JP2529751B2 - Hollow molded polyallylen sulfide resin product and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hollow molded article made of a polyarylene sulfide-based resin and a method for producing the same.

[Conventional technology and its problems]

Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) generally has excellent mechanical strength, heat resistance, chemical resistance, as a composition containing an inorganic filler, etc. Since it has physical properties such as electrical properties, it has been widely used in recent years as a material for parts such as automobiles, electric / electronic parts, and chemical equipment.

However, when the blow molding method that is commonly used for blow molding of general thermoplastic resin is applied to the molding of a hollow molding product, the PAS resin has a weak melt tension most required for blow molding and a molten intermediate parison. Since it is drawn down, it is extremely difficult to carry out blow molding thereafter, and it is inevitable to rely on the injection molding method exclusively, and it is extremely inefficient in producing a hollow molded product. In order to increase the melt tension, it is generally sufficient to use a resin having a high molecular weight and a high melt viscosity.Therefore, even for PAS resins, an attempt was made to increase the melt tension of the resin to be used. It was still not enough to use PAS with viscosity, and the combined use of inorganic filler was not particularly effective.

[Means for solving the problem]

In order to solve the problem of the blow moldability of the PAS resin, the present inventors have further conducted various studies, and as a result, the melt tension of the PAS resin is remarkably improved, and a method for enabling blow molding of the PAS resin. The present invention has been completed and the present invention has been achieved.

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

Further, the inventors of the present invention have found that, together with the above-mentioned alkoxysilane compound, an olefin-based copolymer composed of a copolymer of α-olefin and α, β-unsaturated glycidyl ester, especially this copolymer, and vinyl-based copolymer It has also been found that by using a small amount of a graft copolymer in which a polymer or a copolymer is chemically bonded in a branched or crosslinked structure, the melt tension is further improved and the blow moldability is improved, which is effective.

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

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

Examples of the arylene group Ar include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p'-diphenylene sulfone group, p, p'-
Biphenylene group, p, p'-diphenylene ether group, p,
A p'-diphenylene carbonyl group, a naphthalene group and the like can be used.

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

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

As the copolymer, a combination of two or more different arylene sulfide groups among the above-mentioned arylene sulfide groups can be used. Among them, a copolymer mainly containing a p-phenylene sulfide group and containing this and an m-phenylene sulfide group is used. Polymers are preferably used. Among these, those containing p-phenylene sulfide groups in an amount of 60 mol% or more, preferably 70 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. Further, a copolymer containing m-phenylene sulfide group in an amount of 5 to 40 mol%, particularly 10 to 25 mol%, is preferable. In this case, it is preferable that the repeating unit of the component is contained in a block form rather than the random form (for example, those described in JP-A-61-14228) because it has excellent heat resistance and mechanical properties. Can be used.

Of these, a polymer having a substantially linear structure, which is obtained by polycondensation from a monomer mainly composed of a bifunctional halogen aromatic compound, can be particularly preferably used.

In addition to linear polymer, when polycondensation,
A polymer in which a partially crosslinked structure is formed by using a small amount of a crosslinking agent such as a polyhaloaromatic compound having three or more halogen substituents can be used, and the linear structure polymer can be used at high temperature in the presence of oxygen. It is also possible to use a polymer which is heated to increase the melt viscosity and has improved moldability.

The melt viscosity of the raw material polyarylene sulfide as the base resin used in the present invention (temperature 310 ° C., shear rate 120
(0 / sec) is in the range of 100 to 10000 poise, and especially in the range of 200 to 5000 poise, since the melt tension is large, the blow moldability is excellent, and the balance between mechanical properties and fluidity is excellent, which is particularly preferable. If the melt viscosity is less than 100 poise,
Even with the method of the present invention, it is not preferable because it is difficult to obtain a sufficient melt tension, the blow moldability is insufficient, and the mechanical strength of the molded product is insufficient. Further, when the melt viscosity exceeds 10,000 poise, the fluidity of the resin composition is poor and the molding operation becomes difficult, which is not preferable.

The blow molding method of the PAS resin and the hollow molded article thereof of the present invention are characterized in that the PAS resin is melt-kneaded by adding and blending a specific organic silane compound, particularly an alkoxysilane, and blow molding. By adding and blending such an organic silane compound, the melt tension of the PAS resin was surprisingly improved, and it was difficult to use the PAS resin of any viscosity (molecular weight) to stably perform blow molding of the PAS resin. It has become possible to obtain a hollow molded product of stable quality.

The organic silane compound used here is an alkoxysilane such as vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, allylalkoxysilane, and mercaptoalkoxysilane.
More than one species can be used.

Examples of vinylalkoxysilane include vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β-methoxyethoxy) silane, and examples of epoxyalkoxysilane include γ-glycidoxypropylmethoxysilane and β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, etc. Examples of aminoalkoxysilanes include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,
Examples of allylalkoxysilanes such as N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane include, for example, γ-diallylaminopropyltrimethoxysilane, γ-allylamino Examples of mercaptoalkoxysilanes such as propyltrimethoxysilane and γ-allylthiopropyltrimethoxysilane include alkoxysilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

In the present invention, the amount of the silane compound added to and blended with polyarylene sulfide is 0.01 to 5 parts by weight per 100 parts by weight of polyarylene sulfide, preferably
It is 0.1 to 3 parts by weight. When the amount is less than 0.01 parts by weight, the intended effect cannot be obtained, and when the amount is too large, a side reaction occurs or an abnormally high viscosity is accompanied, which is not preferable.

Next, the α-olefin preferably used in the present invention and the olefin-based copolymer comprising a glycidyl ester of an α, β-unsaturated acid include α-olefins such as ethylene, propylene and butene-1, and acrylic acid. Glycidyl,
Glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconate, and the like, which contains a copolymer with a glycidyl ester of an α, β-unsaturated acid in the molecular structure, among which a copolymer of ethylene and glycidyl methacrylate is It can be preferably used. Further, a graft copolymer in which a vinyl polymer or a copolymer is chemically bonded in a branched or crosslinked structure to the above copolymer is a more preferable combined substance. Here, the vinyl-based (co) polymer segment is a polymer or copolymer made of polystyrene, polyacrylonitrile, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, or the like. Particularly, the olefin-based copolymers preferably used in combination in the blow molding method of the present invention are the same as those described in detail in JP-A-1-198664.

The blending amount of the olefinic copolymer in the present invention is PAS.
30 parts by weight or less based on 100 parts by weight of resin, preferably 0.5 to 20
Parts by weight. If the amount is too small, the blow moldability tends to be slightly unstable. If the amount is more than 30 parts by weight, the melt viscosity is high, extrusion molding becomes difficult, and there is a problem in the physical properties of the molded product.

The PAS-based resin material used in the blow molding of the present invention may further contain a fibrous, powder-granular, or plate-shaped filler depending on 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, stainless steel, aluminum, titanium, Inorganic fibrous substances such as fibrous materials of metals such as copper and brass are exemplified. A particularly representative fibrous filler is glass fiber.

On the other hand, as the granular filler, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, wollastonite such as silicate, iron oxide, Metal oxides such as titanium oxide, zinc oxide and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride, boron nitride, various metals And the like.

Examples of the plate-like filler include mica, glass flakes, various metal foils and the like.

These inorganic fillers can be used alone or in combination of two or more. The combined use of fibrous fillers, especially glass fibers and powdery and / or plate-like fillers is a preferable combination in view of having both mechanical strength, dimensional accuracy and electrical properties of the molded product.

When using these fillers, it is desirable to use a sizing agent or a surface treatment agent. This example is a functional compound such as an epoxy compound, an isocyanate compound, a titanate compound, and a silane compound.

Further, in the blow molding method of the present invention, in addition to the above,
It is also possible to use a small amount of another thermoplastic resin in an auxiliary manner.

The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures. For example, a polyolefin-based (co) polymer other than the above,
Polyethylene terephthalate, aromatic polyester such as polybutylene terephthalate and other aromatic dicarboxylic acid and diol or oxycarboxylic acid, polyamide polymer, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, polyether sulfone, Examples thereof include polyetherimide, polyetherketone, and fluororesin. Further, these thermoplastic resins may be used as a mixture of two or more kinds.

Further, the PAS-based resin of the present invention is a known substance generally added to synthetic resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, Lubricants, mold release agents, crystallization accelerators, crystal nucleating agents and the like can be appropriately added depending on the required performance.

In the blow molding method of the present invention, at least the above-mentioned alkoxysilane is added to the PAS-based resin and melt-kneaded, and more preferably, the olefin-based copolymer is added and mixed,
In some cases, other desired components are also blended and melt-kneaded, and then subjected to blow molding. The melt-kneading of such components is once pelletized using a single-screw or twin-screw extruder and then subjected to blow molding. It is also possible to form a parison for blow molding immediately after melt-kneading and to provide it for molding.

The blow molding of the present invention may be performed by a usual method using a blow molding machine generally used for blow molding of a thermoplastic resin. That is, the above PAS-based resin is plasticized by an extruder or the like, and this is extruded or injected by an annular die to form an annular melted or softened intermediate parison, which is sandwiched by a mold to put a gas inside. It is blown, inflated, cooled and solidified, and molded as a hollow body. As molding conditions for the PAS resin of the present invention, the cylinder and die temperatures are 280 to 350 ° C.
Is preferably performed at 290 to 320 ° C. The mold temperature is preferably 40 to 200 ° C, particularly preferably 80 to 150 ° C. The gas blown inside may be air, nitrogen or the like, but air is usually used in consideration of economy, and the blowing pressure is preferably 4 to 10 kg / cm ² .

〔Example〕

Hereinafter, the present invention will be specifically shown by examples, but the present invention is not limited thereto.

Examples 1 to 5 and Comparative Examples 1 to 3 Melt viscosity (310 ° C., shear rate 1200 / sec) With respect to 2000 poise PPS resin, γ-aminopropyltriethoxysilane and, in some cases, olefin-based copolymer (described later) Note-2) was added in the amount shown in Table-1 and melt-kneaded and extruded at a cylinder temperature of 310 ° C. using a twin-screw extruder to pelletize. Then, using the pellets, a blow molding machine (DA-75 manufactured by Placo Co., Ltd.) was used, and the cylinder temperature was 320.
℃, die (die diameter 60 mm) temperature 310 ℃, mold temperature 120 ℃,
A quadrangular prismatic container having an average thickness of 4 mm was molded at a blowing pressure of 6 kg / cm ² .
At this time, the moldability (draw-down property, film breakage at the time of blowing), the uniformity of the thickness of the molded product, and the appearance (roughness of the surface, unevenness of the surface) were observed. For comparison, the same evaluation was performed when no organic silane compound was added. The results are shown in Table 1. In addition, the measuring method used for evaluation is as follows.

1) Drawdown property of parison Using the blow molding machine, a parison was extruded from a die having a diameter of 60 mm and a die interval of 6 mm to a length of 200 mm, and the parison length after 10 seconds was measured. ~ 250m
m is "small" and 250mm or more is "large". Moreover, what the parison cut and dropped due to its own weight was designated as "DD".

2) Uniformity of molded product The molded product was cut, and the thickness of each surface of the rectangular prism and its upper, central, and lower portions were measured with a micrometer, and the variation (%) in thickness was examined.

3) Breakage at the time of blowing It was determined whether or not the material had broken during molding.

4) Appearance Observe the surface smoothness (irregularity) visually, and
Possible, not ranked.

Examples 6 to 15 and Comparative Examples 4 to 6 For PPS resins having a melt viscosity of 2000 poise, the types and amounts of organic silanes shown in Table 2 (see Note 1 below) and olefin-based graft copolymers (Note 2 below) (See reference)
Pellets were formed in the same manner as in Examples 1 to 5, blow molded, and evaluated by the same method. Table 2 shows the results.

Examples 16 to 20, Comparative Examples 7 to 9 With respect to PPS having a melt viscosity of 1500 poise, the type and amount of the organic silane compound shown in Table 3 and optionally an olefinic copolymer, and a glass fiber (diameter as an inorganic filler) 10μ
m length 3 mm) or calcium carbonate (diameter about 4 μm) was added and blended, and extruded pellets were similarly blow molded and evaluated. The results are shown in Table-3.

[Effects of the Invention] As is apparent from the above description and Examples, the method of the present invention makes it possible to stably perform blow molding of a PAS-based resin, which has been difficult in the past, with stable quality and hollow shape. It is now possible to provide molded products. Moreover, it is a hollow molded product that originally has various excellent physical properties of this PAS resin material and is suitable for applications used under harsh conditions. Pipings around automobile engines, heat resistance, and chemical resistance are required. It is expected to have a wide range of applications such as containers.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B29L 22:00 B29L 22:00 (56) Reference JP-A-1-63115 (JP, A) Kai 52-52958 (JP, A) JP 57-158256 (JP, A) JP 61-95068 (JP, A) JP 62-86050 (JP, A) JP 59-31503 ( JP, A)

Claims (6)

(57) [Claims] 1. When molding a hollow molded article of a polyarylene sulfide resin by blow molding, 0.01 to 5 parts by weight of an alkoxysilane compound is added to 100 parts by weight of the polyarylene sulfide, and melt-kneaded. A method for producing a polyarylene sulfide-based resin hollow molded article, which comprises blow molding using a resin. 2. The polyarylene sulfide system 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 of hollow resin moldings. 3. 0.5 to 30 parts by weight of an olefin copolymer composed of a copolymer of α-olefin and α, β-unsaturated glycidyl ester is added to 100 parts by weight of a polyarylene sulfide resin. The method for producing a polyarylene sulfide-based resin hollow molded article according to claim 1, wherein the melt-kneaded resin composition is blow-molded. 4. An olefin-based copolymer is a copolymer of α-olefin and α, β-unsaturated glycidyl ester,
The method for producing a polyarylene sulfide-based resin hollow molded article according to claim 3, wherein the vinyl-based polymer or copolymer is a graft copolymer in which a branched or cross-linked structure is chemically bonded. 5. The polyarylene sulfide-based resin according to claim 1, further comprising blow molding a resin composition containing 1 to 400 parts by weight per 100 parts by weight of the polyarylene sulfide-based resin. Manufacturing method of hollow molded products. 6. A polyarylene sulfide-based resin hollow molded article obtained by the blow molding method according to any one of claims 1 to 5.