JP3486423B2 - Resin composition and blow molding material comprising the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition comprising polyphenylene sulfide (hereinafter abbreviated as PPS) and a filler, a blow molding material comprising the resin composition, a molded article obtained by blow molding the material, and a product thereof. The present invention relates to a manufacturing method.

[0002]

2. Description of the Related Art PPS is known as a high-performance engineering plastic excellent in chemical resistance, heat resistance and flame retardancy.

However, the PPS that has been used industrially in the past has been difficult to blow-mold from the viewpoint of the molding material because the drawdown is severe.

Therefore, as an attempt to improve such a defect, Japanese Patent Laid-Open No. 61-255832 proposes to perform injection stretch blow molding of a substantially linear PPS having a certain melt viscosity range under special conditions. ing. However, this is not common because it is limited to molding under special conditions, and there is no improvement in drawdown property.

Further, in Japanese Patent Laid-Open No. 3-32816,
Blow moldable thermoplastics made of PPS having a range of melt flow values, methods of forming the same and products thereof have been proposed. However, the melt flow value is a value that reflects the viscosity of the resin, and is a value that is unrelated to blow moldability, especially drawdown.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a PPS resin composition comprising PPS having improved blow moldability of PPS, which has been conventionally difficult to blow mold, and particularly improved drawdown property, a blow molding material, and molding thereof. The present invention provides a product and a manufacturing method thereof.

[0007]

In order to solve the above-mentioned problems, the inventors of the present invention have reached the present invention as a result of extensive studies on blow moldability and melt viscosity or melt tension of PPS to be used. That is, the present invention is alkoxysilane
0.03N obtained by oxidative crosslinking without using a lan compound
P composed of PPS and filler having the above melt tension and MFR of 19 g / 10 min or more and 68 g / 10 min or less
PS resin composition, the resin composition or alkoxysilane
It has a melt tension of 0.05 N or more obtained by oxidative crosslinking without using a compound and has an MFR of 19 g / 10 min or more 53
TECHNICAL FIELD The present invention relates to a blow molding material made of PPS that is g / 10 minutes or less, a molded article obtained by blow molding the material, and a method for producing the same. The present invention will be described in detail below.

The term "melt tension" in the present invention is a tension when a molten resin is formed into a strand, and can be measured by using, for example, a Capillograph manufactured by Toyo Seiki Co., Ltd.

In the present invention, using the above apparatus, the barrel temperature (300 ° C.) and the capillary dimensions (length / diameter = 8 /
2.095 (mm / mm)), piston speed (50
(mm / min), the strand was extruded, and the load detected by a load cell with a tension pulley when the strand was pulled by a take-up roll at a speed of 10 m / min was determined as melt tension (unit: Newton (N)). .

The PPS used in the present invention has the general formula

[0011]

[Chemical 1]

If the PPS contains 70 mol% or more of the structural unit represented by, and the copolymerization component is less than 30 mol%, the meta bond is

[0013]

[Chemical 2]

Ortho coupling

[0015]

[Chemical 3]

Ether bond

[0017]

[Chemical 4]

Sulfone bond

[0019]

[Chemical 5]

Biphenyl bond

[0021]

[Chemical 6]

Carbonyl bond

[0023]

[Chemical 7]

Substituted phenyl sulfide bond

[0025]

[Chemical 8]

(Wherein R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal base of a carboxylic acid )

[0027]

The content of the above components may be within a range that does not significantly affect the crystallinity of the polymer, but the content of the copolymerization component is preferably 10 mol% or less.

Such PPS is 0.05N or more, preferably 0.05N or more and 0.5N or more when the filler is not mixed.
It has a melt tension of less than 0.1 N, and more preferably 0.1 N or more and less than 0.5 N.
03N or more, preferably 0.03N or more and less than 0.5N,
More preferably, it has a melt tension of 0.1 N or more and less than 0.5 N and is not particularly limited as long as it can be obtained by a known method. However, the melt tension is 0.05N
If it is less than (when the filler is not mixed) or less than 0.03 N (when the filler is mixed), the drawdown is severe and it cannot be used for blow molding.

Further, the molecular structure of the PPS is of branched obtained by oxidative crosslinking.

[0031]

If it is a branched product obtained by oxidative crosslinking, the melt viscosity before oxidative crosslinking is 100 or more and 1000 or more.
The melt viscosity after oxidative crosslinking of less than 00, preferably 500 or more and less than 10,000 is 1,000 or more and 1,000,000.
Those that are oxidatively crosslinked to less than 1, preferably 3,000 or more and less than 100,000 are suitably used.

As a concrete method for producing such PPS,
For example, (1) Reaction of halogen-substituted aromatic compound with alkali sulfide (US Pat. No. 2,513,188, JP-B-4)
No. 4-27671 and Japanese Patent Publication No. 45-3368), (2) Coupling reaction in the coexistence of thiophenols with an alkali catalyst or a copper salt (US Pat. No. 3,274,416).
5 and British Patent No. 1160660),
(3) A binding reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (Japanese Patent Publication No. 46-27255 and Belgian Patent No. 29437).

In the present invention, the PPS obtained by the above-mentioned production method or the like is preferably used after being oxidatively crosslinked by appropriately adjusting the temperature, time and atmosphere so as to obtain a desired melt tension.

Such oxidative crosslinking can be carried out using various known methods. Examples thereof include oxidative crosslinking using a ribbon blender, a fluidized bed, an oven, and a rotary mixer for containers. Among them, a method using a ribbon blender is preferable, and PPS is made into powder and is performed in oxygen, ozone or a gas containing these. .

The temperature at which the oxidative crosslinking is carried out is 200 ° C. or higher and lower than the melting point, and preferably 220 in view of productivity.
C. or higher and lower than 270.degree. If the temperature is 200 ° C or lower, the curing rate is slow and not practical, and if it is higher than the melting point, fusion of PPS particles may occur, which is not preferable.

The filler used in the present invention is a reinforcing filler such as glass fiber, carbon fiber, ceramic fiber such as alumina fiber, aramid fiber, wholly aromatic polyester fiber, metal fiber or the like , calcium carbonate, mica, talc, silica. , Barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite,
Nepheline sinite, attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide,
It is an inorganic filler such as graphite, gypsum, glass beads, glass powder, glass balloons, quartz, quartz glass, etc., and one or more of these can be used.
% By weight, preferably 1-40% by weight, more preferably 1
-20% by weight is preferably used.

For example, as the glass fiber, the fiber diameter is 3 to
20 μm, preferably 6 to 15 μm and fiber length 1.5 to 1
Examples include chopped strands having a diameter of 2 mm, preferably 3 to 6 mm, milled fibers having a fiber diameter of 3 to 20 μm and a fiber length of 30 to 500 μm, and glass flakes and glass powder having a mesh of 325 or less.

Further, it is preferable to use the glass fiber treated with an organosilane compound. The organosilane compound is not particularly limited as long as it is a known compound, and examples thereof include an epoxysilane compound, a ureidosilane compound, a mercaptosilane compound, a hydroxysilane compound, a vinylsilane compound, and the like, and one or more of them may be used. good. Particularly preferred organosilane compounds are epoxysilane compounds and ureidosilane compounds.

The epoxysilane compound is an alkoxysilane or halosilane having one or more epoxy groups in the molecule, such as 2-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and β. -(3,4-epoxycyclohexyl)
Examples thereof include ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. One kind or two or more kinds may be used in combination.

The ureidosilane compound is an alkoxysilane or halosilane having one or more ureido groups in the molecule, and examples thereof include 2-ureidopropyltrimethoxysilane and 3-ureidopropyltrimethoxysilane.
3-ureidopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane and the like can be mentioned, and one kind or two or more kinds can be used in combination.

Further, the PPS resin composition and the blow molding material of the present invention can be used in the range not departing from the object of the present invention.
Thermoplastic elastomers such as ethylene-propylene-
Ethylidene norbornene copolymer (EPDM rubber), ethylene-propylene copolymer (EP rubber), ethylene-
A butene-1 copolymer, a styrene-butadiene block copolymer, a styrene block copolymer elastomer, an amide elastomer, an ester elastomer, a urethane elastomer or the like, or a rubbery polymer such as a conjugated diene rubber or an acrylic rubber. It is also possible to add. Furthermore, polyethylene, polystyrene, polybutene,
Polymethylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polyarylate, nylon 6, nylon 66, nylon 4
6, nylon 12, nylon 11, amorphous nylon, polyamide such as aromatic nylon, polyurethane, polyacetal, polycarbonate, polyphenylene ether,
Polysulfone, polyether sulfone, polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyether ether ketone, polyphenylene sulfide ketone, polyimide, polyamideimide,
It is also possible to add a thermoplastic resin such as a homopolymer of a silicone resin, a phenoxy resin, a fluororesin or an epoxy resin, a random polymer or a block, a graft copolymer and a mixture thereof, or a thermosetting resin.

If desired, organic and inorganic pigments may be added.

Further, a plasticizer such as an aromatic hydroxy derivative, a releasing agent , a titanate coupling agent, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a crystal nucleating agent, a foaming agent, a rust preventive agent,
Ion trap agents, flame retardants, flame retardant aids, antioxidants, ultraviolet absorbers, hindered amine light stabilizers, colorants, and metal salts of thiophosphinic acid as crosslinking accelerators for the purpose of controlling the degree of crosslinking of PPS. A crosslinking inhibitor such as dialkyltin dicarboxylate or aminotriazole may be added if necessary.

The PPS resin composition and the blow molding material according to the present invention can be pelletized by adding various components described above and various known methods. For example, a heating melt kneading method using a single screw extruder, a twin screw extruder, a kneader, a Brabender, etc. is most preferable. The kneading temperature at this time is not particularly limited, but can be arbitrarily selected from the range of usually 200 to 400 ° C.

The PPS and the filler may be mixed by dry blending before the heat-melting and kneading, or the filler may be added during the heat-melting and kneading of the PPS.
For example, a method in which a filler is added during heating, melting, and kneading using a twin-screw extruder and a side feeder is preferable.

The blow molding material of the present invention is excellent in drawdown resistance and can be molded using various known devices and methods, but the extrusion blow method and the injection blow method are preferable.

The kneading temperature at this time is not particularly limited, but normally the cylinder temperature and the die temperature are suitably selected from 200 ° C to less than 400 ° C, preferably 250 ° C to less than 370 ° C.

The mold temperature can be suitably selected from 0 ° C. to less than 200 ° C. according to the desired properties of the molded product. For example, if a crystalline molded article is desired, 12
A mold temperature of 0 ° C. or higher, and 80 ° C. or lower if an amorphous molded product is desired, is appropriately selected.

The blow molding material of the present invention has excellent drawdown resistance, and is suitable for bottles, tanks, flasks,
It is possible to make molded products of various shapes such as pipes and ducts.

[0051]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 (Synthesis of PPS) Internal volume 530 equipped with a stirrer, dehydration tower and jacket
110 liters of N-methylpyrrolidone and sodium sulfide (purity: Na ₂ S 60.2 wt%) 61.1
Then, kg was charged, the mixture was heated by a jacket with stirring, and distillation was performed through a dehydration tower until the internal temperature reached about 200 ° C.
At this time, 13.5 l of an extract mainly consisting of water was distilled off. Then, 68.7 kg of p-dichlorobenzene and 48 l of N-methylpyrrolidone were added, and the mixture was added over 2 hours to 2
After heating up to 25 ° C and reacting at 225 ° C for 2 hours,
The temperature was raised to 250 ° C over 30 minutes, and the reaction was further performed at 250 ° C for 3 hours.

After completion of the reaction, the reaction mixture was transferred to a solvent collector equipped with a stirrer, a jacket and a decompression line. At this time, 30 l of N-methylpyrrolidone was added. Subsequently, it was heated under reduced pressure to distill off 210 l of a distillate mainly composed of N-methylpyrrolidone.

Subsequently, 200 l of water was added to form a water slurry, which was heated and stirred at 80 ° C. for 15 minutes and then centrifuged to recover the polymer.

Further, the polymer is returned to the solvent recovery unit, and water 2 is added.
001 was added and heated and stirred at 100 ° C. for 30 minutes,
After cooling, the polymer powder was collected by a centrifuge. This operation was repeated twice. The obtained polymer was transferred to a ribbon blender with a jacket and dried.

The polymer thus obtained has a melt viscosity of 710 poise and is designated as PPS-I.

Reference Example 2 Instead of 68.7 kg of p-dichlorobenzene in Reference Example 1, 69.0 kg of p-dichlorobenzene was used.
PPS was synthesized in the same manner as in Reference Example 1 except that the reaction time at 250 ° C. was 4 hours. The polymer thus obtained has a melt viscosity of 1130 poise,
PS-II.

Reference Examples 3 to 11 15 kg of the PPS obtained in Reference Examples 1 and 2 was charged into a ribbon blender having an internal capacity of 110 l, stirred at a rotation speed of 60 rpm, and air was fed by the amount shown in Table 1 at 265 ° C., respectively. Oxidative crosslinking was performed to synthesize PPS of Reference Examples 3 to 11. Table 1 also shows the types of PPS used for synthesizing the PPS of Reference Examples 3 to 11, the oxidative crosslinking conditions (air amount, oxidative crosslinking time) and the melt viscosity, MFR, and melt tension of PPS after oxidative crosslinking. .

The MFR is measured according to ASTM D123.
8 Procedure B was performed at a temperature of 315 ° C. and a load of 5 kg.
The unit is g / 10 minutes.

[0060]

[Table 1]

Examples 1 to 12 and Comparative Examples 1 to 6 PPS obtained in Reference Examples 3 to 11 was dry blended with glass fiber or calcium carbonate having the composition shown in Table 2 to obtain 2
Melt-kneading is performed under the condition of a screw rotation speed of 200 rpm using a co-rotating twin-screw extruder set to 50 to 340 ° C.,
The extruded strands were pelletized.

The pellets thus obtained are treated at 150 ° C.
And dried for 5 hours. 55 dry PPS pellets
Blow molding was performed using a mm in-line screw type blow molding machine. Molding conditions are cylinder temperature 285 ℃, die temperature 285 ℃, mold temperature 135 ℃, die bush diameter 3
2 mm, core diameter 27 mm, screw rotation speed 50 rp
m, blowing pressure 5 kg / cm ² . The results of blow molding are shown in Table 2.

[0063]

[Table 2]

From these results, the blow moldability is closely related to the melt tension, not the melt viscosity. When the filler is not blended, the melt tension of PPS is 0.05 N or more, and when the filler is blended. Has a PPS melt tension of 0.03N
It can be seen that in the above case, good blow moldability is exhibited.

[0065]

The blow molding material according to the present invention is excellent in heat resistance, flame retardancy and chemical resistance, and can be used in bottles, tanks,
Since it can be molded into various shapes such as flasks, pipes and ducts, it can be widely used as an excellent molding material in the field of industrial materials such as automobiles, electricity, electronics and machinery.

Front page continued (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 81/02 C08G 75/02 B29C 49/00 B29K 81/00 B29K 22/00

Claims (5)

(57) [Claims] 1. An oxidation rack without using an alkoxysilane compound.
A ) Polyphenylene sulfide obtained by cross-linking and having a melt tension of 0.03 N or more and a melt flow rate (MFR) of 19 g / 10 min or more and 68 g / 10 min or less (however, using a trifunctional group-containing monomer) A polyphenylene sulfide resin composition comprising 99 to 50% by weight of a copolymer and b) 1 to 50% by weight of a filler. 2. A blow molding material comprising the polyphenylene sulfide resin composition according to claim 1. 3. An oxidation rack without using an alkoxysilane compound.
The bridge has a melt tension of 0.05 N or more and a melt flow rate (MFR) of 19 g / 10 min or more 53
A blow molding material composed of polyphenylene sulfide (excluding a copolymer using a trifunctional group-containing monomer) having a content of not more than 10 minutes. 4. A polyphenylene sulfide blow molded product obtained by blow molding the material according to claim 2. 5. A method for producing a blow-molded product, which comprises using the material according to claims 2-3.