strength and elongation)

Tensile test pieces were molded at an injection molding machine at a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., and the tensile strength and elongation were measured in accordance with ASTM D-638.

[Long-term moisture heat resistance]

The tensile test piece was shape | molded at the cylinder temperature of 320 degreeC, and the mold temperature of 150 degreeC by the injection molding machine, The test piece was processed for 500 hours in 95 degreeC hot water, and tensile strength was measured according to ASTMD-638.

Claims (7)

A polyarylene sulfide resin composition comprising 100 parts by weight of (A) polyarylene sulfide resin and 0.05 to 3 parts by weight of (B) zinc oxide whisker. The method of claim 1, Furthermore, the composition containing 0.05-2 weight part of 1 or more types chosen from the group which consists of (C) phosphoric acid, hypophosphoric acid, and these salts with respect to 100 weight part of (A) polyarylene sulfide resin. The method of claim 2, (C) The composition is hypophosphite. The method according to claim 1 or 2, Furthermore, the composition containing 1 to 75 weight% of inorganic or organic fillers selected from the group which consists of fibrous fillers, granular fillers, plate-shaped fillers, and mixtures which are not (B) component as (D) component. . The method of claim 1, The composition of the zinc oxide whisker as (B) component previously treated with 1 or more types chosen from the group which consists of an epoxyalkoxysilane and an aminoalkoxysilane. The method of claim 1, (A) The composition whose polyarylene sulfide resin is deionized after superposition | polymerization and whose chlorine content and alkali metal content are each 500 ppm or less. The method of claim 4, wherein (D) The composition contains 3 to 70 weight% of glass fiber or carbon fiber.