JP2834639B2 - Polyarylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to an improved polyarylene sulfide resin composition. More particularly, the present invention relates to a reinforced polyarylene sulfide resin composition having improved corrosion and stain resistance to metals.

[0002]

2. Description of the Related Art In recent years,
Electrical and electronic equipment parts materials, automobile equipment parts materials, and chemical equipment parts materials are required to have thermoplastic resins having high heat resistance, chemical resistance, and flame retardancy. Polyarylene sulfide resins represented by polyphenylene sulfide are also one of the resins that meet this demand, and demand is growing due to their good cost-performance ratio. However, this resin has the feature that it has sulfur atoms in its molecular structure, and the disadvantage that the raw materials for production contain sulfur atoms and chlorine atoms, and by-products containing chlorine and sulfur are produced during resin synthesis. If you have long-term use of metal equipment, especially molding dies, in the area of contact with the molding machine during molding of the resin for a long period of time, these harmful substances and gases generated by decomposition of the resin Corrosion or contamination of the metal part occurs, and, when used as a molded part material such as a metal insert molded article for a long period of time at a high temperature for a molded article used in contact with the metal,
There is a problem that the plated or vapor-deposited metal surface is eroded and contaminated, and cannot perform its function sufficiently.
As a technique for solving this problem, the following has conventionally been proposed. (1) Strengthen the purification process in the resin manufacturing process and reduce the amount of impurities mixed into the resin. (2) Actively add scavengers for harmful substances to the resin to suppress the generation of corrosive impurities. For example, lithium carbonate (Japanese
JP-A-54-162752, JP-A-60-229949), hydrotalcite (JP-A-61-275353), zinc oxide (JP-A-59-181408), zinc carbonate, zinc hydroxide ( JP-A-2-105857) and the like. (3) Treat the resin at a high temperature of 200 ° C or higher to reduce corrosive gas before use. However, each of these methods has a problem and is not a sufficient solution. In other words, in the follow-up test by the present inventors, the method of strengthening the resin washing by the method (1) has a limit that the content of harmful impurities can be greatly reduced, but the metal corrosion property is not sufficiently improved, and It is not preferable because the cost of the resin is high. Regarding the method (2), in the additional tests by the present inventors, certain additives have a certain effect in preventing metal corrosion, but they are still insufficient, and
There is also a problem that a small amount of the compound causes a decrease in mechanical properties, and further improvement is desired. The method (3) has a large influence of side effects such as discoloration and deterioration of the resin main body at a high temperature, is complicated in operation, and is not a satisfactory method.

[0003]

Means for Solving the Problems The present inventors deteriorate the excellent mechanical properties, heat resistance, solvent resistance, flame retardancy, etc. of a polyarylene sulfide resin composition, particularly a polyphenylene sulfide resin composition. In order to improve metal corrosion and contamination during and after molding, attention was paid to metal corrosive substances contained in resin or its composition and gas generated when heated, and these harmful substances were effectively treated. To significantly reduce metal corrosion and contamination, and to improve other physical properties such as mechanical properties , especially of glass fiber as a reinforcing agent.
An additive that does not adversely affect the reinforcing effect was searched. As a result, the addition of a small amount of zinc borate is particularly effective, and significantly suppresses the corrosiveness and contamination of various metals, and has a bad effect on other physical properties , particularly on the reinforcing effect of glass fiber as a reinforcing agent. > We found that there was no effect and completed the present invention. That is, the present invention comprises (A) 100 parts by weight of a polyarylene sulfide resin, (B) 0.05 to 10 parts by weight of zinc borate having an average particle size of 50 μm or less, and (C) 10 to 250 parts by weight of glass fiber as a reinforcing agent. A reinforced polyarylene sulfide resin composition having improved corrosion and contamination properties for metals.

[0004] The polyarylene sulfide (hereinafter abbreviated as PAS) resin as the component (A) in the composition of the present invention is mainly composed of repeating units (-Ar-S-) (where Ar is an arylene group). It is. Arylene group (-A
Examples of r-) include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group (provided that the substituent is an alkyl group, preferably a C _{1 to} C ₅ alkyl group, or a phenyl group), , p'-diphenylene sulfone group, p, p '
-Biphenylene group, p, p'-diphenylene ether group, p,
p'-diphenylenecarbonyl group, naphthalene group and the like. In this case, in the arylene sulfide group composed of the above-mentioned arylene group, a polymer having the same repeating unit, that is, a homopolymer can be used,
From the viewpoint of processability of the composition, a copolymer containing a heterogeneous repeating unit may be preferable in some cases. As the homopolymer, polyphenylene sulfide (hereinafter abbreviated as PPS) using p-phenylene sulfide group as a repeating unit using p-phenylene group as an arylene group
Is a typical one, and among them, substantially linear PPS is particularly preferably used. As the copolymer, an arylene sulfide group composed of the above-described arylene group can be used as a main component, and a copolymer composed of two or more different combinations can be used. Among them, a p-phenylene sulfide group is mainly used, and a combination with another repeating unit is mainly used. Is particularly preferably used. Among them, a substantially linear one containing at least 60 mol%, more preferably at least 70 mol% of a p-phenylene sulfide group is suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. In this case, those in which the repeating unit of the component is contained in a block shape rather than in a random shape have good workability, and are excellent in heat resistance and mechanical properties, and can be preferably used. A preferable copolymerization component is, for example, an m-phenylene group, but is not limited thereto. The PAS resin used in the present invention is 2
A high molecular weight polymer having a substantially linear structure obtained by polycondensation from a functional monomer is preferable, but a branched or crosslinked PAS resin polymerized by using a small amount of a monomer having three or more functional groups as a part of the monomer is also used. You can do it. Also, a blended resin obtained by blending these branched or crosslinked PAS with the above-mentioned linear polymer can be preferably used. Further, a polymer obtained by increasing the melt viscosity of a linear polymer having a relatively low molecular weight by oxidative crosslinking or thermal crosslinking to improve moldability may be used. The PAS resin used in the present invention is a modified PS resin having various substituents introduced therein.
It may be an AS.

Further, in the present invention, other thermoplastic resins may be used in addition to the PAS resin in a small amount as long as the purpose is not hindered. The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures. For example, aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate and aromatic dicarboxylic acids and diols or oxycarboxylic acids, polyethylene, polypropylene or modified polyolefins thereof, polyamide, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate , Polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, fluororesin, and the like. These thermoplastic resins can be used as a mixture of two or more kinds.

The zinc borate of the component (B) used in the present invention includes all of so-called zinc borates such as tetraborate, zinc metaborate, basic zinc borate and the like, and is prepared by a conventional method. May be used, or a commercially available product may be used , but the average particle size is 50 μm or less, more preferably
It is 30 μm or less. If the particle size is too large, the desired effect of the present invention is not sufficient, and the surface smoothness of the molded product is hindered, which is not preferable. The amount of zinc borate as the component (B) is 0.05 to 10 parts by weight based on 100 parts by weight of the PAS resin (A). If it is less than 0.05 parts by weight, the effect of preventing corrosion of metals and the effect of suppressing contamination are not sufficient. On the other hand, if the amount exceeds 10 parts by weight, it is not preferable because mechanical properties are reduced and viscosity is increased.

Next , in the present invention, as a reinforcing agent (C),
(A) 10-250 parts by weight of glass per 100 parts by weight of PAS resin
Fiber is blended. Glass fibers are typically
It is well known as a filler, but its reinforcing effect is
Can vary considerably depending on the type of additive
As shown in the comparative examples described above, zinc carbonate or acid was used as the corrosion inhibitor.
Although the combination of zinc oxide and the like has excellent corrosion resistance, glass fiber
Adversely affect the reinforcing effect of glass fiber when used in combination with
This has been shown to be undesirable. Therefore, the present invention
In particular, select zinc borate (B) as a corrosion inhibitor
And the combination of this and glass fiber (C)
Without reducing the reinforcing effect of glass fiber,
It is characterized by significantly improved corrosion resistance and contamination.
The particular combination of components (B) and (C) of the present invention is significant. This
That is specifically shown in Examples and Comparative Examples described later.
As you are. In addition, the blending amount of glass fiber is too small
If the reinforcing effect is not sufficient, and if it is excessive,
Manufacturing and forming work becomes difficult, and there is also a problem with mechanical strength.
Is not preferred. In the composition of the present invention,
But not powdery or plate-like other than glass fiber (C)
The filler (D) can be used together with the glass fiber.
Examples of the particulate filler include carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, iron oxide, Oxides of metals such as titanium oxide and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and other metal powders such as silicon carbide, silicon nitride, boron nitride, etc. No. Examples of the plate-like filler include mica, glass flake, various metal foils, and the like. These inorganic fillers can be used alone or in combination of two or more . And glass textiles in particular, the combination of the granular or tabular filler is a preferable combination in order to combine particular mechanical strength and dimensional accuracy, electric properties, and the like. When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. In this example,
Functional compounds such as epoxy compounds, isocyanate compounds, silane compounds and titanate compounds.
These compounds may be used after being subjected to a surface treatment or a convergence treatment in advance, or may be added simultaneously with the preparation of the material. The amount of filler total ((C) + (D) ) is less than 400 parts by weight of Ri per 100 parts by weight of polyarylene sulfide resin, preferably less than 250 parts by weight. If it is excessively large, the molding operation becomes difficult, and the mechanical strength of the molded product also poses a problem.

In the composition of the present invention, known substances added to general thermoplastic resins and thermosetting resins within a range not to impair the object of the present invention, that is, plasticizers, antioxidants and ultraviolet absorbers Stabilizers, antistatic agents, surface treatment agents,
Surfactants, flame retardants, coloring agents such as dyes and pigments, and lubricants, lubricants and crystallization accelerators (nucleating agents) for improving fluidity and releasability can also be used as appropriate according to the required performance. I can do it.

The resin composition of the present invention can be prepared by the equipment and method used for preparing general synthetic resin compositions. That is, necessary components are mixed, kneaded using a single-screw or twin-screw extruder, and extruded into molding pellets. A method of mixing and molding a part of the necessary components as a master batch, In order to improve the dispersion and mixing of the components, any of the methods of pulverizing, mixing, and extruding a part or all of the resin components is also possible.

[0010]

As apparent from the above description, the PAS resin composition containing zinc borate of the present invention has the following effects. (1) To significantly reduce metal corrosion and contamination (adhesion) at the point of contact with resin such as molds, bases, rolls, etc. during molding, and to obtain molded products with accurate dimensions and surface condition over a long period of time. Can be done. (2) Corrosion and contamination of metal can be significantly reduced even when a molded product in contact with metal is used for a long period of time at high temperature, so corrosion and contamination of metal parts as electric / electronic parts and mechanical parts combined with metal The troubles caused by the above are significantly reduced. (3) There is no decrease in mechanical properties, and excellent heat resistance, solvent resistance, and flame retardancy characteristic of PAS resin are maintained.

(4) PA generated during melt-kneading or molding,
The odor peculiar to the S resin composition is reduced, and the working environment is improved. In addition, there is little corrosion and contamination of the cylinder and the mold at the time of molding, the life is extended, and economical and efficient processing can be performed.

[0012]

The present invention is not limited to the following examples. Examples 1 to 7 and Comparative Examples 1 to 10 As shown in Table 1, as component (A), a substantially linear polyphenylene sulfide resin (trade name “FORTRON KPS” manufactured by Kureha Chemical Industry Co., Ltd.) B) As a component, zinc borate shown in Table 1 and others were added in the amounts shown in Table 1, and mixed with a Henschel mixer for 2 minutes. Further, an inorganic filler was added as a component (C) in an amount shown in Table 1, and the mixture was mixed with a blender for 30 seconds. This was kneaded with an extruder having a cylinder temperature of 310 ° C. to produce pellets of the polyphenylene sulfide resin composition. Next, 90 g of the above-mentioned pellets were placed in the bottom of a container having an outer diameter of 55 mm and a height of 120 mm, and a test piece (5 ×) of a mold material (SLD manufactured by Hitachi Metals, Ltd.) mainly composed of iron, chromium and carbon was used. 5 × 10mm) in a predetermined position, cover the top of the container with a glass plate, place in an oven and heat at 330 ° C for 5 hours, take out the test piece, wash off the adhered substance, and visually or The surface was observed with a magnifying glass, and the state of corrosion was examined. In addition, cylinder temperature 320 ℃ in the injection molding machine using the pellets,
Molding was performed at a mold temperature of 150 ° C. for a certain period of time, and the degree of deposits on the mold surface was visually observed, and the relative grade was similarly evaluated. Table 1 shows the results. In addition, SUS-304,
The same evaluation was performed for STAVAX (Woodholm), but the relative results were almost the same. Evaluation criteria

[0013]

(Equation 1)

Table 1 also shows the results of the tensile test using the ASTM test piece.

[0015]

[Table 1]

Claims (2)

(57) [Claims] (A) Polyarylene sulfide resin 100
(B) 0.05 to 10 parts by weight of zinc borate having an average particle size of 50 μm or less, and (C) 10 to 250 parts by weight of glass fiber as a reinforcing agent . A reinforced polyarylene sulfide resin composition having improved resistance. 2. Powder or granular filling together with glass fiber (C)
Agent (D) is combined and the total amount ((C) + (D))
(A) less than 400 parts by weight per 100 parts by weight of the component
The composition of claim 1.