JPH107907A - Reinforced polyarylene sulfide resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reinforced PAS resin compsn. which, when brought into contact with water, an acid, an alkali or the like or placed under stress, exhibits suppressed lowering in mechanical properties by incorporating a particular glass fiber into a polyarylene sulfide resin. SOLUTION: This reinforced polyarylene sulfide resin compsn. comprises: (A) 100 pts.wt. polyarylene sulfide resin; and (B) 1 to 300 pts.wt. glass fiber contg. 5 to 40wt.% Zr compd. as ZrO2 . Pref., the reinforced polyarylene sulfide resin compsn. further comprises (C) an alkoxysilane compd. in an amt. of 0.05 to 5 pts.wt. based on 100 pts.wt. polyarylene sulfide resin. Still pref., the reinforced polyarylene sulfide resin compsn. further comprises (D) a polyolefin thermoplastic elastomer in an amt. of 0.5 to 30 pts.wt. based on 100 pts.wt. polyarylene sulfide resin. Still pref., the reinforced polyarylene sulfide resin compsn. further comprises (E) a filler other than the component (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reinforced polyarylene sulfide resin composition containing a specific glass fiber and a molded product thereof. More specifically, it relates to a reinforced polyarylene sulfide resin composition and a molded product having excellent chemical resistance such as acid resistance and alkali resistance and also having excellent stress resistance. It is suitably used as a material or a molded article requiring physical properties.

[0002]

2. Description of the Related Art In recent years, materials for electrical and electronic equipment parts, materials for automobile equipment, parts for chemical equipment, and the like have high heat resistance,
There has been a demand for a flame-retardant thermoplastic resin having mechanical properties, chemical resistance, dimensional stability, and flame retardancy. Polyarylene sulfide (hereinafter abbreviated as PAS) resin typified by polyphenylene sulfide (hereinafter abbreviated as PPS) is also one of the resins that meet this requirement. In general, physical properties are improved by blending a fibrous reinforcing material such as glass fiber. , Its demand is growing. However, PAS resins have the feature of having a sulfur atom in the molecular structure, and their production is mainly based on compounds containing sulfur and chlorine atoms, and by-products containing chlorine and sulfur are produced during synthesis. Due to the manufacturing process, due to impurities and long-term decomposition products, etc., due to the incorporation of glass fiber etc., it initially shows excellent mechanical properties, but gradually decreases its properties,
Particularly under severe conditions, this tendency is remarkable, and improvement is desired. In particular, in recent years, daily living parts that come into contact with water, such as parts for kitchens, bathrooms, toilets, etc., often come into contact with acidic or alkaline cleaning liquids for washing, etc. In many cases, the contact with alkalis or the like increases, and in such applications, the mechanical properties are particularly seriously degraded, and the use is often limited. In addition, these parts are often insert-molded with metal or other members, or after being molded, press-fitted or screwed with metal members, and are often used under stress in these applications. Therefore, a decrease in mechanical properties is a serious problem even when used under such stress. This tendency is more remarkable in applications that come into contact with water, acids, alkalis, and the like, particularly under stress, and becomes a major drawback.
There is a long-awaited improvement.

[0003]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is intended to reduce the mechanical properties of a molded article made of a PAS resin composition reinforced with glass fibers during use, especially
Provided is a reinforced PAS resin composition and a molded product thereof, which are capable of improving the mechanical properties under the conditions of contact with water, acid, alkali or the like, or the conditions of use under stress, and withstanding use under severe conditions. Aim.

[0004]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that a PAS resin composition reinforced with glass fibers or a molded product thereof has a mechanical property such as strength for long-term use. The decrease in physical properties, particularly the decrease in mechanical properties when used under contact with water, acid, alkali, etc. or under stress, is not surprisingly due to aging (deterioration) of the resin itself, but aging of glass fiber used as a reinforcing agent. Caused by the reduction of the reinforcing effect due to the fact that there is considerable difference depending on the type of glass fiber used, and as a result of extensively comparing various glass fibers, as described below, as a general plastic reinforcing agent, Never used,
By selectively using a specific glass fiber containing a Zr compound such as ZrO _2, a reduction in the reinforcing effect over time, particularly, a reduction in the reinforcing effect in the presence of water, acid, alkali, or the like, or under stress. The inventors have found that the present invention is improved, and have completed the present invention. That contrast invention (A) polyarylene sulfide resin 100 parts by weight, and the basic configuration that by blending a glass fiber 1 to 300 parts by weight containing 5 to 40% by weight of (B) Zr compound as ZrO ₂ Reinforced PAS resin composition or molded article. In addition, in addition to the basic structure of the present invention, it is recognized that the effects of the present invention can be further improved by further combining (C) an alkoxysilane compound or (D) an olefin-based thermoplastic elastomer,
Some include such a configuration.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, components constituting the composition of the present invention will be described. The base resin used in the composition of the present invention or its molded product is mainly composed of a PAS resin, and is mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit. Examples of the arylene group include a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, a p, p′-diphenylene sulfone group, a p, p′-biphenylene group, and p, p′-.
A diphenylene ether group, a p, p'-diphenylenecarbonyl group, a naphthalene group and the like can be used. In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, in addition to a polymer using the same repeating unit, that is, a homopolymer, from the viewpoint of processability of the composition,
Copolymers containing heterogeneous repeat units may be preferred. As the homopolymer, one having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group is particularly preferably used. or,
As the copolymer, two or more different combinations among the above-mentioned arylene sulfide groups composed of an arylene group can be used. Among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. Among them, the p-phenylene sulfide group accounts for 70 mol% or more, preferably 80 mol%.
Those containing the above are suitable in terms of physical properties such as heat resistance, moldability, and mechanical properties. Among these PASs, 2
A high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a functional halogen aromatic compound can be particularly preferably used. Alternatively, a polymer having a partially branched or cross-linked structure formed by using a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents can be used, and a low-molecular-weight linear polymer can be used. It is also possible to use a polymer which is heated at a high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by oxidative crosslinking or thermal crosslinking, thereby improving moldability. Also, (A)
The component PAS resin is mainly composed of the linear PAS (having a viscosity of 10 to 300 Pa · s at 310 ° C. and a shear rate of 1200 sec ⁻¹ ), and a part thereof (1 to 30% by weight, preferably 2 to 25% by weight). %) Has a relatively high viscosity (300 to 3000 Pa · s, preferably
A mixed system with a branched or crosslinked PAS resin of 500 to 2000 Pa · s) is also suitable. Further, it is natural that the PAS used in the present invention is preferably one obtained by conducting acid washing, hot water washing and organic solvent washing (or a combination thereof) after polymerization to remove and purify by-product impurities and the like.

[0006] Then the glass fibers used as a reinforcing agent (B) in the present invention, a-described Zr compound ZrO ₂ as ZrO ₂ 5
It is characterized in that it is a glass fiber containing up to 40% by weight, and by containing such a specific component, the continuation of the reinforcing effect as a reinforcing composition aimed at by the present invention, particularly acid resistance, alkali resistance and stress resistance A noticeable improvement in the persistence of the reinforcing effect below is observed. Such a specific glass fiber is known as an AR glass (alkali resistant glass) mainly as a reinforcing material for cement, but is generally used as a reinforcing agent for a synthetic resin, and is substantially free of ZrO ₂ , E glass and C glass. As described above, when used as a reinforcing agent for PAS, it is excellent not only in alkali resistance but also in acid resistance, and also has an excellent effect under stress. The composition of the glass fiber (B) used in the present invention is a silicon compound (SiO ₂ ), which is a main component of general glass, in addition to the above ZrO _2.
And alkali metal compounds (Na ₂ O, K ₂ O,
Li ₂ O), alkaline earth metal compounds (CaO, MgO, etc.),
General glass components such as Al, Fe, and Ti compounds may be contained. The content of the essential component is Zr compound of glass fiber for use in the present invention (B) is 5 to 40 wt% as ZrO _2, preferably 10 to 30 wt%. If the amount is less than 5% by weight, the desired effect of the present invention cannot be obtained, and if it exceeds 40% by weight, the melting temperature of the glass rises, which makes it difficult to form and process fibrous materials. The shape of the glass fiber (B) used in the present invention is not particularly limited and may be appropriately adjusted and used depending on the purpose. Generally, the average diameter is 3 to 25 μm, preferably 5 to 20 μm, and the length is 50 μm.
μm to several mm, the aspect ratio of which is at least 5 or more,
It is preferably 10 or more, and when dispersed in the final molded product, the average length is 30 μm to 1 mm, and the average aspect ratio is 5 to 200.
And preferably about 10 to 100. From the viewpoint of the reinforcing effect, the average length and the average aspect ratio are preferably as large as possible.
When the processability and the anisotropy of the molded product become large and the dimensional accuracy (warpage deformation) tends to be difficult, the fiber length and the aspect ratio are relatively small when the processability and the anisotropy are problematic. In some cases, smaller ones (so-called milled fibers) are preferred. The amount of the glass fiber (B) is at least 1 part by weight, preferably at least 5 parts by weight, particularly preferably at least 5 parts by weight, based on 100 parts by weight of the PAS resin (A) in terms of rigidity and mechanical properties.
The amount is at least 10 parts by weight, and the upper limit is at most 300 parts by weight, preferably at most 250 parts by weight, particularly preferably at most 200 parts by weight, from the viewpoint of the preparation and processability of the composition. In using the glass fiber as the component (B), it is preferable to use a glass fiber which has been subjected to a surface treatment or a convergence treatment from the viewpoint of improving mechanical strength and handling properties. Examples of the surface treatment agent include functional compounds such as an epoxy compound, an isocyanate compound, a silane compound, and a titanate compound. In particular, the silane compounds described below are also particularly suitable as a surface treatment agent, and are secondarily effective in obtaining the desired effects of the present invention. As the sizing agent, a sizing agent generally used such as urethane type, epoxy type and acrylic type is used.

Next, the composition of the present invention is preferably, but not necessarily, further added with an alkoxysilane compound (C). The alkoxysilane (C) comprises at least one selected from the group consisting of aminoalkoxysilane, vinylalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane and allylalkoxysilane. As aminoalkoxysilane,
One molecule has one or more amino groups and two alkoxy groups
Any of the silane compounds having three or three is effective, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane , N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like. As the vinylalkoxysilane, any silane compound having one or more vinyl groups in one molecule and having two or three alkoxy groups is effective. For example, vinyltriethoxysilane, vinyltrimethoxysilane , Vinyl tris (β-methoxyethoxy)
Silane and the like. As the epoxyalkoxysilane, any silane compound having one or more epoxy groups in one molecule and having two or three alkoxy groups is effective. For example, γ-glycidoxypropyltrimethoxysilane is effective. , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like. As a mercaptoalkoxysilane, any silane compound having one or more mercapto groups in one molecule and having two or three alkoxy groups is effective.
For example, γ-mercaptopropyltrimethoxysilane, γ
-Mercaptopropyltriethoxysilane and the like. As the allylalkoxysilane, one molecule has at least one allyl group and two or three alkoxy groups.
Any silane compound is effective as long as it has, for example, γ-diallylaminopropyltrimethoxysilane, γ-allylaminopropyltrimethoxysilane,
γ-allylthiopropyltrimethoxysilane and the like. The combined use of the alkoxysilane compound is particularly effective in increasing the affinity between the specific glass fiber (B) of the present invention and the PAS resin to obtain the desired effects of the present invention. Among them, for the purpose of the present invention, Among the above silane compounds, aminoalkoxysilane is most preferred. The amount of the alkoxysilane (C) is 5 parts by weight per 100 parts by weight of the PAS resin (A).
It is not more than 0.1 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight. If it is too large, the viscosity of the composition increases, which is not preferable. The above-mentioned alkoxysilane may be added to the surface of the glass fiber (B) in advance as a surface treating agent as described above, or may be added separately from the glass fiber (B). Especially effective.

Next, although not necessarily an essential component of the composition of the present invention, the combined use of a polyolefin-based thermoplastic elastomer (D) improves the toughness and the stress applied to the filled glass fibers. Is effective in maintaining physical properties under stress, and particularly, acid resistance and alkali resistance under stress can be improved. The olefin-based thermoplastic elastomer (D) used herein is a copolymer or a graft copolymer mainly composed of the following α-olefin. That is, a) ethylene and an α-olefin having 3 or more carbon atoms (eg, propylene, 1-butene, 1-hexene, 4-methyl-
B) α-olefin (eg, ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc.)
Copolymer of α, β-unsaturated carboxylic acid or an ester thereof (eg, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, or their alkyl esters, glycidyl esters, anhydrides, etc.) c-1) In the above a), an α, β-unsaturated carboxylic acid or a derivative thereof (for example, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, or an alkyl ester, glycidyl ester, or anhydride thereof) is used. C-2) Graft copolymer obtained by graft-polymerizing at least one of a vinyl compound such as styrene and acrylonitrile or an α, β-unsaturated carboxylic acid or a derivative thereof to the copolymer of b) above. And the like. These a) to c) olefin-based copolymers or graft copolymers may be used alone or as a mixture of two or more kinds. Further, each of them may be (co) polymerized or graft-polymerized stepwise. Also preferred are polymers having a multilayer structure. These olefin-based elastomers have a higher affinity with the PAS resin than other elastomers, and have a good interaction with the glass fiber (B), and are extremely effective in promoting the effects aimed at by the present invention. . Particularly preferred substances are a graft-modified product obtained by graft copolymerizing maleic anhydride or maleic imide onto a copolymer of ethylene and propylene or 1-butene, an ethylene-alkyl acrylate copolymer, and maleic anhydride. A graft modified product obtained by graft copolymerization of α-olefin, especially a copolymer of ethylene with glycidyl acrylate or glycidyl methacrylate, and styrene, acrylonitrile, alkyl acrylate, alkyl methacrylate, etc. And a graft copolymer obtained by graft polymerization of at least one of the above. Polyolefin-based thermoplastic elastomer
The amount of (D) is 30 parts by weight or less, preferably 0.5 to 30 parts by weight, particularly preferably 2 to 20 parts by weight, per 100 parts by weight of the PAS resin (A). If it is too small, the effect is not enough,
If it is too large, there is a problem in heat resistance, which is not preferable.

The composition of the present invention may further contain other thermoplastic resins such as a polyester resin, a polyamide resin (including any liquid crystal), a polystyrene resin, and the like, depending on the purpose. You can do it.

In addition to the specific glass fiber reinforcing agent (B), which is an essential component of the present invention, the composition of the present invention comprises the component (E) for improving the dimensional stability and electrical properties of the molded article. And other fibrous reinforcing agents and / or non-fibrous fillers (granular or plate-like fillers) can be used in combination. Examples of the fibrous filler belonging to the component (E) include inorganic fibrous substances such as organic fibers represented by aramid fibers, carbon fibers, and potassium titanate fibers.

[0011] The particulate fillers include carbon black, graphite, silica, quartz powder, glass beads or glass powder (preferably the same as the component (B)), calcium silicate, aluminum silicate, talc, clay. Silicates, such as diatomaceous earth, diatomaceous earth, wollastonite, and oxides of metals such as iron oxide, titanium oxide, zinc oxide, and alumina, as well as metal carbonates such as calcium carbonate and magnesium carbonate, and sulfuric acid Sulfates of metals such as calcium and barium sulfate, other silicon carbide, silicon nitride, and various metal powders. Examples of the plate-like filler include mica, glass flake (preferably the same as the component (B)), graphite, metal foil, and the like. In addition, a hollow filler such as a shirasu balloon, a metal balloon, or a glass balloon may be added from the viewpoint of weight reduction. These fillers can be used alone or in combination of two or more. In particular, the combination of glass fiber (B) with carbon fiber or potassium titanate fiber, or the combination of granular and / or plate-like fillers is a combination that is particularly preferable in terms of having both mechanical strength, dimensional accuracy, and electrical properties. It is. The total amount of the filler used is 300 parts by weight or less, preferably 5 to 250 parts by weight, particularly preferably 10 to 200 parts by weight, per 100 parts by weight of the polyarylene sulfide resin including the component (B). If the total amount of the filler is excessive, the molding operation becomes difficult, and the mechanical properties of the molded product are disadvantageously undesirably increased. These fillers are component (B)
It is preferable to use a functional compound such as an epoxy compound, an isocyanate compound, a silane compound or a titanate compound or a polymer which has been subjected to a surface treatment or a convergence treatment in the same manner as described above.

The composition of the present invention may contain, if necessary, various stabilizers such as a flame retardant, an antioxidant, an ultraviolet ray inhibitor, a lubricant, a release agent, a nucleating agent, a foaming agent, a crosslinking agent, a coloring agent, etc. It is also possible to add known additives.

The composition of the present invention can be prepared by various known methods. Generally, it is prepared by adding the glass fiber (B) to the PAS resin (A) and, if necessary, further adding other components as described above, followed by heating, melting and kneading. For example, necessary components are uniformly mixed in advance with a mixer such as a tumbler or a Henschel mixer, and then supplied to a single-screw or twin-screw extruder to perform a melt-kneading process to produce pellets.
At this time, all the components may be added simultaneously or separately. The kneading temperature is 5 times higher than the temperature at which the resin component melts.
C. to 100.degree. C., particularly preferably 10 to 60.degree. C. higher than the melting point of the resin. The composition of the present invention is applicable to various molding methods and can be molded into various molded articles. That is, not only is it suitable for injection molding,
It can also be applied to extrusion molding (round bars, pipes, etc.), blow molding (various hollow molded products), vacuum molding or compression molding. In particular, it is suitable for a molded product having any one of a metal insert portion, a press-fit portion, and a screw portion, which is used in applications that come into contact with water, an acid, an alkali, or the like under stress.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. The components shown in the table were mixed with a Henschel mixer for 5 minutes, and the mixture was melt-kneaded in a twin-screw extruder having a cylinder temperature of 310 ° C. to produce resin composition pellets. Then, the pellets are subjected to injection molding machine at a cylinder temperature of 320 ° C and a mold temperature of 320 ° C.
At 150 ° C, bend test specimens are formed in accordance with ASTM D790, and the test specimens are subjected to the following liquids (or atmospheres) in a state where no stress is applied or in a state where predetermined stress is applied by using a specific fixture. ) For 500 hours (or left), and measure the bending strength and strain of the test piece before and after that (ASTM D790
), And its retention was determined. The test liquid (or atmosphere) used is as follows. (I) 10% hydrochloric acid aqueous solution (23 ° C) (II) 10% sulfuric acid aqueous solution (23 ° C) (III) 10% caustic soda aqueous solution (23 ° C) (IV) Water (80 ° C) (V) Air (120 ° C) Specific substances of each component used in Examples and Comparative Examples are as follows. (A) Polyphenylene sulfide (PPS) resin Fortron KPS manufactured by Kureha Chemical Industry Co., Ltd. (B) Glass fiber AR glass: (AR-1: about 20% of ZrO ₂ , and AR-2:
ZrO _2: about 15%) does not include E glass :( substantially ZrO ₂₎ C glass :( substantially ZrO ₂ not included) (C) alkoxysilane aminopropyltriethoxysilane (D) an olefin-based elastomer D-1: ethylene D-2: A graft copolymer obtained by grafting a styrene / acrylonitrile copolymer onto a glycidyl methacrylate copolymer and maleic anhydride onto an ethylene / ethyl acrylate copolymer Examples 1-4 Comparative Examples 1 to 4 Table 1 shows a comparison according to the type of glass fiber when immersion treatment was performed in an aqueous hydrochloric acid solution (I) under no stress. Examples 5 to 9 and Comparative Examples 5 to 10 Table 2 shows a comparison according to the type of glass fiber when immersed in an aqueous hydrochloric acid solution (I) with a predetermined stress applied. Examples 10 to 11 and Comparative Examples 11 to 14 Table 3 shows a comparison in the case of immersion in a sulfuric acid aqueous solution (II) or a caustic soda aqueous solution (III) under no stress. Examples 12 to 13 and Comparative Examples 15 to 18 Table 4 shows a comparison in the case of immersion treatment in a sulfuric acid aqueous solution (II) or a caustic soda aqueous solution (III) under a predetermined stress. Examples 14 to 15, Comparative Examples 19 to 22 Under predetermined stress, water (80 ° C) (IV) or air (120
Table 5 shows the results when the sample was left at (° C.) (V). Examples 16 to 20, Comparative Examples 23 to 27 In addition to the (A) (B) component, and further (C) alkoxysilane and / or (D) a test piece blended with an olefin elastomer under no stress, or a predetermined stress Table 6 shows a comparison in the case of immersion in a hydrochloric acid aqueous solution (I) below.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

[Table 3]

[0018]

[Table 4]

[0019]

[Table 5]

[0020]

[Table 6]

[0021]

As described in the above description and the examples, the reinforced PAS resin composition containing the specific glass fiber of the present invention, and the molded product thereof may be subjected to severe conditions, especially contact with water, acid, alkali or the like or application of stress. The decrease in mechanical properties under the specified conditions is remarkably improved, and the composition is suitable for applications used under such conditions.

Claims (6)

[Claims] (A) Polyarylene sulfide resin 100
The weight part, (B) Zr compound by blending the glass fiber 1 to 300 parts by weight containing 5 to 40 wt% as ZrO ₂ reinforced polyarylene sulfide resin composition. 2. The method according to claim 1, wherein the alkoxysilane compound (C) is used in an amount of 0.05 to 100 parts by weight of the polyarylene sulfide resin.
The reinforced polyarylene sulfide resin composition according to claim 1, which is blended in an amount of 5 parts by weight. 3. The reinforced polyarylene sulfide resin composition according to claim 1, further comprising 0.5 to 30 parts by weight of (D) a polyolefin-based thermoplastic elastomer per 100 parts by weight of the polyarylene sulfide resin. 4. The reinforced polyarylene sulfide resin composition according to claim 1, further comprising a filler other than the component (B) as the component (E). 5. A molded article comprising the reinforced polyarylene sulfide resin composition according to claim 1. 6. A molded article comprising the reinforced polyarylene sulfide resin composition according to any one of claims 1 to 4, and having any one of a metal insert portion, a press-fit portion, and a screw portion.