WO1999016830A1

WO1999016830A1 - Polyarylene sulfide resin composition

Info

Publication number: WO1999016830A1
Application number: PCT/JP1998/004265
Authority: WO
Inventors: Masaaki Nakamura; Hiroyuki Amano
Original assignee: Polyplastics Co., Ltd.
Priority date: 1997-09-29
Filing date: 1998-09-22
Publication date: 1999-04-08
Also published as: JP3624077B2; KR20010030731A; DE19882709T1; TW492988B; JPH11100505A; CN1272124A; DE19882709B4; CN1165583C; KR100527220B1

Abstract

A polyarylene sulfide resin composition excellent in moldability and particularly capable of forming moldings having excellent mechanical properties without corroding or staining metallic parts such as molds in the course of the molding, which comprises 100 parts by weight of (A) a polyarylene sulfide resin and 0.05 to 3 parts by weight of (B) zinc oxide whiskers.

Description

Description Polyarylene Sulfide Resin Composition Background of the Invention

Technical field:

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 or contaminate a metal part such as a mold during molding, and has excellent mechanical properties of a molded product.

Conventional technology:

Polyarylene sulfide (hereinafter abbreviated as PAS) represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. It is widely used in electrical and electronic equipment parts materials, automotive equipment parts materials, chemical equipment parts materials, and so on.

However, this resin has an iodine atom in its molecular structure, and the raw material for production has an alkyd metal such as iodine and sodium. It has the disadvantage that by-products containing a large amount of, etc. are generated, has the disadvantage of corroding and contaminating metal materials such as molds during molding, There are problems such as corrosion and contamination of the inserted metal, plating or deposited metal, which causes problems.

As a means to solve this problem, the polymerized PAS resin should be deionized with acid, hot water, organic solvent, etc., washed and reduced to 500 ppm or less, and even 200 ppm or less. Although PAS resins and their compositions are extremely effective at molding temperatures of at least 280 or higher, these Even after removal and purification of impurities, corrosive gas is generated during molding, and the corrosion resistance to metals is not sufficient.

As a technique for solving this problem, proposals have been made to add a harmful substance supplement to the resin to suppress the corrosiveness and the generation of impurities. For example, lithium carbonate (JP-A-54-162752), hydrated talcite (JP-A-61-275353), zinc carbonate, zinc hydroxide (JP-A-2-105857), zinc borate (Japanese No. 6-306288). However, in the additional tests by the present inventors, although certain additives have a certain effect in preventing metal corrosion, they are still inadequate, and the addition of a small amount causes problems such as a decrease in mechanical properties. Admitted. Japanese Patent Application Laid-Open No. 4-1644961 shows an example in which a specific zinc oxide is added, but it is still difficult to say that the mechanical properties are sufficient, and further improvement is desired.

In view of the above problems, the present invention improves the corrosion and contamination of a metal during the molding of the PAS resin composition and the metal when the PAS resin composition is used, and improves the bow I tensile strength and elongation even when a relatively large amount of a corrosion inhibitor is used. An object of the present invention is to provide a PAS resin composition having excellent metal corrosion resistance and mechanical properties without causing any adverse effects on mechanical properties such as impact strength and toughness. DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to achieve the above object, and as a result, by adding specific zinc oxide to PAS resin, corrosion and contamination of metals have been significantly improved, The present inventors have found that the adverse effect on the mechanical properties due to the strong corrosion inhibitor has been eliminated, the excellent mechanical properties have been maintained, and both properties have been obtained, and the present invention has been completed.

That is, the present invention

(A) 100 parts by weight of polyarylene sulfide resin (B) Zinc oxide whisker 0.05-3 parts by weight

Is a polyarylene sulfide resin composition prepared by blending as a basic constituent and melt-kneading.

That is, the present invention is a polyarylene sulfide resin composition containing (A) 100 parts by weight and (B) 0.05 to 3 parts by weight. DETAILED DESCRIPTION OF THE INVENTION:

Hereinafter, the components of the present invention are described in detail.

The PAS resin as the component (A) in the composition of the present invention is mainly composed of-(Ar-S)-(where AT is an arylene group) as a repeating unit. Examples of the arylene group include p-phenylene group, m-phenylene group, 0-phenylene group, substituted phenylene group, ρ, ρ′-diphenylene sulfone group, ρ, ρ′— Biphenylene group, ρ'ρ'-diphenylene ether group, ρ, ρ'-diphenylenecarponyl group, naphthylene group and the like can be used. In this case, in the arylene sulfide group composed of the above-mentioned arylene group, in addition to a polymer using the same repeating unit, that is, a homopolymer, a heterogeneous repeating unit is used from the viewpoint of processability of the composition. Included copolymers may be preferred.

As the homopolymer, those having a phenylene sulfide group as a repeating unit using a ρ-phenylene group as an arylene group are particularly preferably used. As the copolymer, two or more different combinations of the arylene sulfide groups consisting of the above-mentioned arylene groups can be used. Combinations are particularly preferred. Among them, those containing a P-phenylene sulfide group in an amount of 70 mol% or more, preferably 80 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. Among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used. In addition to the PAS resin having a structure, a polymer in which a partially branched or crosslinked structure is formed by using a small amount of a monomer such as a polyhaloaromatic compound having three or more halogen substituents during condensation polymerization. One can also be used, or a polymer with a low molecular weight linear structure polymer heated at high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by oxidative crosslinking or thermal crosslinking and improve moldability. It is possible.

Further, (A) component PAS resin, the linear PAS (310 ", a viscosity at shear rate 1200sec one ¹ 10 to 300 Pa 's) as a main component, a part (1 to 30 wt%, preferably Is 2 to 25% by weight), but a mixed system with a branched or cross-linked PAS resin having a relatively high viscosity (300 to 3000 Pa · s, preferably 500 to 2000 Pa · s) is also suitable.

After polymerization, the PAS resin used in the present invention is subjected to deionization treatment such as acid washing, hot water washing, and organic solvent washing (or a combination thereof) to remove and purify by-product impurities. It is preferable that the content of chlorine and the content of alkali metal are each 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 (minor diameter) of 0.1 to 5 m and an average fiber length (major diameter) of 2 to 2 at the needle portion measured by microscopy. It is preferable that the average aspect ratio is 5 to 100 urn. Among commercially available products, zinc oxide having a three-dimensional tetrapot shape is one of the compounds suitable as a whisker having the above-mentioned shape, but is not limited thereto.

The amount of the component (B) is 0.05 to 3 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the polyarylene sulfide resin. At 0.05 parts by weight, the effect of preventing corrosion of metals and the effect of suppressing contamination are not sufficient. 3 parts by weight If it exceeds P, the same mechanical properties as in the case where the component (B) is not blended cannot be maintained.

Further, it is preferable to previously treat the surface of the component (B) having zinc oxide wiping power with epoxyalkoxysilane and / or aminoalkoxysilane from the viewpoint of maintaining dispersibility and mechanical properties. Epoxyalkoxysilane is effective as long as it is a silane compound having one or more epoxy groups in one molecule and having two or three alkoxy groups, for example, α-glycidoxypropyl trimethoxy. Examples thereof include silane and α-glycidoxypropyltriethoxysilane. As the aminoalkoxysilane, any silane compound having one or more amino groups in one molecule and having two or three alkoxy groups is effective. For example, aminopropyltrimethoxy can be used. Examples include silane, araminopropyltriethoxysilane, and N-(-aminoethyl) 1-aminopropyltrimethoxysilane.

The amount of these alkoxysilanes is preferably 0.05 to 5% by weight based on the zinc oxide wiping power of the component (B).

In the present invention, it is preferable that phosphoric acid or hypophosphorous acid or a salt thereof is further blended as the component (C) because long-term wet heat resistance can be improved.

The (C) phosphoric acid or hypophosphorous acid or a salt thereof used herein includes, for example, primary phosphoric acid, hypophosphorous acid, calcium phosphate monobasic, sodium phosphate monobasic, calcium hypophosphite, zinc hypophosphite, At least one or two or more selected from salts of zinc, alkali metal, and alkaline earth metal such as magnesium hypophosphite and sodium hypophosphite, and preferably calcium hypophosphite, Magnesium phosphate and zinc hypophosphite. The above components are compounded in the following amounts: (A) polyarylene sulfide resin

It is 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight. If the amount is too small, the desired effect of improving the long-term wet heat resistance cannot be obtained. If it is, there is a problem such as gas generation during molding, which is not preferable.

By coexisting component (C) with component (B), surprisingly, the interaction between both components is prevented without impairing the effect of preventing the corrosion of metals and the effect of suppressing the contamination of component (B). It was confirmed that the long-term wet heat resistance was improved. In particular, it is effective to mix the component (C) as it is, but it is effective to pre-adhere part or all of it to the inorganic or organic filler, which is the component (D) described later, and mix it with other components Is also effective. There is no particular limitation on the method of adhering the component (C). For example, a solution containing the above compound may be sprayed onto the filler, and the filler may be adhered. Alternatively, the above solution may be applied by applying the solution. It is also possible to treat with a sizing agent based on epoxy resin or urethane resin, which is generally used as a surface treatment agent for glass fiber, or a coupling agent such as aminosilane or epoxysilane.

The inorganic or organic filler of the component (D) used in the present invention is not necessarily an essential component, but may have performance such as mechanical strength, heat resistance, dimensional stability (warpage, deformation), and electrical properties. In order to obtain an excellent molded product, it is preferable to mix them, and for this purpose, a fibrous, powdery, or plate-like filler or a mixture thereof is used according to the purpose. Examples of the fibrous filler 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, and stainless steel. And inorganic fibrous materials such as fibrous materials of metals such as aluminum, titanium, copper, and brass. Particularly typical fibrous fillers are glass fibers, carbon fibers or potassium titanate fibers. In addition, a high melting point organic fibrous substance such as an aromatic polyamide, an acrylic resin, or a fluororesin can also be used.

On the other hand, the granular fillers include carbon black, graphite, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, and tar. Silicates such as clay, clay, diatomaceous earth, wollastonite, oxides of metals such as iron oxide, titanium oxide, and alumina; carbonates of metals such as calcium carbonate and magnesium carbonate; metals such as calcium sulfate and barium sulfate And silicon carbide, silicon nitride, and various metal powders. Particularly typical ones are carbon black, silica, glass beads or glass powder, calcium carbonate, talc and the like.

Further, examples of the plate-like filler include My force, glass flake, various metal foils, and the like.

These fillers can be used alone or in combination of two or more. The combined use of a fibrous filler, particularly a glass fiber or a carbon fiber, and a powdery or plate-like filler is a preferable combination, particularly in terms of having both mechanical strength, dimensional accuracy, electrical properties and the like.

When using these fillers, it is desirable to use surface treatment or convergence with a sizing agent or a surface treatment agent if necessary. Examples of the treating agent include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds.

The amount of the component (D) is from 1 to 75% by weight, preferably from 3 to 70% by weight, based on the total amount of the composition. If it is too large, the molding operation becomes difficult, and there is a problem in the mechanical strength of the molded product.

Further, as the molded article composition used in the present invention, known substances generally added to thermoplastic resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, flame retardants, coloring agents such as dyes and pigments, A lubricant, a crystallization accelerator, a crystal nucleating agent, and the like can be appropriately added according to required performance.

The resin composition of the present invention can be prepared by equipment and methods generally used for preparing a synthetic resin composition. Generally, necessary components can be mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form a pellet for molding. In addition, the resin component is melt-extruded, and an inorganic component such as glass fiber is added during the extrusion. Mixing is one of the preferred methods.

The material pellets obtained in this manner can be molded by a generally known thermoplastic resin molding method such as injection molding, extrusion molding, vacuum molding, compression molding, etc., but the most preferred is injection molding. . EXAMPLES Next, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. -Examples 1 to 14 and Comparative Examples 1 to 10

As the component (A), a substantially linear polyphenylene sulfide resin (Kureha Chemical Industry Co., Ltd., “Fortron KPS”) having a viscosity of 50 Pa · s (310, 1200 sec- ¹ ) 100 parts by weight, The components (B) were added and mixed for 2 minutes with a Henschel mixer as shown in Tables 1 and 2. Further, the components (C) and (D) were added in the amounts shown in Tables 1 and 2 and mixed with a blender for 30 seconds. Was kneaded with an extruder at a cylinder temperature of 310 ° C. to prepare a pellet of a polyphenylene sulfide resin composition.Corrosion properties to metals, mechanical properties and long-term wet heat resistance of this pellet were measured. Example 15

A solution of (C) calcium hypophosphite dissolved in a solvent was applied to the glass fiber of component (D) in the ratio shown in Table 2, dried sufficiently, and used in a state where it was adhered in advance. Except for the above, a composition was prepared and evaluated under the same conditions as in the above example. Table 2 shows the results.

The evaluation method is as follows.

(Corrosion resistance)

Add 4 g of the above pellet to the bottom of a test tube with an inner diameter of 18 mm and a height of 160 mm. A test piece (15 X 160 X 2 mm) of a mold material (SKD-11) mainly composed of chromium and carbon was hung at a predetermined position. After stoppering the top of the test tube and heating at 320T for 3 hours, take out the test piece and observe it visually and with a microscope to examine the corrosion state.Relative grading according to the degree of the corrosion state is as follows. went.

A B C D E Small corrosive Large corrosive

(Tensile strength and elongation)

Tensile test pieces were molded using an injection molding machine at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C, and the test pieces were measured for bow I tensile strength and tensile elongation in accordance with ASTM D-638. (Long-term wet heat resistance)

Tensile test specimens were molded using an injection molding machine at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C. The test specimens were treated in hot water at 95 ° C for 500 hours, and in accordance with ASTM D-638, The tensile strength was measured.

Table 1 Composition evaluation

(A) PPS (B) Male male (Q component (D) 3¾ ^ 'J Erosive Tensile old work force After inspection Army top type Armpit type Armpit type Cliff (MPa) (%) Tension

(MPa) Difficult case 1 100 B-1 0.05 C 89 4.9 89

100 B-1 0.5 A 90 5.0 90

Wmwi 3 100 B-1 1 1 1 1 1 A 90 5.0 90

1 100 E 89 4.8 89 Row 4 100 B-1 0.05 Glass fiber 40 Β 190 1.9 133 σ Row b 100 B-1 0.5 Glass fiber 40 A 190 1.9 133 Sample 6 100 B-1 1 Glass β 40 A 189 1.8 132 Case 7 100 B-1 3 Glass fiber II 40 A 189 1.7 131 Row 8 100 B-1 0.5 Glass fiber 30 A 135 1.1 95 Charcoal art ゥ 30

Bell row 9 100 B-2 0.5 Glass thread 40 A 189 1.9 132

10 100 B-3 0.5 Glass thread 40 A 184 1.7 128 Row 11 100 B-1 0.5 C-1 0.3 Glass thread 40 A 190 1.9 181 \ 12 100 B-1 1 C-1 0.3 Glass thread 40 A 189 1.8 180 None 13 100 B-1 0.5 C-1 0.3 Glass 30 A 135 1.1 127 Fiber-¾ 30

Table 2 Composition evaluation

(A) PPS (B) Erosion-resistant (Q component (D) ¾¾¾ Erosive Tensile old Tensile elongation After moisture treatment Weight part type Car wash part type Military halo part type Military halo% (MPa) (%)

(MPa) Vulgar 2 100 Glass fiber 40 E 190 1.9 133 Contract 3 100 B-4 0.5 Glass fiber release 40 A 152 1.3 106 Fine 4 100 B-5 0.5 Glass fiber ίέ 40 A 161 1.4 113 Vulgar 5 100 B-6 0.5 Glass β 40 A 162 1.4 113

J: 6 100 ZnC0 ₃ 0.5 Glass fiber ET 40 A 164 1.4 107 Fine 7 100 Ii ₂ C0 ₃ 0.5 Glass fiber PLUS 40, B 166 1.4 116 m 8 100 CaC0 ₃ 0.5 Glass suspension ft 40 E 181 1.7 129 Row 9 100 Glass citrine 30 D 135 1.1 95 Chargeum 30

Example 14 A-1 100 Bl 0.05 Glass fiber 40 B 188 1.9 132 m 10 A-1 100 Glass gallery 40 D 188 1.9 132 132 Example 15 100 Bl 0.5 C-1 0.3 Glass complexity 40 A 190 1.9 183

note:

(A) PPS

(A-l); Use deionized PPS

(B) Corrosion inhibitor

(B-1) Matsushita Amtec Co., Ltd., zinc oxide whisker (epoxysilane treatment), average fiber diameter (short diameter) = 0.3, average fiber length (long diameter) = 4 m

(B-2) Matsushita Amtech Co., Ltd., zinc oxide whisker (aminosilane treatment), average fiber diameter (short diameter) = 0.3 m, average fiber length (long diameter) = 4 z _m

(B-3) Matsushita Amtech Co., Ltd., zinc oxide whisker (untreated), average fiber diameter (short diameter)

= 0.3 μ-m, average fiber length (major diameter) = 4

(B-4) Mitsui Kinzoku Mining Co., Ltd., zinc oxide (dry method), average particle size = 0.7 iim

(B-5) Sakai Chemical Co., Ltd., zinc oxide (dry method), average particle size = 0.04 m

(B-6) Sakai Chemical Co., zinc oxide (wet method), average particle size = 0.02 im

(C) Ingredient

rc-i) Calcium hypophosphite

Claims

The scope of the claims

1. A polyarylene sulfide resin composition comprising (A) 100 parts by weight of a polyarylene sulfide resin and (B) 0.05 to 3 parts by weight of a zinc oxide whisker.

2. In addition, (C) 0.05 to 2 parts by weight of (C) at least one selected from the group consisting of phosphoric acid, hypophosphorous acid and salts thereof with respect to 100 parts by weight of polyarylene sulfide resin. A composition according to claim 1.

3. The composition according to claim 2, wherein the component (C) is hypophosphite.

4. In addition, as the component (D), an inorganic or organic filler selected from the group consisting of fibrous fillers, granular fillers, plate-like fillers, and mixtures thereof other than the component (B) is 1 to 75 weight%. The composition according to claim 1 or 2, wherein the composition comprises the total amount of the composition.

5. The composition according to claim 1, wherein the surface of the zinc oxide wiping power of the component (B) is treated in advance with at least one member selected from the group consisting of epoxyalkoxysilanes and aminoalkoxysilanes.

6. The composition according to claim 1, wherein (A) the polyarylene sulfide resin is deionized after polymerization, and has a chlorine content and an aluminum metal content of 500 ppm or less, respectively.

7. The composition according to claim 4, wherein the component (D) is glass fiber or carbon fiber and contains 3 to 70% by weight.