JPWO2012147185A1 - Method for producing polyarylene sulfide-based resin composition - Google Patents

Abstract

In addition to the effects of aminosilane addition such as suppression of burrs and improvement of weld strength, a technique for significantly removing residuals such as unreacted raw materials when producing a polyarylene sulfide resin composition is provided. . The position of the plasticizing part and the pressure raising part of the screw arranged in the cylinder of the extruder and the position of the vent part provided in the cylinder are adjusted. Further, in the present invention, water is injected in the boosting unit. Moreover, it is preferable that a pressure | voltage rise part has a seal ring in both ends. In the present invention, a screw having a plurality of boosting sections may be used.

Description

  The present invention relates to a method for producing a polyarylene sulfide-based resin composition.

  In the thermoplastic resin, unreacted monomers, side reaction products and solvents during polymerization remain. Even if these residues become a thermoplastic resin composition through an extrusion process, they remain in the composition. It has been found that, during injection molding, extrusion molding, and the like of the composition, it becomes a gas, volatilizes and becomes odor, or has an adverse effect such as mold contamination.

  As one of the thermoplastic resins having the problem of the residue, polyarylene sulfide resin can be given. Specifically, unreacted raw material (for example, paradichlorobenzene (p-DCB)) remains in the polyarylene sulfide resin, and a technique for removing this is demanded.

  A method of removing unreacted raw materials such as paradichlorobenzene from the polymer in the polymerization process of the polyarylene sulfide resin has also been studied. Moreover, the method of removing these residues by fully devolatilizing in the extrusion process which manufactures a polyarylene sulfide type-resin composition is also examined. Currently, the latter tends to be studied for the reason that no new equipment cost is required.

  For example, in Patent Document 1, when polyarylene sulfide-based resin is melt-extruded, a twin-screw extruder provided with a gas body supply port and a vent portion is used, and melt extrusion is performed while supplying a gas body to the extruder. And a technique for removing residues such as oligomer components from the vent. Furthermore, it is described that it is preferable to provide two or more vent parts, and the position may be a melted part of polyarylene sulfide-based resin.

  However, when an active gas such as air or oxygen is used as the gas body, the thermoplastic resin undergoes a crosslinking reaction to reduce the fluidity of the composition, the color changes due to oxidation, or the mechanical properties due to deterioration. It may cause problems such as lowering. On the other hand, when an inert gas typified by nitrogen is used, there is a disadvantage in that the oxygen concentration around the extruder is lowered, and the worker may be exposed to danger.

  In Patent Document 2, a polyarylene sulfide resin is held in a molten state by using an extruder having a heating device and a vent part, and at the same time, water, water vapor, or an organic solvent is injected into the extruder, A technique is described in which an oligomer component or the like contained in an arylene sulfide-based resin is separated and extruded while discharging the oligomer component from a vent together with water vapor or an organic solvent.

  However, when a method of supplying a liquid or a vapor thereof, such as the technique described in Patent Document 2, there is a concern that the extrudability is deteriorated such that the molten resin in the extruder is cooled by the liquid or the vapor and solidified. .

  Patent Document 3 discloses a method for reducing the residue without supplying a gas body, water, water vapor, organic solvent, or the like into the twin-screw extruder. In Patent Document 3, specifically, the residual matter is reduced by adjusting the length of a screw used for deaeration.

  However, even if any of the methods described in Patent Document 1 to Patent Document 3 is adopted, the effect of reducing the residual material is not sufficient, and improvement is required.

Japanese Patent Laid-Open No. 06-306170 Japanese Patent Laid-Open No. 06-306171 JP 2010-228408 A

  The present invention has been made to solve the above-mentioned problems, and its purpose is to produce effects of adding aminosilane such as suppression of burr generation and improvement of weld strength, and to produce a polyarylene sulfide-based resin composition. In addition, an object of the present invention is to provide a technique that has the effect of greatly removing residuals such as unreacted raw materials.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by adjusting the positions of the plasticizing part and the pressure raising part of the screw disposed in the cylinder of the extruder and the position of the vent part provided in the cylinder, and the present invention is completed. It came to. More specifically, the present invention provides the following.

  (1) A polyarylene containing a polyarylene sulfide resin that has been previously dried using an extruder in which a screw having a supply unit, a plasticizing unit, and a pressurizing unit is arranged in a cylinder from the upstream side, which is a raw material supply side. A method for producing a sulfide-based resin composition, wherein the cylinder is provided with a first vent part provided with a decompression means between the plasticizing part and the pressurization part, and a decompression process downstream of the pressurization part. A second vent part provided with means, and a water injection port for injecting water into the cylinder downstream from the plasticizing part, and from the downstream end of the plasticizing part, L1 / D, which is a ratio of the length L1 to the upstream end and the diameter D of the screw, is 3.0 or more and 25.0 or less, and from the downstream end of the pressurizing unit to the downstream side of the screw A length L2 to the end, L2 / D, which is a ratio to the diameter D of the clew, is 5.0 or more and 15.0 or less, a raw material containing polyarylene sulfide resin and aminosilane is supplied from the supply unit, and the pressure increase is made from the water inlet. The manufacturing method of the polyarylene sulfide-type resin composition which inject | pours the said water toward a part.

  (2) The method for producing a polyarylene sulfide-based resin composition according to (1), which has seal rings at both ends of the pressurizing unit.

  (3) A poly having been dried in advance using an extruder in which a screw having a supply section, a plasticizing section, a first pressurizing section, and a second pressurizing section is arranged on the cylinder from the upstream side which is the raw material supply side A method for producing a polyarylene sulfide-based resin composition containing an arylene sulfide resin, wherein the cylinder includes a first vent portion provided with a decompression means between the first pressure increase portion and the second pressure increase portion. A second vent part provided with a pressure reducing means downstream from the second pressure increasing part, and a water inlet for injecting water into the cylinder downstream from the plasticizing part, L3 / D, which is the ratio of the length L3 from the downstream end of the booster to the upstream end of the second booster and the diameter D of the screw, is 3.0 or more and 15.0 or less, The screw from the downstream end of the second pressurizing unit L2 / D, which is the ratio of the length L2 to the downstream end and the diameter D of the screw, is 5.0 or more and 15.0 or less, and is a raw material containing polyarylene sulfide resin and aminosilane from the supply unit And the water is injected from the water injection port toward the first pressure-increasing part and / or the second pressure-increasing part. A method for producing a polyarylene sulfide-based resin composition.

  (4) From the upstream side which is the raw material supply side, a poly having been subjected to a drying process in advance using an extruder in which a screw having a supply unit, a plasticizing unit, a first pressurizing unit and a second pressurizing unit is arranged in a cylinder A method for producing a polyarylene sulfide-based resin composition containing an arylene sulfide resin, wherein the cylinder includes a first vent portion provided with a decompression means between the plasticizing portion and the first pressure increase portion, A second vent part provided with a pressure reducing means downstream from the second pressure raising part; and a water inlet for injecting water into the cylinder downstream from the plasticizing part, the plasticizing part L4 / D, which is the ratio of the length L4 from the downstream end of the first pressure increasing portion to the upstream end of the first pressure increasing portion and the diameter D of the screw, is 3.0 or more and 15.0 or less. Under the screw from the downstream end of the second booster L2 / D, which is the ratio of the length L2 to the side end and the diameter D of the screw, is 5.0 or more and 15.0 or less, and a raw material containing polyarylene sulfide resin and aminosilane from the supply unit. A method for producing a polyarylene sulfide-based resin composition that is supplied and injected from the water injection port toward the first pressure-increasing part and / or the second pressure-increasing part.

  (5) The method for producing a polyarylene sulfide-based resin composition according to (3) or (4), wherein seal rings are provided at both ends of the first booster and / or the second booster.

  According to the present invention, residues such as unreacted raw materials can be largely removed when producing a polyarylene sulfide-based resin composition.

It is a figure which shows typically the cross section of the extruder of 1st embodiment. It is a figure which shows typically the cross section of the extruder of 2nd embodiment. It is a figure which shows typically the cross section of the extruder of 3rd embodiment. 1 is a schematic diagram of an extruder used in Example 1 and Comparative Example 1. FIG. 6 is a schematic diagram of an extruder used in Comparative Example 2. FIG. 4 is a schematic diagram of an extruder used in Example 2 and Comparative Example 3. FIG. 6 is a schematic diagram of an extruder used in Comparative Example 4. FIG. 6 is a schematic diagram of an extruder used in Example 3 and Comparative Example 5. FIG. 10 is a schematic diagram of an extruder used in Comparative Example 6. FIG.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment.

<Method for producing polyarylene sulfide-based resin composition>
The method for producing a polyarylene sulfide-based resin composition of the present invention uses a raw material containing a polyarylene sulfide resin and aminosilane. First, these raw materials will be described.

[material]
The polyarylene sulfide resin is composed mainly of-(Ar-S)-as a repeating unit (Ar represents an arylene group). In the present invention, polyarylene sulfide resins having a generally known molecular structure can be used. For example, a polyarylene sulfide resin similar to the resin described in JP2009-138039A can be used.

  Among the residues to be removed in the present invention, one of the particularly problematic residues is a monomer that remains unreacted in the raw material monomers used in the production of the polyarylene sulfide resin.

The production of polyarylene sulfide resin is, for example,
A method of polymerizing a dihalogenoaromatic compound and, if necessary, another copolymerizable monomer in the presence of sulfur and sodium carbonate;
A method of polymerizing a dihalogenoaromatic compound and, if necessary, another copolymerizable monomer in a polar solvent in the presence of a sulfidizing agent,
a method of self-condensing p-chlorothiophenol and, if necessary, other copolymerization monomers,
In an organic polar solvent, it can be performed by a method of reacting a sulfidizing agent, a dihalogenoaromatic compound, and, if necessary, another copolymerization monomer.

  In particular, in the polyarylene sulfide-based resin, the remaining of the dihalogenoaromatic compound becomes a problem. However, if the production method of the present invention is employed, this remaining material can be easily removed.

  Next, aminosilane will be described. Aminosilane is used for the purpose of suppressing the generation of burrs during the production of a molded article and the purpose of improving the weld strength.

  Specific examples of aminosilane compounds include γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-aminopropyltrimethoxysilane. , Γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and the like.

  As a conventional method for removing a residue, a method using water is known (Patent Document 2 and the like). In the method described in Patent Document 2 and the like, water is injected into a melted portion of polyarylene sulfide resin. Furthermore, the polyarylene sulfide resin charged in the extruder may be a wet powder resin containing moisture. However, as will be described later, the removal effect of paradichlorobenzene cannot be sufficiently obtained unless water is injected into the pressure increasing portion. In the present invention, when water is supplied from a hopper, aminosilane reacts with water and is hydrolyzed. When aminosilane is hydrolyzed, the effects obtained by using aminosilane described above are lost. Therefore, in the present invention, it is necessary to use a polyarylene sulfide resin that has been previously dried. The degree of drying is not particularly limited, but the water content of the dried polyarylene sulfide resin is usually 0.2% by mass or less with respect to 100% by mass of the polyarylene sulfide resin.

  In the present invention, the residue can be sufficiently removed without introducing water from the hopper, but as polyarylene sulfide resin before being introduced into the hopper, acid washing, hot water washing, organic solvent washing ( Alternatively, the necessity of introducing water from the hopper can be further reduced by using a product obtained by removing by-product impurities and purifying by performing a combination thereof.

  Next, other components will be described. Depending on the purpose, in addition to the above components, a small amount of other thermoplastic resins may be used in combination. Other thermoplastic resins include, for example, aromatic dicarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate and diol or oxycarboxylic acid, polyamide, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polysulfone, Examples include polyether sulfone, polyether imide, polyether ketone, fluororesin, and polyarylate. These thermoplastic resins can be used in combination of two or more.

  Further, known substances generally added to thermoplastic resins within a range not impairing the effects of the present invention, that is, reinforcing agents such as glass fibers, stabilizers such as antioxidants, colorants such as flame retardants, dyes and pigments, etc. Further, a lubricant, a crystallization accelerator, a crystal nucleating agent, and the like can be appropriately added according to the required performance.

[Extruder]
Then, the extruder of 1st embodiment used for the manufacturing method of this invention is demonstrated. FIG. 1A is a diagram schematically showing a cross section of the extruder according to the first embodiment.

  The extruder 1 used in the present invention includes a screw 10, a cylinder 11 whose upstream end is closed, and a discharge die 12 connected to the downstream end of the cylinder 11. Here, the upstream side and the downstream side mean “upstream in the extrusion direction of the extruder” and “downstream in the extrusion direction of the extruder”, respectively.

  The screw 10 is disposed in the cylinder 11. The screw 10 includes a supply unit, a plasticizing unit, and a pressure increasing unit from the upstream side. In the present invention, the ratio (L1 / D) of the length L1 from the downstream end portion of the plasticizing portion to the upstream end portion of the pressurizing portion and the diameter D of the screw is 3.0 or more and 25.0 or less. It adjusts and ratio (L2 / D) of the length L2 from the downstream edge part of a pressure | voltage rise part to the downstream edge part of a screw and the diameter D of a screw is adjusted to 5.0 or more and 15.0 or less. It is necessary to adjust L1 and L2 to the above ranges in order to obtain the effects of the present invention.

  In particular, when the ratio (L1 / D) or ratio (L2 / D) is less than or equal to the lower limit of the above numerical range, there arises a problem that the effect of removing paradichlorobenzene is lowered. In addition, the range of more preferable ratio (L1 / D) is 5.0 or more and 15.0 or less, and the range of more preferable ratio (L2 / D) is 7.0 or more and 15.0 or less.

  The supply unit has a function of conveying the raw material supplied into the cylinder 11 in the extrusion direction (downstream direction). Specifically, the screw element for conveyance comprised from a forward flight is used, and a raw material is conveyed in an extrusion direction by rotating a screw.

  The plasticizing part has a function of sufficiently melting the polyarylene sulfide resin by applying shearing force to the raw material polyarylene sulfide resin and generating heat. A screw element having plasticizing ability (ability to melt resin) is used for the plasticizing part. For example, screw elements such as reverse flight, seal ring, forward kneading disk, reverse kneading disk, and neutral kneading disk can be exemplified. A plurality of screw elements having these kneading actions may be used in combination. In addition, even if it is a forward flight, if a deep thing and a shallow thing are combined, it will become a screw element which has a plasticizing ability.

  The pressurizing unit has a function of sufficiently kneading a molten raw material (polyarylene sulfide resin or the like). If the raw material contains a plurality of components, they are mixed more uniformly here. A screw element that can apply a compressive stress, a shear stress, or the like to a molten raw material can be used for the pressure increasing portion as well as the plasticizing portion.

  The cylinder 11 includes a hopper 111 for supplying the raw material in the vicinity of the upstream end portion, a first vent portion 112 having a pressure reducing means between the plasticizing portion and the pressure increasing portion, and a downstream side from the pressure increasing portion. It has the 2nd vent part 113 provided with the pressure reduction means, and the water injection port 114 which inject | pours water into a cylinder inside downstream from a plasticization part.

  Both the first vent part 112 and the second vent part 113 are provided with a decompression means, and perform decompression deaeration. An example of the pressure reducing means is a vacuum pump. The magnitude of the degree of reduced pressure is not particularly limited, and can be set to a preferable value as appropriate according to the molding conditions, the type of raw material, and the like, as described later.

  The water inlet 114 is provided on the downstream side of the plasticizing part. If the water injection port 114 is provided on the upstream side of the plasticizing part, water is supplied to the raw material in which unreacted aminosilane remains, the aminosilane reacts with water and hydrolyzes, The effect of using it cannot be obtained. Moreover, since the position where water is supplied is immediately before the first vent part or the second vent part, the foaming effect is not exerted, and therefore, it is not preferable.

  Next, the extruder according to the second embodiment used in the production method of the present invention will be described. FIG. 1B is a diagram schematically showing a cross section of the extruder. In the description after the second embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.

  The extruder according to the second embodiment has a configuration having a booster at two locations (a configuration having a first booster and a second booster), a configuration that defines L3 instead of defining a length L1, In the structure by which a 1st vent part is arrange | positioned between a 1st pressure | voltage rise part and a 2nd pressure | voltage rise part, it differs from the extruder of 1st embodiment. Here, L3 indicates the length from the downstream end of the first booster to the upstream end of the second booster.

  Next, an extruder according to a third embodiment used in the production method of the present invention will be described. FIG. 1C is a diagram schematically showing a cross section of the extruder.

  The extruder according to the third embodiment has a configuration having two boosters (a configuration having a first booster and a second booster), a configuration in which L4 is defined instead of length L1, and plasticity In the structure by which a 1st vent part is arrange | positioned between a conversion part and a 1st pressure | voltage rise part, it differs from the extruder of 1st embodiment. Here, L4 indicates the length from the downstream end of the plasticizing section to the upstream end of the first boosting section.

[Method for Producing Resin Composition]
Next, the method for producing the polyarylene sulfide-based resin composition of the present invention will be described by taking the case of using the extruder of the first embodiment as an example. First, a raw material containing polyarylene sulfide resin and aminosilane is charged from the hopper 111. And the raw material is conveyed in the extrusion direction by rotating the screw 10. The raw material is conveyed to the plasticizing part, and plasticized by applying shearing force to the raw material in the plasticizing part. The raw material that has passed through the plasticizing section and has been plasticized is conveyed further downstream toward the pressurizing section.

  When the raw material that has passed through the plasticizing part goes to the pressure increasing part, the first vent part 112 performs degassing under reduced pressure in the range of the length L1. The residue is removed by this vacuum degassing. As described above, since the ratio (L1 / D) is 3.0 or more, the residual removal effect as the whole of the present invention is increased.

  As described above, the deaeration is performed by the decompression unit of the first vent portion 112, and the degree of decompression is preferably, for example, 10 Torr or more and 100 Torr or less. If it is 10 Torr or more, it is preferable because it can be handled by a vacuum pump of standard specifications, and if it is 100 Torr or less, it is preferable because it can be produced without specially managing the degree of vacuum. A more preferable degree of reduced pressure is 10 Torr or more and 80 Torr or less.

  The raw material from which the residue has been removed by the first vent portion 112 is sent to the pressure raising portion by the rotation of the screw 10. In the booster, water is supplied from the water inlet 114. The amount of water to be supplied is not particularly limited, but is preferably 2 g / Hr or more and 10 g / Hr or less per 1 kg / Hr of discharge (that is, 0.2% by mass to 1.0% by mass with respect to the discharge amount). % Water is preferred). If it is 2 g / Hr or more with respect to the discharge amount of 1 kg / Hr, it is preferable because it can be handled by the standard infusion pump specifications. It is preferable because it is not necessary to remove excessive moisture with a vacuum vent. More preferably, it is 2 g / Hr or more and 6 g / Hr or less with respect to the discharge amount of 1 kg / Hr.

  It is preferable to use a method of press-fitting water using an apparatus such as a cylinder pump. This is because by supplying water in this way, the effect of kneading is high and the effect of foaming by supplying water is sufficiently exhibited. The pressurizing part is a part for kneading the molten resin composition by applying pressure, and it is difficult to supply water unless a method of press-fitting using a device such as a cylinder pump is employed. Usually, the reaction between the polyarylene sulfide resin and aminosilane has been completed in the pressure increasing section.

  In the present embodiment, water is supplied to the booster, but the position for supplying water is not limited to the position adopted in the present embodiment. As long as the water supply position is a pressure increasing portion provided downstream of the reaction end point of the polyarylene sulfide resin and aminosilane, either upstream or downstream of the position in the present embodiment. Good.

  Here, the effect of injecting water will be described. The supplied water is mixed with the raw material in the molten state, and immediately after mixing, the water becomes steam by the heat of the raw material. Foaming occurs when water becomes steam in the raw material. Residue in the raw material is separated from the raw material by this foaming, and is discharged from the second vent portion together with water vapor.

  In order to enhance the effect of removing the residue due to foaming of water as described above, it is necessary to promote foaming of the molten raw material. In order to promote foaming of the raw material in the molten state, water needs to be sufficiently mixed inside the raw material in the molten state. Therefore, it is preferable to supply water to the raw material being kneaded in the pressure raising unit. This is because the mixing of water with the raw material is promoted, and a larger residual removal effect can be obtained.

  And when a pressure | voltage rise part has a neutral kneading disc, it is preferable to supply water to the part of a neutral kneading disc. This is because the neutral kneading disk is a screw element having a very high kneading effect, and if water is supplied to the raw material kneaded by this element, the kneading of water and the raw material can be further promoted.

  Further, as a method for enhancing the effect obtained by supplying water, there is a method in which seal rings are provided at both ends of the booster and water is supplied to the booster. By making both ends of the pressurizing unit airtight with seal rings, the amount of water that becomes steam immediately after being supplied without being mixed with the raw material can be significantly reduced. As a result, the amount of water contributing to foaming in the raw material increases, and the effect obtained by supplying water is enhanced.

  On the other hand, even if water is supplied to the conveying screw part composed of forward flights, etc., the water only slips off the surface of the molten resin composition, and the supplied water and the resin composition are kneaded. Not. As a result, the foaming of water in the resin composition does not occur, and the water just vaporizes as it is, so that the effect of supplying water cannot be obtained.

  The raw material that has passed through the pressure raising unit is conveyed to the discharge die 12. In this process, vacuum deaeration is performed in the range of the length L2 by the second vent portion 113. The residue is removed by this vacuum degassing. As described above, since the ratio (L2 / D) is 5.0 or more, the residual removal effect as the whole of the present invention is increased.

  In this way, deaeration is performed by the decompression means of the second vent portion 113, and the degree of decompression is preferably, for example, 10 Torr or more and 100 Torr or less. If it is 10 Torr or more, it is preferable because it can be handled by a vacuum pump of standard specifications, and if it is 100 Torr or less, it is preferable because it can be produced without specially managing the degree of vacuum. A more preferable degree of reduced pressure is 10 Torr or more and 80 Torr or less.

  Finally, the molten raw material is extruded from the discharge die 12 to obtain a polyarylene sulfide-based resin composition.

  As described above, according to the production method of the present invention, residues such as unreacted raw materials can be largely removed when producing a polyarylene sulfide-based resin composition. The said residue is discharged | emitted from the 1st vent part 112 and the 2nd vent part 113 out of an extruder. In the present invention, the position of the first vent 112 is between two screw elements having a kneading action, and the distance (L1 / D) between the two screw elements is set to a specific range. The discharge of the residue at the first vent portion is promoted. That is, in the case of the extruder according to the second embodiment, the L3 / D between the first pressurization unit and the second pressurization unit is set to a specific range, and similarly, the residue in the first vent unit 112 Can be promoted. Moreover, in the case of the extruder of 3rd embodiment, by making L4 / D between a plasticization part and a 1st pressurization part into a specific range, similarly, the said residue in the 1st vent part 112 is the same. Emission can be promoted.

  Note that each of the extruder of the first embodiment, the extruder of the second embodiment, and the extruder of the third embodiment has the second vent portion 113 on the downstream side of the pressure increasing portion, and water is injected at the pressure increasing portion. The Therefore, even if it is the extruder of 2nd embodiment and the extruder of 3rd embodiment, discharge | emission of the said residue in the 2nd vent part 113 can be accelerated | stimulated similarly to the extruder of 1st embodiment. it can.

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

<Evaluation 1>
In Example 1, the following extruder 1 (manufactured by Nippon Steel Works, “Tex-44αII”) was used.
An outline of the screw of the extruder 1 is shown in FIG. 2A.
C0: Hopper (raw material supply unit) (111)
C3: Plasticization part C8: First vent part (112)
C9: Booster, water inlet (114)
C11: Second vent part (113)
Discharge die (12)
The ratio (L1 / D) and ratio (L2 / D) are shown in Table 1.

  In Example 1, 99.3% by mass of polyphenylene sulfide resin (manufactured by Kureha Co., Ltd., “Fortron KPS W-220A”) and 0.7% by mass of aminosilane (γ-aminopropyltriethoxysilane) are included as raw materials. I used something. The polyphenylene sulfide resin contained 20 to 50 ppm of paradichlorobenzene (p-DCB). The content of paradichlorobenzene was measured by headspace gas chromatography using a flame ionization detector under the conditions of a sample amount of 0.05 g and a heating condition of 180 ° C. × 1 hour.

Using the raw materials of Example 1, extrusion molding was performed under the following molding conditions to obtain pellets.
(Extrusion conditions)
Screw rotation speed: 180rpm
Discharge rate: 60kg / Hr
Cylinder temperature: From the resin feed side to the die head side as follows.
(C1) 50- (C2) 150- (C3) 250- (C4) 250- (C5) 320- (C6) 300- (C7) 260- (C8) 260- (C9) 260- (C10) 260- (C11) 260- (C12) 260- (Die) 300
Degree of vacuum: listed in Table 1 Amount of water supplied: listed in Table 1

  About the obtained extrudate of Example 1, the content of paradichlorobenzene was measured by a method similar to the above method. The measurement results are shown in Table 1.

  Next, Comparative Example 1 will be described. Extrudates were prepared in the same manner as in Example 1 except that water was not supplied, and the content of paradichlorobenzene contained in the extrudates was measured. The measurement results are shown in Table 1.

  Next, Comparative Example 2 will be described. Extrudates were prepared in the same manner as in Example 1 except that the extruder 2 was used instead of the extruder 1, and the content of paradichlorobenzene contained in the extrudate was measured. The measurement results are shown in Table 1. The extruder 2 is the same as the extruder 1 except that the cylinder does not have the first vent portion. An outline of the screw of the extruder 2 is shown in FIG. 2B.

  From the result of evaluation 1, in the first embodiment, it was confirmed that the content of paradichlorobenzene can be significantly reduced by supplying water and providing two vent portions.

<Evaluation 2>
Example 2 will be described. Extruder 1 was prepared in the same manner as in Example 1 except that the extruder 1 was changed to the extruder 3 and the degree of vacuum was adjusted to the degree of vacuum shown in Table 2, and the content of paradichlorobenzene contained in the extrudate was changed. It was measured. The measurement results are shown in Table 2. The extruder 3 is the following extruder. An outline of the screw of the extruder 3 is shown in FIG. 2C.
C0: Hopper (raw material supply unit) (111)
C4: Plasticizing part C6: First pressure raising part C9: First vent part (112)
C10: Second pressure increasing unit, water inlet (114)
C11: Second vent part (113)
Discharge die (12)
The ratio (L3 / D) and ratio (L2 / D) are shown in Table 2.

  Comparative Example 3 will be described. Extrudates were prepared in the same manner as in Example 2 except that water was not supplied, and the content of paradichlorobenzene contained in the extrudates was measured. The measurement results are shown in Table 2.

  Next, Comparative Example 4 will be described. An extrudate was prepared in the same manner as in Example 2 except that the extruder 4 was used instead of the extruder 3 and the water supply amount was changed to the conditions shown in Table 2, and paradichlorobenzene contained in the extrudate. The content of was measured. The measurement results are shown in Table 2. The extruder 4 is the same as the extruder 3 except that the cylinder does not have the first vent portion. An outline of the screw of the extruder 4 is shown in FIG. 2D.

  From the result of evaluation 2, it was confirmed that the content of paradichlorobenzene can be significantly reduced by supplying water and providing two vent portions also in the second embodiment.

<Evaluation 3>
Example 3 will be described. Extruder was produced in the same manner as in Example 1 except that the extruder 1 was changed to the extruder 5 and the degree of vacuum was adjusted to the degree of vacuum shown in Table 3, and the inclusion of paradichlorobenzene contained in the extrudate. The amount was measured. The measurement results are shown in Table 3. The extruder 5 is the following extruder. An outline of the screw of the extruder 5 is shown in FIG. 2E.
C0: Hopper (raw material supply unit) (111)
C5: Plasticization part C6: First vent part (112)
C7: First booster C10: Second booster, water inlet (114)
C11: Second vent part (113)
Discharge die (12)
The ratio (L4 / D) and ratio (L2 / D) are shown in Table 3.

  Next, Comparative Example 5 will be described. Extrudates were prepared in the same manner as in Example 3 except that water was not supplied, and the content of paradichlorobenzene contained in the extrudates was measured. The measurement results are shown in Table 3.

  Next, Comparative Example 6 will be described. Extrudates were prepared in the same manner as in Example 3 except that the extruder 6 was used instead of the extruder 5, and the content of paradichlorobenzene contained in the extrudate was measured. The measurement results are shown in Table 3. The extruder 6 is the same as the extruder 5 except that the cylinder does not have the first vent part. An outline of the screw of the extruder 6 is shown in FIG. 2F.

  Next, Comparative Example 7 will be described. Extrudates were prepared in the same manner as in Example 3 except that the extruder 7 was used instead of the extruder 5, and the content of paradichlorobenzene contained in the extrudate was measured. The measurement results are shown in Table 3. The extruder 7 is the same as the extruder 5 except that L4 / D is set to 2.5.

  From the result of evaluation 3, it was confirmed that the content of paradichlorobenzene can be significantly reduced by supplying water and providing two vent portions also in the third embodiment. From Comparative Example 7 and Examples 1 to 3, L4 / D (in the case of Example 3), L1 / D (in the case of Example 1), or L3 / D (in the case of Example 2) and L2 // It was confirmed that the effects of the present invention were achieved by adjusting the length of D and making these totals 10 or more.

<Evaluation 4>
Example 4 will be described. Extrudates were produced in the same manner as in Example 2 except that the extruder 3 was changed to the extruder 7, and the content of paradichlorobenzene contained in the extrudate was measured. The measurement result was 0.2 ppm. In addition, the extruder 7 is the same as the extruder 3 except having a seal ring at both ends of the second pressure increasing portion.

  From a comparison between Example 4 and Example 2, it was confirmed that the effect of the present invention was enhanced by providing a seal ring.

<Evaluation 5>
Comparative Example 8 will be described. Extrudates were prepared in the same manner as in Example 2 except that the extruder 8 in which the water inlet of the extruder 3 used in Example 2 was changed from C10 to C7 was used, and the paradichlorobenzene contained in the extrudate was produced. The content was measured. The measurement result was 0.9 ppm.

  From a comparison between Example 2 and Comparative Example 8, it was confirmed that the effect of reducing the amount of p-DCB was low even when water was injected at a portion other than the pressure boosting portion of the resin.

<Evaluation 6>
In order to examine the timing of water supply, the raw material during plasticization was extracted at five locations to prepare samples. The melt viscosity at 310 ° C. and a shear rate of 1000 sec ⁻¹ of each sample was measured by a test method based on the test standard: ISO 11443. Moreover, the weight average molecular weight was measured by high temperature GPC measurement based on test standard: JISK7252-1 about each sample. 1-chloronaphthalene was used as a solvent, and the molecular weight was determined in terms of standard polystyrene. From these measurement results, the melt viscosity at a shear rate of 1000 sec ⁻¹ was calculated, and the viscosity increase ratio (melt viscosity calculated from the sample melt viscosity / polymer molecular weight) of aminosilane was calculated. It can be considered that the reaction between the polyarylene sulfide resin and the aminosilane has been completed when the thickening factor becomes constant. From the measurement results, the reaction end point of the polyarylene sulfide resin and aminosilane was confirmed, and it was confirmed that a water inlet should be provided in the pressure increasing portion of the resin downstream from this point.

DESCRIPTION OF SYMBOLS 1 Extruder 10 Screw 11 Cylinder 111 Hopper 112 1st vent part 113 2nd vent part 114 Water inlet 12 Discharge die 2 Seal ring

Claims (5)

A polyarylene sulfide-based resin including a polyarylene sulfide resin that has been previously dried using an extruder in which a screw having a supply unit, a plasticizing unit, and a pressurizing unit is arranged in a cylinder from the upstream side that is the raw material supply side A method for producing a composition comprising:
The cylinder has a first vent part provided with a decompression means between the plasticizing part and the pressure raising part,
A second vent part provided with a pressure reducing means downstream from the pressure raising part;
A water inlet for injecting water into the cylinder downstream from the plasticizing part,
L1 / D, which is the ratio of the length L1 from the downstream end of the plasticizing section to the upstream end of the pressure increasing section and the diameter D of the screw, is 3.0 or more and 25.0 or less. ,
L2 / D, which is the ratio of the length L2 from the downstream end of the boosting portion to the downstream end of the screw and the diameter D of the screw, is 5.0 or more and 15.0 or less,
A method for producing a polyarylene sulfide-based resin composition, wherein a raw material containing a polyarylene sulfide resin and aminosilane is supplied from the supply unit, and the water is injected from the water injection port toward the pressurization unit.   The manufacturing method of the polyarylene sulfide-type resin composition of Claim 1 which has a seal ring in the both ends of the said pressure | voltage rise part. Polyarylene sulfide resin that has been dried in advance using an extruder in which a screw having a supply unit, a plasticizing unit, a first pressurizing unit, and a second pressurizing unit is arranged in a cylinder from the upstream side which is the raw material supply side A process for producing a polyarylene sulfide-based resin composition comprising:
The cylinder includes a first vent portion provided with a pressure reducing means between the first pressure increasing portion and the second pressure increasing portion,
A second vent part provided with a pressure reducing means downstream from the second pressure raising part;
A water inlet for injecting water into the cylinder downstream from the plasticizing part,
L3 / D, which is the ratio of the length L3 from the downstream end of the first booster to the upstream end of the second booster and the diameter D of the screw, is 3.0 or more and 15.0 or less. And
L2 / D, which is the ratio of the length L2 from the downstream end of the second pressurizing unit to the downstream end of the screw and the diameter D of the screw, is 5.0 or more and 15.0 or less,
A polyarylene sulfide system in which a raw material containing polyarylene sulfide resin and aminosilane is supplied from the supply unit, and the water is injected from the water injection port toward the first pressure increase unit and / or the second pressure increase unit. A method for producing a resin composition. Polyarylene sulfide resin that has been dried in advance using an extruder in which a screw having a supply unit, a plasticizing unit, a first pressurizing unit, and a second pressurizing unit is arranged in a cylinder from the upstream side which is the raw material supply side A process for producing a polyarylene sulfide-based resin composition comprising:
The cylinder has a first vent part provided with a decompression means between the plasticizing part and the first pressure raising part,
A second vent part provided with a pressure reducing means downstream from the second pressure raising part;
A water inlet for injecting water into the cylinder downstream from the plasticizing part,
L4 / D, which is the ratio of the length L4 from the downstream end of the plasticizing section to the upstream end of the first pressure increasing section and the diameter D of the screw, is 3.0 or more and 15.0 or less. Yes,
L2 / D, which is the ratio of the length L2 from the downstream end of the second pressurizing unit to the downstream end of the screw and the diameter D of the screw, is 5.0 or more and 15.0 or less,
A polyarylene sulfide system in which a raw material containing polyarylene sulfide resin and aminosilane is supplied from the supply unit, and the water is injected from the water injection port toward the first pressure increase unit and / or the second pressure increase unit. A method for producing a resin composition.   The manufacturing method of the polyarylene sulfide-type resin composition of Claim 3 or 4 which has a seal ring in the both ends of said 1st pressure | voltage rise part and / or said 2nd pressure | voltage rise part.

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