JPH0698673B2 - Blow hollow molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a blow hollow molded article having excellent heat resistance, chemical resistance and impact resistance.

<Prior art> Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) is an engineering plastic with excellent heat resistance, chemical resistance, flame retardancy, and electrical characteristics.
Demand for electronic parts, automobile parts, precision machine parts and the like has been increasing in recent years. However, the method of molding PPS resin is mostly limited to injection molding because the melt flowability of PPS resin is very large, so most of the molded product shapes are small and bottle molding by blow molding, for example. Also, it has not been applied to large parts such as tanks. As an example of blow molding, for example, a blow molding container of PPS resin described in JP-A-61-255832 and a method for producing the same are known, but this uses a PPS resin having a remarkably high degree of polymerization, and It is a combination of special injection stretch blow molding methods, and it cannot be said that general blow molding technology for PPS resin has been established.

On the other hand, for automobile parts, the method of manufacturing ducts in the engine room by blow molding is widespread,
Currently, polyamide-based materials are mainly used,
Since the polyamide-based material has insufficient heat resistance, it is a fact that a blow molding material having high heat resistance, chemical resistance and impact resistance is required.

<Problems to be Solved by the Invention> Therefore, the inventors of the present invention have earnestly studied as a problem to obtain blow hollow molded articles satisfying the above-mentioned various requirements by using a PPS resin without applying a special molding method. As a result, a resin composition comprising a deionized PPS resin and an epoxy group-containing olefin-based copolymer can give a good molded product by using a generally known blow molding method, and the molded product obtained. Have found that the above requirements are satisfied, and have reached the present invention.

<Means for Solving the Problems> That is, the present invention is a deionized PPS resin 95-6
0% by weight and epoxy group-containing olefinic copolymer 5
A blow hollow molded article characterized by comprising a PPS resin composition obtained by adding 0 to 200 parts by weight of an inorganic filler to 100 parts by weight of a resin component consisting of -40% by weight as a main constituent component. Is.

The PPS resin used in the present invention has a structural formula 70 mol% or more of the repeating unit represented by, more preferably
A polymer containing 90 mol% or more, wherein the repeating unit is 70
If it is less than mol%, heat resistance is impaired, which is not preferable.

PPS resin is generally a polymer having a relatively small molecular weight obtained by a production method represented by JP-B-45-3368 and an essentially linear polymer obtained by a production method represented by JP-B-52-12240. There is a polymer having a relatively high molecular weight and the like, and in the polymer obtained by the method described in the above Japanese Patent Publication No. 45-3368, the polymerization is carried out by heating in an oxygen atmosphere or crosslinking such as a peroxide. It is also possible to increase the degree of polymerization by adding an agent and heating it. In the present invention, the PPS resin obtained by any method can be used, but an essentially linear polymer having a relatively high molecular weight is more preferably used.

Further, the PPS resin can be composed of less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

It is essential that the PPS resin used in the present invention has been subjected to deionization treatment by acid treatment, hot water treatment or washing with an organic solvent after being produced through the above-mentioned polymerization step.

When a PPS resin that has not been deionized is used, the compatibility with the epoxy group-containing polyolefin is poor, the appearance of the resin composition is poor, and the impact resistance is significantly reduced. Absent.

The case of performing acid treatment is as follows. The acid used for the acid treatment of the PPS resin in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid can be more preferably used, but nitric acid and the like that decompose and deteriorate the PPS resin are not preferable.

The acid treatment method includes a method of immersing the PPS resin in an acid or an aqueous solution of the acid, and if necessary, it is possible to appropriately stir or heat. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in a pH 4 aqueous solution heated to 80 to 90 ° C. and stirring for 30 minutes. The acid-treated PPS resin needs to be washed several times with water or warm water in order to physically remove the residual acid or salt.

Water used for washing is preferably distilled water or deionized water in the sense that the effect of preferable chemical modification of the PPS resin by acid treatment is not impaired.

When performing hot water treatment, it is as follows.

In the hot water treatment of the PPS resin used in the present invention, the temperature of the hot water is 100 ° C or higher, more preferably 120 ° C or higher, further preferably 150 ° C or higher, and particularly preferably 170 ° C.
The above is important, and if the temperature is lower than 100 ° C., the effect of preferable chemical modification of the PPS resin is small, which is not preferable.

The water used is preferably distilled water or deionized water in order to exert the preferable effect of chemically modifying the PPS resin by the hot water washing of the present invention. The operation of hot water treatment is usually performed by charging a predetermined amount of water with a predetermined amount of PPS resin and heating and stirring in a pressure vessel. The ratio of PPS resin to water is preferably as much as possible, but usually a bath ratio of 200 g or less of PPS resin to 1 part of water is selected.

In addition, since the decomposition of the terminal group is not preferable for the treatment atmosphere, an inert atmosphere is preferably used to avoid this. Furthermore, it is preferable that the PPS resin that has undergone this hot water treatment operation be washed several times with warm water in order to physically remove the remaining components.

The following is the case of washing with an organic solvent.

The organic solvent used for washing the PPS resin in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin, and examples thereof include N-methylpyrrolidone, dimethylformamide, dimethylacetamide and 1,3-dimethylimidazo. Nitrogen-containing polar solvents such as lydinone, hexamethylphosphorus amide, piberazinones, sulfoxide / sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone and sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone, dimethyl ether, di Ether solvents such as propyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane,
Halogen-based solvents such as tetrachloroethane, perchlorethane, chlorobenzene, methanol, ethanol, propanol, butanol. Examples thereof include alcohol / phenol solvents such as pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol and polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, it is particularly preferable to use N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like. Further, these organic solvents are used alone or as a mixture of two or more kinds.

As a method of washing with an organic solvent, PPS in an organic solvent is used.
There is a method of immersing the resin, and if necessary, it is possible to appropriately stir or heat.

The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and any temperature from normal temperature to 300 ° C can be selected. The higher the cleaning temperature is, the higher the cleaning efficiency tends to be, but normally, the cleaning temperature of room temperature to 150 ° C. is sufficient to obtain the effect.

It is also possible to wash under pressure at a temperature above the boiling point of the organic solvent in a pressure vessel. Also, the washing time is not particularly limited. Although it depends on the washing conditions, in the case of batch type washing, a sufficient effect is usually obtained by washing for 5 minutes or more. It is also possible to wash in a continuous manner.

It is sufficient to wash the PPS resin produced by polymerization with an organic solvent, but it is preferable to combine it with water washing or warm water washing in order to further exert the effects of the present invention. When a high-boiling-point water-soluble organic solvent such as N-methylpyrrolidone is used, it is preferable to wash the organic solvent and then wash with water or warm water to easily remove the residual organic solvent. Water used for these washings is preferably distilled water or deionized water.

The melt viscosity of the PPS resin used in the present invention is not particularly limited, and any melt viscosity can be used as long as it can be kneaded with polyolefins, but usually 320 ° C., the melt viscosity at a shear rate of 10 sec ⁻¹ is 100. ~ 10,000 poise is used.

The epoxy group-containing olefin polymer used in the present invention is an olefin polymer having an epoxy group in its side chain or main chain, and does not include ordinary epoxy resins. Examples of the epoxy group-containing olefin polymer include olefin polymers having a glycidyl group such as glycidyl ester, glycidyl ether, and glycidyl amine in the side chain, and those obtained by epoxidizing a double bond of a double bond-containing olefin polymer. Can be mentioned. In the present invention, among these epoxy group-containing olefin polymers, α-olefin and α,
A copolymer composed of glycidyl ester of β-unsaturated acid is preferably used. Examples of the α-olefin include ethylene, propylene and butene-1. Further, the glycidyl ester of α, β-unsaturated acid has the general formula (R represents a hydrogen atom or a lower alkyl group), and specific examples thereof include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate. The content of the epoxy group in the epoxy group-containing olefin polymer is 0.1 to 30% by weight, particularly 0.2 to
20% by weight is preferable, and if less than 0.1% by weight, the desired effect cannot be obtained, and if more than 30% by weight, gelation occurs during melt kneading with PPS resin, and extrusion stability, moldability and mechanical properties deteriorate. Therefore, it is not preferable.

The epoxy group-containing olefin-based polymer may be copolymerized with other olefin-based monomers such as methyl acrylate, methyl methacrylate, acrylonitrile, styrene, vinyl acetate and vinyl ether as long as the effects of the present invention are not impaired. Good.

The compounding ratio of the PPS resin and the epoxy group-containing olefin polymer in the resin composition used in the present invention is 95/5 to 60/4.
It is 0% by weight, preferably in the range of 90/10 to 65/35% by weight, and by adopting the blending ratio in this range, the drawdown of the parison during molding is small and good blow moldability is exhibited, and heat resistance and resistance It is possible to obtain blow hollow molded products with excellent chemical properties. The compounding amount of PPS resin is 9
If it exceeds 5% by weight, blow moldability is deteriorated, and if it is less than 60% by weight, heat resistance and chemical resistance are impaired, which is not preferable.

In the present invention, the fibrous and / or granular reinforcing agent is not an essential component, but if necessary, it may be 2 parts by weight based on 100 parts by weight of the total of the PPS resin and the epoxy group-containing olefin copolymer.
It is possible to mix in a range that does not exceed 00 parts by weight,
Strength by normally compounding in the range of 10 to 150 parts by weight,
It is possible to improve rigidity, heat resistance and dimensional stability.

Such fiber reinforcing agents include glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers,
Examples include gypsum fibers, metal fibers and carbon fibers.

Further, as the granular reinforcing agent, silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, and alumina silicate, metal oxides such as alumina, silicon chloride, magnesium oxide, zirconium oxide, and titanium oxide. Substances, calcium carbonate, magnesium carbonate, dolomite, and other carbonates, calcium sulfate, barium sulfate, and other sulfates, glass beads, boron nitride, silicon carbide, and silica, which may be hollow. Two or more of these reinforcing agents can be used in combination, and if necessary, they can be used after pretreatment with a coupling agent such as a silane-based or titanium-based coupling agent.

The method for preparing the resin composition used in the present invention is not particularly limited, and powders, pellets, and pieces of PPS resin epoxy group-containing olefin copolymer and, if necessary, a reinforcing material may be added to a ribbon blender, a Henschel mixer, a V blender. And the like, and then melt-kneading using a Banbury mixer, a mixing roll, a single-acting or twin-screw extruder, a kneader, and the like. Of these, a typical method is melt kneading using a single-screw or twin-screw extruder having a sufficient kneading force.

Further, in the resin composition comprising the PPS resin and the epoxy group-containing olefin polymer used in the present invention, as long as the effect of the present invention is not impaired, an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, an anti-UV agent. Conventional additives such as agents, colorants, flame retardants and small amounts of other polymers can be added.
For the purpose of controlling the crosslinking degree of the PPS resin, a conventional peroxide and a crosslinking accelerator such as a metal thiophosphinic acid salt described in JP-A-59-131650 or JP-A-58-20404.
It is also possible to add a crosslinking inhibitor such as dialkyltin dicarboxylate and aminotriazole described in JP-A No. 5 and JP-A No. 58-204046.

The blow hollow molded article of the present invention is a known blow molding method for the resin composition obtained as described above, that is, basically, the resin composition is fed to an extruder and melt-extruded to form a parison. It can be obtained by subjecting it to a two-dimensional hollow molded article of interest. Typical examples of commonly known blow molding methods include a direct blow method, an accumulator blow method, and a multidimensional blow method, and a multilayer blow molding method and an exchange blow molding method used in combination with other materials. Of course, it is also possible to apply.

Specific examples of the blow hollow molded article of the present invention molded in this manner include bottles, tanks and ducts, which are hollow molded articles excellent in heat resistance, chemical resistance and impact resistance, and are containers for chemical liquids. It is useful for air conditioning ducts, ducts and pipes in automobile engine rooms.

<Examples> The present invention will be described in more detail with reference to Examples.

The properties described in Examples and Comparative Examples were measured by the following methods.

(1) Molding method: The resin composition pellets are supplied to a blow molding machine equipped with a 50 mmφ extruder and extruded at a cylinder temperature of 320 ° C. to mold a parison having an outer diameter of 100 mm and a wall thickness of 4 mm, and then in a mold. Air was blown into the container to form a regular prismatic container having a side of 150 mm and a height of 500 mm. The thickness of each of the upper part and the lower part of the body of this molded product was measured, and if the difference between the upper average thickness and the lower average thickness was within 1 mm, the moldability was good and the thickness difference was 1 mm.
Those exceeding the above were judged to be defective.

(2) Heat resistance: The maximum temperature at which the amount of deformation was within 2 mm when the load of 2.5 kg was applied to the container body at a predetermined temperature for 1 hour was measured and used as a guide for heat resistance.

(3) Impact resistance: The above container was dropped from a height of 1 m onto a concrete floor, and the presence or absence of damage and cracks in the container was visually judged. The test was carried out with n = 20, the number of those that did not break was counted, and the non-breakdown rate was expressed as a percentage of 100, which was used as a measure of impact resistance.

Reference Example 1 (Polymerization of PPS Resin) 3.20 kg of sodium sulfide (25 mol, containing 40% of water of crystallization), 4 g of sodium hydroxide, 1.36 kg (about 10 mol) of sodium acetate trihydrate and N-methyl-in an autoclave. 7.9 kg of 2-pyrrolidone (hereinafter abbreviated as NMP) was charged, the temperature was gradually raised to 205 ° C. with stirring, and about 1.5 l of distilled water containing 1.36 kg of water was removed. To the remaining mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added, and the mixture was stirred at 265 ° C for 4 hours.
Stir for hours. The reaction product was washed 5 times with hot water at 70 ° C,
It is dried under reduced pressure at 80 ℃ for 24 hours, and the melt viscosity is about 2500 poise (32
0 ° C., powdered PPS resin shear rate of 10 sec ^-1) (P-1) to about 2kg
Got

The same operation was repeated and used in the examples described below.

Reference Example 2 (acid treatment of PPS resin) About 2 kg of the PPS resin powder obtained in Reference Example 1 was put into 20 liters of an acetic acid aqueous solution of pH 4 heated to 90 ° C., and the mixture was stirred for about 30 minutes and then passed. The product was washed with deionized water at about 90 ° C. until the pH of the solution reached 7, and dried under reduced pressure at 120 ° C. for 24 hours to give a powder, thereby obtaining an acid-treated PPS resin (P-2).

Reference Example 3 (hot water treatment of PPS resin) About 2 kg of the PPS resin powder obtained in Reference Example 1 and deionized water 10
After charging and l into an autoclave and sealing at normal pressure, 1
The temperature was raised to 75 ° C., the temperature was maintained for about 30 minutes while stirring, and then the mixture was cooled. Take out the contents, and further immerse PPS in approximately 10 liters of deionized water at 70 ° C, stir it, and pass it.
Repeated times. Then, it was dried under reduced pressure at 120 ° C. for 24 hours to obtain hot water washed PPS resin (P-3).

Reference Example 4 (Washing of PPS Resin with Solvent) About 2 kg of the PPS resin powder obtained in Reference Example 1 was put into 20 ml of NMP heated to 100 ° C., stirred for about 30 minutes, and then passed.
Then, it was washed with ion-exchanged water at about 90 ° C. This one 12
It was dried under reduced pressure at 0 ° C. for 24 hours to obtain NMP-washed PPS resin (P-4).

Example 1 70% by weight of PPS resin (P-2) obtained in Reference Example 2, 10% by weight of ethylene / glycidyl methacrylate copolymer (88/12% by weight) and 20% by weight of glass fiber were dry blended with a Henschel mixer. After that, the mixture was fed to the hopper of a 65 mmφ single screw extruder, melt-kneaded under the conditions of a cylinder temperature of 32 ° C. and a screw rotation speed of 50 rpm to form pellets. The pellets were dried with hot air at 130 ° C. for 3 hours, and then, using the blow molding machine, a regular square columnar container having a side of 150 mm and a height of 500 mm was molded. As a result, a hollow molded article having a good surface appearance was obtained without drawdown of the parison. The physical properties of this hollow molded article are as shown in Table 1, and it was found that the hollow molded article has extremely high practical value with no uneven thickness in the molded article and good heat resistance and impact resistance.

Comparative Example 1 80% by weight of PPS resin (P-2) and 20% by weight of glass fiber without using ethylene / glycidyl methacrylate copolymer
Melt kneading was carried out in the same manner as in Example 1 except that the composition was changed to 1. Then, the obtained pellets were dried and then subjected to a blow molding machine to try molding, but this had a very large draw town of the parison, Only a molded product with a large uneven thickness could be obtained.

Example 2 65% by weight of the PPS resin (P-3) obtained in Reference Example 3, 20% by weight of the ethylene / glycidyl methacrylate copolymer used in Example 1 and 15% by weight of mica were used in the same procedure as in Example 1. Was melt-kneaded, followed by blow molding. Here again, a blow hollow molded product having a small parison drawdown and a good surface appearance was obtained. As shown in Table 1, this product was a molded product having no uneven thickness and good heat resistance and impact resistance.

Comparative Example 2 Melt kneading and blow molding were carried out in exactly the same manner as in Example 1 except that the PPS resin (P-1) obtained in Reference Example 1 was used instead of P-2. Only a molded product having a poor appearance could be obtained, and its impact resistance was extremely poor as shown in Table 1 and was not practical.

Examples 3 to 6 PPS resin, ethylene / glycidyl methacrylate copolymer and the kind and blending amount of the filler were changed as shown in Table 1, and melt kneading and blow molding were carried out in the same procedure as in Example 1. did. In all cases, blow hollow molded articles with good surface appearance were obtained without drawdown of the parison. The various physical properties are shown in Table 1, and the uniformity, heat resistance and impact resistance of the molded product were all good.

<Effect of the Invention> The blow hollow molded article of the present invention has excellent blow moldability,
It has impact resistance and heat resistance, and is a chemical resistant tank,
It can be beneficially used for applications such as bottles and automobile ducts.

Claims (4)

[Claims] 1. An inorganic filler of 0 to 200 parts by weight per 100 parts by weight of a resin component composed of 95 to 60% by weight of a deionized polyphenylene sulfide resin and 5 to 40% by weight of an epoxy group-containing olefin copolymer. A blow hollow molded article comprising a polyphenylene sulfide resin composition obtained by adding a part thereof as a main constituent. 2. A blow hollow molded article according to claim 1, wherein the deionization treatment comprises treating with an aqueous acid solution and then washing with water. 3. The blow hollow molded article according to claim 1, wherein the deionization treatment comprises treating with hot water and then washing with water. 4. The blow hollow molded article according to claim 1, wherein the deionization treatment comprises washing with an organic solvent and then washing with water.