JPH03247436A - Hollow molded item of polyarylene sulfide resin and preparation thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a hollow molded article made of polyarylene sulfide resin and a method for producing the same.

[Issues with conventional technology]

Polyarylene sulfide (hereinafter referred to as PAS)-based resins, represented by polyphenylene sulfide (hereinafter referred to as PPS), generally have excellent mechanical strength, heat resistance, and chemical resistance as compositions containing inorganic fillers. In recent years, it has been widely used as a component material for automobiles, electric/electronic parts, chemical equipment, etc. due to its physical properties such as electrical properties.

However, when trying to apply the blow molding method commonly used for blow molded products of general thermoplastic resins when molding hollow molded products, PAS resins have a weak melt tension, which is the most required for blow molding, and cannot be used as a molten intermediate. Since the parison draws down, it is extremely difficult to perform subsequent blow molding, and injection molding must be relied upon, which is extremely inefficient for producing hollow molded products.

Considering that it is generally sufficient to use a resin with a high molecular weight and high melt viscosity to increase the melt tension, attempts were made to increase the molecular weight of the resin used in order to increase the melt tension for PAS resins, but the result was simply a high molecular weight resin. The use of PAS with a low viscosity was still insufficient, and the combined use of inorganic fillers was not particularly effective.

[Means to solve the problem]

In order to solve the problem of blow moldability of PAS resin, the present inventors have conducted various studies and found a method that significantly improves the melt tension of PAS resin and enables blow molding of PAS resin. This discovery led to the present invention.

That is, in molding a hollow molded article of polyarylene sulfide resin by blow molding, the present invention adds vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, allylalkoxysilane, and mercaptoalkoxysilane to 100 parts by weight of polyarylene sulfide. At least one organic silane compound selected from alkoxysilane compounds consisting of 0.01 to 5
A method for producing a polyarylene sulfide resin hollow molded article, which is characterized in that blow molding is performed using a polyarylene sulfide resin that is blended in parts by weight and melt-kneaded, and the blow molded article thereof.

In addition to the alkoxysilane compound described above, the present inventors have also added to an olefin copolymer consisting of a copolymer of an α-olefin and an α,β-unsaturated glycidyl ester, particularly to this copolymer, and a vinyl polymer. It has also been found that the combined use of a small amount of a graft copolymer in which the polymer or copolymer is chemically bonded in a branched or crosslinked structure is effective in further improving melt tension and improving blow moldability.

The constituent elements of the present invention will be explained in detail below.

The base resin used in the present invention is mainly composed of PAS resin, and is mainly composed of repeating units +Ar-3-)- (where ^r is an arylene group).

Examples of the arylene group -+A r+ include p-phenylene group, m-phenylene group, 0-phenylene group, substituted phenylene group, p, p'-diphenylene sulfone group, p, p'-biphenylene group, p, A p-diphenylene ether group, p,p'-diphenylenecarbonyl group, naphthalene group, etc. can be used.

In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, a polymer using the same repeating unit, that is, a homopolymer, can be used, and a copolymer containing different types of repeating units may be preferable.

As the homopolymer, one in which a p-phenylene group is used as an arylene group and a p-phenylene sulfide group is used as a repeating unit is particularly preferably used.

As a copolymer, a combination of two or more different types of arylene sulfide groups consisting of the above-mentioned arylene groups can be used, but among them, p-7 sulfide groups are mainly used, and p-phenylene sulfide groups and m-phenylene sulfide groups are mainly used. Copolymers containing groups are preferably used. Among these, those containing 60 mol% or more, preferably 70 mol% or more of p-phenylene sulfide groups have good heat resistance, moldability,
This is suitable from the viewpoint of physical properties such as mechanical properties. Also, m-
The phenylene sulfide group is 5 to 40 mol%, especially 10
A copolymer containing up to 25 mol% is preferable. In this case, components whose repeating units are contained in blocks rather than randomly (for example, JP-A-61-1
4228) has excellent heat resistance and mechanical properties and can be preferably used.

Among these, polymers having a substantially linear structure obtained by condensation polymerization from monomers mainly composed of difunctional halogen aromatic compounds can be particularly preferably used.

In addition to polymers with a linear structure, when performing condensation polymerization, 3
Polymers in which a partially crosslinked structure is formed by using a small amount of a crosslinking agent such as a polyhaloaromatic compound having halogen substituents or more can also be used, or the above-mentioned linear structured polymer is heated at high temperature in the presence of oxygen. Polymers whose melt viscosity is increased and moldability is improved can also be used.

Melt viscosity of the raw material polyarylene sulfide as the base resin used in the present invention (temperature 310°C, shear rate 1
200/sec) is 100 to 10,000 poise, especially 20
Those in the range of 0 to 5000 voids are particularly preferred because they have high melt tension, excellent blow moldability, and an excellent balance between mechanical properties and fluidity. If the melt viscosity is less than 100 voids, it is difficult to obtain sufficient melt tension even by the method of the present invention, resulting in insufficient blow moldability and insufficient mechanical strength of the molded product, which is not preferred. On the other hand, when the melt viscosity exceeds 10,000 poise, the fluidity of the resin composition is poor and molding operations become difficult, which is not preferable.

The feature of the blow molding method for PAS resin and the blow molded product of the present invention is that a PAS resin is melt-kneaded with a specific organic silane compound, especially an alkoxysilane, and then blow molded. By adding and blending such an organic silane compound, the melt tension of PAS resin was surprisingly improved, and blow molding of PAS resin, which was extremely difficult no matter what viscosity (molecular weight) of PAS was used, could be carried out stably. This made it possible to obtain hollow molded products of stable quality.

The organic silane compounds used here are alkoxysilanes such as vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, allylalkoxysilane, and mercaptoalkoxysilane, and one type or two or more types can be used.

Examples of vinyl alkoxysilanes include hahinyltriethoxysilane, vinyltris)oxysilane, and vinyltris(β-methoxyethoxy)silane. Examples of epoxyalkoxysilanes include T-glycidoxypropyltrimethoxysilane, β-(3,4 -Epoxycyclohexyl)ethyltrimethoxysilane, T
-glycidoxypropyltriethoxysilane, etc. Aminoalkoxysilanes include, for example, T-aminopropyltrimethoxysilane, T-aminofurobiltriethoxysilane, T-aminopropylmethyldimethoxysilane, T-aminopropylmethyljethoxysilane , N
-(β-aminoethyl)-T-aminopropyltrimethoxysilane, N-phenyl-T-aminopropyltrimethoxysilane, etc. Allylalkoxysilanes include, for example, T-diallylaminopropyltrimethoxysilane, T-allylaminopropyltrimethoxysilane, etc. Examples of the mercaptoalkoxysilane include alkoxysilanes such as T-mercaptopropyltrimethoxysilane and γ-melfcaptopropyltriethoxysilane, such as methoxysilane and T-allylthiopropyltrimethoxysilane.

In the present invention, the amount of the silane compound added to the polyarylene sulfide is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the polyarylene sulfide. If the amount is less than 0.01 part by weight, the intended effect cannot be obtained, and if it is too much, side reactions may occur or abnormally high viscosity may occur, which is not preferable.

Next, the olefinic copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid which is preferably used in combination in the present invention is ethylene, propylene, butene-based copolymer.
The molecular structure contains a copolymer of α-olefin such as 1 and glycidyl ester of α,β-unsaturated acid such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate,
Among them, a copolymer of ethylene and glycidyl methacrylate can be preferably used. Further, a graft copolymer in which a vinyl polymer or copolymer is chemically bonded to such a copolymer in a branched or crosslinked structure is a more preferable combination material. Here, the vinyl (co)polymer segment is a polymer or copolymer made of polystyrene, polyacrylonitrile, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, or the like. In particular, the olefin copolymer preferably used in combination in the blow molding method of the present invention is the same as that detailed in JP-A-1-198664.

The blending amount of the olefin copolymer in the present invention is PAS
30 parts by weight or less, preferably 0 parts by weight per 100 parts by weight of resin
．． It is 5 to 20 parts by weight. If the amount is too small, blow moldability tends to become somewhat unstable, and if it exceeds 30 parts by weight, the melt viscosity is high, making extrusion molding difficult and causing problems in the physical properties of the molded product.

Depending on the purpose, fibrous, granular, or plate-like fillers may be added to the PAS resin material used in the blow molding of the present invention.

Fibrous fillers include glass fiber, asbestos fiber,
Inorganic materials such as carbon fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and fibrous materials of metals such as stainless steel, aluminum, titanium, copper, and brass. Examples include fibrous substances. A particularly typical fibrous filler is glass fiber.

On the other hand, powdery fillers include carbon black, silica, quartz powder, glass peas, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, iron oxide, Metal oxides such as titanium oxide, zinc oxide, alumina, metal carbonates such as calcium carbonate, magnesium carbonate,
metal sulfates, such as calcium sulfate and barium sulfate;
Other examples include silicon carbide, silicon nitride, boron nitride, and various metal powders.

In addition, examples of the plate-shaped filler include mica, glass flakes, and various metal foils.

These inorganic fillers can be used alone or in combination of two or more. Fibrous fillers, especially glass fibers and granular and/or
Alternatively, the combined use of a plate-like filler is a preferable combination in order to provide the molded article with good mechanical strength, dimensional accuracy, electrical properties, etc.

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

Furthermore, in the blow molding method of the present invention, it is also possible to use a small amount of other thermoplastic resins in addition to those mentioned above.

The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures. For example, polyolefin (co)polymers other than those mentioned above, aromatic polyesters made of aromatic dicarboxylic acids and diols or oxycarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate, polyamide polymers, polycarbonates, and ABS.

Examples include polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, and fluororesin. Moreover, two or more types of these thermoplastic resins can also be used in combination.

Furthermore, the PAS resin of the present invention contains known substances that are generally added to synthetic resins, such as stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, A lubricant, a mold release agent, a crystallization promoter, a crystal nucleating agent, etc. can also be added as appropriate depending on the required performance.

The blow molding method of the present invention includes adding and blending at least the above-mentioned alkoxysilane to a PAS resin, melt-kneading the mixture, and preferably adding and blending the above-mentioned olefin copolymer.
In some cases, other desired components are also blended and melt-kneaded, and then subjected to blow molding.The melt-kneading of these components is performed by once forming pellets using a l-screw or twin-screw extruder, and then subjecting them to blow molding. It is also possible to mold the mixture into a parison for blow molding immediately after melt-kneading.

The blow molding of the present invention may be carried out in a conventional manner using a blow molding machine used for blow molding thermoplastic resins on boats. That is, the above-mentioned PAS resin is plasticized using an extruder or the like, and then extruded or injected through an annular die to form an annular molten or softened intermediate parison, which is then inserted between molds and gas is injected into the inside. It is blown, inflated, cooled, and solidified to form a hollow body. As molding conditions for the PAS resin of the present invention, the cylinder and die temperatures are 280~280~
It is preferable to carry out at 350 t:, particularly preferably at 29 t.
0 to 320 t. Also, the mold temperature is 40 to 200
The temperature is preferably 80°C to 150°C. The gas to be blown into the interior may be air, nitrogen, or any other gas, but air is usually used in view of economic efficiency, and the blowing pressure is preferably 4 to 10 kg/cI11.

[Example] 2 The present invention will be specifically illustrated by examples below, but the present invention is not limited thereto.

Examples 1-5. Comparative Examples 1 to 3 Melt viscosity (310°C, shear rate 1200/5ec)
Add γ-aminopropyltriethoxysilane and optionally an olefin copolymer (see property-2 below) to a PPS resin of 2000 voids in the amounts shown in Table 1, and extrude into a cylinder using a twin-screw extruder. The mixture was melt-kneaded and extruded into pellets at a temperature of 310°C. Next, the pellets were molded using a blow molding machine (0A-75 manufactured by Braco), with a cylinder temperature of &320°C and a die (die diameter 6o door) temperature of 310°C.
t, a mold temperature of 120° C., and a blowing pressure of 6 kg/a+f to form rectangular prism containers with an average thickness of 4. At this time, the moldability (drawdown property, membrane tearing during blowing), uniformity of wall thickness, and appearance (rough skin, surface irregularities) of the molded product were observed. For comparison, a case in which no organic silane compound was added was also evaluated in the same manner. The results are shown in Table-1. The measurement method used for the evaluation is as follows.

1) Drawdown property of parison Extrude the parison to a length of 200 mm through a die with a diameter of 60 mm and a die interval of 6 using the above-mentioned blow molding machine, measure the length of the parison after 10 seconds, and measure the length of the parison within 210 mm.
A fine J of 210 to 250 mm was defined as "small", and a value of 250 mm or more was defined as "large". In addition, a parison cut and fallen due to its own weight was designated as r DDJ.

2) Uniformity of the molded product Cut the molded product and cut each side of the square prism, its upper part, the center part,
Measure the thickness of the lower part with a micrometer and note the variation in thickness (%
) was investigated.

3) Breakage during blowing: Determination was made by visual observation during molding to determine whether or not the material had deformed.

4) Visually observe the surface smoothness (unevenness) and rate it as excellent, good, fair, or
Ranked as poor.

Examples 6-15. Comparative Examples 4 to 6 Organic silane (see property-1 below) and olefin graft copolymer (see property-2 below) of the type and amount shown in Table 2 were added to a PPS resin with a melt viscosity of 2000 poise. , pelletized and blow molded in the same manner as in Examples 1 to 5, and evaluated in the same manner. The results are shown in Table-2.

Examples 16-20. Comparative Examples 7 to 9 For PPS with a melt viscosity of 1500 voids, organic silane compounds of the type and amount shown in Table 3, optionally an olefin copolymer, and glass fiber (diameter 10 μm length 3 mm) or Calcium carbonate (about 4 μm in diameter
) and extruded pellets were similarly blow molded and evaluated.

The results are shown in Table-3.

Note-1) Organic silane compound A: γ-aminopropyltriethoxysilane B: γ-glycidoxypropyltrimethoxysilane C: T-mercaptopropyltrimethoxysilane D: Vinyltrimethoxysilane E: T-diallylaminopropyl Trimethoxysilane Note-2) Olefin copolymer B/GMA: Ethylene/glycidyl methacrylate ester copolymer (85-15 weight ratio) E/GMA-gPAM: Graft copolymerization of B/GMA with polymethyl methacrylate Coalescing (70-30 weight ratio) B/GMA=gST: B/GMA and polystyrene graft copolymer (70-30 weight ratio) E/GMA-gAN: E/GMA and polyacrylonitrile graft copolymer (TO -30 weight ratio) Note 3) GF Niglass fiber [Effects of the invention] As is clear from the above explanation and examples, the method of the present invention allows stable blow molding of PAS resin, which has been extremely difficult in the past. This makes it possible to provide hollow molded products with stable quality and shape. Moreover, originally this PAS
It is a hollow molded product that has various excellent physical properties of resin materials and is suitable for applications that are used under harsh conditions, such as piping around automobile engines, containers that require heat resistance and chemical resistance, etc. It is expected to have a wide range of uses.

Claims (1)

[Claims] 1. When molding a polyarylene sulfide resin hollow molded product by blow molding, 100 parts by weight of polyarylene sulfide contains 0 alkoxysilane compound.
．． 1. A method for producing a polyarylene sulfide resin blow molded article, which comprises blow molding the polyarylene sulfide resin which has been melt-kneaded with 1 to 5 parts by weight of the polyarylene sulfide resin. 2. The polyarylene sulfide resin blow molded article according to claim 1, wherein the alkoxysilane compound is at least one selected from organic silane compounds consisting of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, allylalkoxysilane, and mercaptoalkoxysilane. manufacturing method. 3 0 parts by weight of an olefin copolymer made of a copolymer of α-olefin and α,β-unsaturated glycidyl ester based on 100 parts by weight of polyarylene sulfide resin.
．． 3. The method for producing a polyarylene sulfide resin blow molded article according to claim 1 or 2, wherein the resin composition is blended in an amount of 5 to 30 parts by weight and melted and kneaded. 4 Olefin copolymer has α-olefin and α,β
- The polyarylene sulfide resin blow molded article according to claim 3, which is a graft copolymer in which a vinyl polymer or copolymer is chemically bonded in a branched or crosslinked structure to the copolymer with an unsaturated glycidyl ester. manufacturing method. 5. The polyarylene sulfide resin blow molded product according to any one of claims 1 to 4, wherein a resin composition further contains an inorganic filler in an amount of 1 to 400 parts by weight per 100 parts by weight of the polyarylene sulfide resin. Manufacturing method. 6. A polyarylene sulfide resin hollow molded article obtained by the blow molding method according to any one of claims 1 to 5.