JP2730811B2 - Polyarylene sulfide resin composition for blow molding and hollow molded article thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyarylene sulfide resin composition for blow molding and a hollow molded article thereof.

[0002]

2. Description of the Related Art Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) is generally used as a composition containing an inorganic filler or the like. Due to its excellent properties such as mechanical strength, heat resistance, chemical resistance, and electrical properties, it is widely used in recent years for component materials such as automobiles, electric / electronic parts, and chemical devices. However,
In the case of PAS-based resin, when the blow molding method commonly used for general thermoplastic resin hollow molded products is applied to the molding of hollow molded products, the melt tension required most for blow molding is weak, and the molten intermediate parison is drawn. It is extremely difficult to perform blow molding because it goes down, and it is necessary to rely exclusively on the injection molding method and it is extremely inefficient for producing hollow molded products, so mechanical strength, heat resistance, chemical resistance In spite of being expected to have many properties as a hollow molded article with excellent physical properties such as properties, its practical use is actually limited. In order to increase the melt tension, it is generally advisable to use a resin with a high molecular weight and a high melt viscosity.In order to increase the melt tension of PAS-based resins, we attempted to increase the molecular weight of the resin used. Yes, it is not enough to simply use high viscosity PAS, and the combined use of inorganic fillers has not been particularly effective. The present invention solves these problems and develops a PAS resin composition having excellent blow moldability, particularly melt tension, and utilizes the mechanical, thermal, and chemical characteristics of the PAS resin under severe conditions. Provide hollow molded articles that can be used, for example, intake manifolds for automobiles, intake and exhaust parts around engines, containers for high-temperature liquids, chemicals, solvents, containers such as pipes and floats, and tubular articles (including irregular shapes). The purpose is to:

[0003]

SUMMARY OF THE INVENTION The present inventors have developed such a PAS.
In order to solve the problem of blow moldability of resin-based resin, various studies were conducted.As a result, the melt tension of PAS-based resin was significantly improved by using a specific PAS-based resin and, if necessary, blending a specific olefin-based resin. However, they have found that blow molding of a PAS-based resin is possible and the above object can be achieved, and the present invention has been accomplished. That is, the present invention provides: (a) a melt viscosity measured at 310 ° C. and a shear rate of 1200 sec ⁻¹
5 to 100% by weight of a polyarylene sulfide resin having a branched structure of 2500 to 20000 poise (preferably 5 to 95 % by weight)
% ) And (b) 95 to 0% by weight (preferably 95 to 5% by weight ) of a substantially linear polyarylene sulfide resin having a melt viscosity of 300 to 3000 poise measured under the same conditions. The present invention relates to an arylene sulfide resin composition and a hollow molded article obtained by blow molding the polyarylene sulfide resin composition. Further, more preferably, 100 parts by weight of the PAS resin (a + b) is
The present invention relates to a blow-molded polyarylene sulfide resin composition comprising an olefin copolymer containing, as essential components, 30 parts by weight or less of an α-olefin and an α, β-unsaturated glycidyl ester, and a hollow molded article thereof.

[0004] The constituent components of the composition of the present invention will be described in detail below. PAS resin used in the present invention comprises the component (a) at least 5 wt% or more, further the component (b) consists of PAS resin under 95 wt% or less.

(A) PAS having a branched structure of a component is -Ar-
S- (however, Ar is an arylene group) as a main repeating unit, and a melt viscosity in which a branched or cross-linked structure is introduced into the main repeating unit (condition: 310 ° C., shear rate: 1200 sec ^-1 or less) 2500 to 20000 poise; Preferably, it is a 3000-15000 poise PAS resin. If the viscosity is less than 2500 poise, the melt tension during blow molding is weak and the moldability is poor.
If it exceeds 0 poise, the fluidity is poor, which is also unfavorable for molding. In addition, the branched or crosslinked structure has a main repeating unit of 10
It is about 0.01 to 10 mol, preferably 0.02 to 5 mol per 0 mol. If the degree of branching or cross-linking is too small, the melt tension is poor and draw-down occurs. (a) The main repeating unit constituting the component is-(Ar-S)-(where Ar is an arylene group). As the arylene group Ar, for example, a p-phenylene group, an m-phenylene group,
o-phenylene group, substituted phenylene group, p, p'-diphenylene sulfone group, p, p'-biphenylene group, p, 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-described arylene groups, a homopolymer using the same repeating unit may be used, and a copolymer containing a different type of repeating unit may be preferable. As the homopolymer, those having a p-phenylene sulfide group as a main repeating unit using a p-phenylene group as an arylene group are particularly preferably used. As the copolymer, two or more different combinations among the above-mentioned arylene sulfide groups comprising an arylene group can be used. Among them, a p-phenylene sulfide group is mainly used, and a copolymer containing an Polymers are preferably used. In this,
Those containing a p-phenylene sulfide group 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. The branched PAS (a) used in the present invention has a molecular structure in which such structural units are linked in a branched or crosslinked structure. Such a branched PAS resin (a) is disclosed in Japanese Unexamined Patent Publication No.
According to the method described in JP-A-66720, it can be produced by reacting an alkali metal sulfide with a dihalo aromatic compound and a small amount of a branching or crosslinking agent such as a small amount of a polyhalo aromatic compound having three or more functional groups. For example, a branching or cross-linking agent such as a polyhalo-aromatic compound having three or more halogen substituents is used in an amount of about 0.
The mixture is mixed from about 01 mol to about 10 mol, and if necessary, water or an alkali metal carboxylate is added and reacted, and the mixture is polymerized and prepared under the condition of a desired viscosity (molecular weight). PAS resin
The introduction rate of the branching unit (a) is adjusted by the amount of the above-mentioned branching, cross-linking agent or the like. Incidentally, even a branched or crosslinked PAS resin prepared by curing a linear PAS having an extremely low viscosity and increasing the viscosity by oxidative crosslinking or thermal crosslinking is not preferred.

The linear PAS (b) is not always essential but is preferably used in combination, because it is not necessary to use a branching agent or a crosslinking agent in the branched PAS (a).
Or a straight-chain PAS resin having substantially no branched or cross-linked structure in molecular structure. good. The melt viscosity of linear PAS (b) is 300
It is in the range of 30003000 poise, preferably 500 to 2500 poise. The linear PAS (b) has better mechanical properties, especially impact strength, than the branched PAS (a), and is effective in imparting such properties to a molded article. However, such linear PAS resins
Since sufficient melt tension cannot be obtained by only (b), it is necessary to use at least the branched PAS (a). However, if the viscosity is less than 300 poise, there is no effect of using it together.
Those with more than 3000 poise are not preferable because of their own manufacturing problems. The amount of the branched PAS (a) is 5 to 100% by weight, preferably 5 to 95% by weight , and the linear PAS (b) is 0 to 100% by weight.
95% by weight, preferably 5-95% by weight , particularly preferably (a) 10-90% by weight (b) 90-10% by weight. This mixing ratio is appropriately selected depending on the melt viscosity of PAS (a) and (b), the physical properties of the intended hollow molded article, the application, and the like.

Next, the composition of the present invention preferably contains an olefin copolymer containing an α-olefin and a glycidyl ester of an α, β-unsaturated acid as essential components.
Such olefin-based copolymers include α-olefins such as ethylene, propylene, and butene-1, and glycidyl esters of α, β-unsaturated acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate. Is included in the molecular structure. Among them, a copolymer of ethylene and glycidyl methacrylate is preferable, and a multi-component copolymer using other vinyl monomers in combination may also be used. Among such olefin copolymers, grafts in which the above-mentioned copolymer of α-olefin and α, β-unsaturated glycidyl ester and vinyl polymer or copolymer are chemically bonded in a branched or cross-linked structure. Copolymers are more preferred concomitant substances. Here, the vinyl-based (co) polymer segment is a polymer or copolymer composed of polystyrene, polyacrylonitrile, polyacrylate alkylester, polymethacrylate alkylester, and the like. As a preferable example of such a graft copolymer, a multi-phase structure prepared by a preparation method described in JP-A-63-313313 can be mentioned. That is, for example, in the presence of a glycidyl group-containing olefin copolymer, at least one vinyl monomer is copolymerized with a specific radical (co) polymerizable organic peroxide to form a peroxide group-containing copolymer. This is heated and kneaded, and the both polymers are crosslinked by a reaction of a peroxide group in the vinyl copolymer to prepare a graft polymer. Particularly, olefin-based graft copolymers which are preferably used in combination in the blow molding method of the present invention are described in detail in JP-A-1-198664. The amount of the olefin copolymer in the present invention is 30 parts by weight or less, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the PAS resin (a + b). If the amount is too small, the blow moldability tends to be slightly unstable,
If the amount exceeds 30 parts by weight, the melt viscosity is high, molding becomes difficult, and there are problems in physical properties such as chemical resistance of the hollow molded article, which is not preferable depending on its use.

The PAS-based resin material used in the blow molding of the present invention may further contain a fibrous, powdery or plate-like filler depending on the purpose. Such a filler is effective for imparting mechanical properties, particularly strength and rigidity, to the molded article.
As the fibrous filler, 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 metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass Fibrous substances. Particularly typical fibrous fillers are glass fibers. On the other hand, as the granular filler, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin,
Metal oxides such as talc, clay, diatomaceous earth, wollastonite, iron oxide, titanium oxide, zinc oxide, alumina, metal carbonates such as calcium carbonate and magnesium carbonate, calcium sulfate, barium sulfate Metal sulfates, silicon carbide, silicon nitride, boron nitride, and various metal powders. 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. The combined use of fibrous fillers, especially glass fibers and powdery or plate-like fillers, is a preferred combination in terms of having both mechanical strength, dimensional accuracy, electrical properties, etc. of the molded product, and particularly improving blow moldability. It is also effective. In 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. The amount of the filler in the present invention is 1 to 100 parts by weight of the PAS resin (a + b).
It is at most 50 parts by weight, preferably at most 100 parts by weight. If the amount is small, rigidity, strength, etc. tend to be low,
On the other hand, if the amount exceeds 150 parts by weight, the molding is hindered, which is not preferable.

Further, in addition to the above, other small amounts of other thermoplastic resins can be used together with the PAS resin composition of the present invention. The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures. For example, other than the above, polyolefin (co) polymers, aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate and aromatic dicarboxylic acids and diols or oxycarboxylic acids, polyamide polymers, polycarbonates, AB
S, polyferrenine oxide, polyalkyl acrylate, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, fluorine resin and the like can be mentioned. These thermoplastic resins can be used as a mixture of two or more kinds.

Further, the PAS resin of the present invention contains known substances which are generally added to synthetic resins, such as stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, dyes and pigments. A coloring agent, a lubricant, a release agent, a crystallization accelerator, a crystal nucleating agent, and the like can be appropriately added according to required performance.

In the blow molding method of the present invention, the above-mentioned specific PAS-based resin is melt-kneaded by adding the above-mentioned olefin-based copolymer if necessary and, if necessary, blending other desired components. The melt-kneading of each component, which is kneaded and then subjected to blow molding, may be performed by pelletizing once using a single-screw or twin-screw extruder and then subject to blow molding, or for blow molding immediately after melt-kneading. It is also possible to use it as a parison 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 PAS-based resin or composition is plasticized by an extruder or the like, and is extruded or injected by an annular die to form an annular molten or softened intermediate parison. Gas is blown into the air, inflated, cooled and solidified, and formed as a hollow body. Molding conditions for the PAS-based resin or composition of the present invention include cylinder and die temperatures of 280 to 350.
C., preferably 290-320.degree. The mold temperature is preferably from 40 to 200 ° C, particularly preferably from 80 to 160 ° C. The gas blown into the inside may be air, nitrogen or any other gas, but air is usually used in consideration of economy, and the blowing pressure is preferably 4 to 10 kg / cm ² . Furthermore, it can be molded by a special blow molding machine such as a three-dimensional blow molding machine. Further, the composition of the present invention may be composed of one or more layers, and may be combined with a layer of another material to form a multilayer blow molded article.

[0012]

As described above, the PAS resin composition of the present invention has an improved melt tension as compared with the conventional PAS resin or its composition, does not have a drawdown of the parison at the time of blow molding, and has significantly improved blow moldability. A hollow molded product having a uniform thickness and a good appearance can be obtained, and also has excellent physical properties, such as automobile intake manifolds, intake and exhaust parts around the engine,
It is possible to provide a hollow molded product that can be used under severe conditions such as containers for high-temperature liquids, chemicals, solvents, containers such as pipes and floats, and tubular articles (including deformed shapes).

[0013]

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited thereto.

Examples 1 to 25 and Comparative Examples 1 to 9 Trichlorobenzene was added to 1, 0.3, 0.1 and 0.1
% Dichlorobenzene and sodium sulfide
It was prepared by coupling reaction, the melt viscosity of each 10000 poise (a-
1), 5000 poise (a-2), 3000 poise (a-3) and 1500 poise
Branched polyphenylene sulfide (PPS) (a) of is (a'-1; comparative product) , linear PPS (b) having a viscosity of 1500 poise (Fortron KPS manufactured by Kureha Chemical Industry Co., Ltd.), and ethylene glycidyl meta Acrylate copolymer (E / GMA) or E
/ GMA grafted with styrene-acrylonitrile copolymer (E / GMA-g-AS),
Further, glass fibers and the like were added in the amounts shown in the table, and were melt-kneaded and extruded into pellets at a cylinder temperature of 310 ° C. using a twin-screw extruder. Then, using these pellets, blow molding machine
In Placo S-45ND manufactured), cylinder temperature 320 ° C., a die (die diameter 50 mm, die gap 3mm) Temperature 310 ° C., a mold temperature of 0.99 ° C., with blow pressure 5 kg / cm ^2, the average thickness of 2.5 mm, Contents 5
A 00 cc cylindrical container was formed. At this time, the moldability (draw-down property, 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 evaluated. Table 1 shows the results
3 are shown.

The measuring method used for the evaluation is as follows. 1) Draw-down property of parison
Extrude to the length of 10 seconds, measure the parison length after 10 seconds 210 m
m is fine, 210-240mm is small, 240-270mm
Is “medium” and 270 mm or more is “large”. In addition, the parison that was cut and dropped by its own weight was designated as “DD”. 2) Uniformity of molded product Cut the molded product and measure the thickness of the circumference of the cylinder and its upper, middle and lower parts with a micrometer, and change in thickness (%)
Was examined. 3) Breakage at the time of blow It was determined whether or not the material had broken during blow molding. 4) Appearance Observe the surface smoothness (irregularity) visually, and
Not ranked. 5) Tensile strength A test piece prepared by injection molding was separately measured according to ASTM D638.

6) Impact strength A test piece prepared by injection molding was separately measured according to ASTM D256.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B29L 22:00

Claims (7)

(57) [Claims] (1) 5 to 100% by weight of a polyarylene sulfide resin having a branched structure having a melt viscosity of 2500 to 20,000 poise measured at 310 ° C. and a shear rate of 1200 sec ⁻¹ , and (b) measured under the same conditions. A polyarylene sulfide resin composition for blow molding comprising 95 to 0% by weight of a substantially linear polyarylene sulfide resin having a melt viscosity of 300 to 3000 poise. 2. (a) Polyarylene sal having a branched structure
Polyimide having three or more reactive functional groups
Dihaloaromatization containing 0.01 to 10 mol% of haloaromatic compound
From the polymerization reaction of the compound and the alkali metal sulfide.
2. A polyarylene sulfide resin.
Polyarylene Sulfide Resin Composition for Blow Molding
Stuff. 3. The compounding ratio of (a) and (b) is 5 to 5 by weight.
The polyarylene sulfide resin composition for blow molding according to claim 1 or 2, wherein the ratio is 95:95 to 5. 4. A polyant according to any one of claims 1 to 3.
-More than 100 parts by weight of sulfide resin (a + b)
α-olefin and α, β-unsaturated glycidyl ester
Olefin copolymer containing as an essential component 0.5 to 30 weight
Polyarylene Sulfur for Blow Molding
A resin composition. 5. The olefin-based copolymer is an α-olefin.
And a copolymer of α, β-unsaturated glycidyl ester,
Furthermore, the vinyl polymer or copolymer has a branched or crosslinked structure.
The graft copolymer according to claim 4, which is a graft copolymer chemically bonded to
Polyarylene sulfide resin composition for blow molding. 6. A polyarylene sulfide resin (a + b) 1
1 to 150 parts by weight of the fibrous filler, relative to 00 parts by weight,
A mixture of at least one of powdery and granular fillers and plate-like fillers
The polyary for blow molding according to any one of claims 1 to 5,
Rensulfide resin composition. 7. The polyant according to any one of claims 1 to 6, wherein
-Obtained by blow molding the sulfide resin composition.
Hollow molded product.