CN111823531A - Method for producing polyphenylene ether resin composition - Google Patents

Method for producing polyphenylene ether resin composition Download PDF

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Publication number
CN111823531A
CN111823531A CN202010235038.2A CN202010235038A CN111823531A CN 111823531 A CN111823531 A CN 111823531A CN 202010235038 A CN202010235038 A CN 202010235038A CN 111823531 A CN111823531 A CN 111823531A
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China
Prior art keywords
resin composition
melt
mass
zone
barrel
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Chinese (zh)
Inventor
山口徹
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B7/00—Mixing; Kneading
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    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
    • B29C48/143—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration at a location before or in the feed unit, e.g. influencing the material in the hopper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/287—Raw material pre-treatment while feeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/76—Venting, drying means; Degassing means
    • B29C48/762—Vapour stripping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • B29C48/802—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • B29C48/83—Heating or cooling the cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
    • B29K2071/12—PPO, i.e. polyphenylene oxide; PPE, i.e. polyphenylene ether
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The invention provides a method for producing a polyphenylene ether resin composition, in which the generation of build-up around a die nozzle is significantly suppressed, extrusion productivity is improved, and a resin composition having good toughness and reduced contamination of impurities derived from polyphenylene ether can be obtained. The present invention is a method for producing a resin composition using an extruder, wherein the resin composition contains 10 mass% or more of PPE (A), the extruder is a twin-screw extruder having a solid-conveying zone, a melt-kneading zone and a melt-conveying zone, 30 to 60% of the upstream side of the extruder is the solid-conveying zone, and the remaining 40 to 70% are the melt-kneading zone and the melt-conveying zone, and in a cylinder constituting the solid-conveying zone, when the length of a cylinder other than the cylinder provided with the first supply port is 100%, the set temperature of 75% or more of the cylinders is in the range of 50 to 190 ℃, the set temperature of the cylinder constituting the melt-kneading zone and the cylinder constituting the melt-conveying zone is in the range of 250 to 320 ℃, and the oxygen concentration in the collecting hopper is 3% or less by volume.

Description

Method for producing polyphenylene ether resin composition
Technical Field
The present invention relates to a method for producing a polyphenylene ether resin composition.
Background
The polyphenylene ether resin composition is obtained by blending a thermoplastic elastomer with a polyphenylene ether resin alone or with a polyphenylene ether resin and a styrene resin as needed, or further blending additive components such as a flame retardant, a heat stabilizer, a release agent, a lubricant, and an inorganic filler.
Polyphenylene ether resin compositions are widely used as materials for home electric appliances, OA equipment, office equipment, information equipment, automobiles, and the like because they are excellent in mechanical properties, electrical properties, acid/alkali resistance, and heat resistance, and have various properties such as low specific gravity, low water absorption, and good dimensional stability.
However, since the polyphenylene ether resin composition generally has a high melt viscosity, when the polyphenylene ether resin composition is melt-kneaded using an extruder or the like to prepare a resin composition (pellet), the resin composition after melt-kneading is brought into contact with oxygen under high temperature conditions, whereby oxidative crosslinking of the polyphenylene ether resin can be promoted. Finally, the resin is gelled and carbonized, and these are mixed as impurities into the resin composition, which may cause a reduction in appearance, toughness, and the like of the molded article.
In addition, when a polyphenylene ether resin composition is produced by an extruder, the resin composition adheres to the periphery of a circular discharge port (die nozzle) at the tip of the extruder for discharging the melt-kneaded resin composition, and as the production continues, the adhered matter (buildup) is exposed to heat and outside air for a long time, oxidatively cross-links occur, grows into a whisker shape, and finally adheres to the extruded resin and is mixed into the resin composition, which may still cause a reduction in the appearance, toughness, and the like of a molded article.
Further, the grown build-up exists so as not to be separated from the periphery of the die nozzle, and therefore, in a step of drawing a resin (strand) continuously discharged in a string form from the die nozzle by a cutter (pelletizer) and simultaneously cutting (pelletizing), the strand flow becomes unstable finally, and there is a possibility that the strand is broken, and a production failure such as a drawing failure of the strand by the pelletizer may be caused.
Patent document 1 discloses the following technique: the oxygen concentration of a specific polyphenylene ether resin composition in the interior of a first feed hopper through which a raw material of an extruder is fed is adjusted to 1.0% by volume or less, thereby reducing deterioration of a polyphenylene ether resin generated in the interior of a cylinder of the extruder.
Patent document 2 discloses the following technique: when the polyphenylene ether resin composition is extruded by an extruder, the upstream length of 45-75% is set as an unmelted mixing zone when the total length of the barrel of the extruder is set to 100%, thereby suppressing thermal deterioration of the resin and improving impact resistance and thermal aging resistance.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-255046
Patent document 2: japanese patent laid-open No. 2008-274035
Disclosure of Invention
Problems to be solved by the invention
However, the technique described in patent document 1 does reduce the deterioration of the polyphenylene ether resin generated in the barrel of the extruder, but is not necessarily sufficient for reducing the material deposition around the die nozzle.
The technique described in patent document 2 has a certain effect of reducing the generation of impurities in the barrel of the extruder and suppressing the reduction in the physical properties of the resin composition, but is still insufficient in suppressing the build-up during extrusion.
Accordingly, an object of the present invention is to provide a production method in which the formation of a polyphenylene ether resin-deteriorated product and the formation of a build-up around a die nozzle, which are generally generated in a cylinder of an extruder at the time of extrusion, are significantly suppressed, the extrusion productivity is improved, and a resin composition having reduced contamination of impurities derived from a polyphenylene ether and good toughness can be obtained.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a polyphenylene ether resin composition containing a polyphenylene ether in an amount of a certain amount or more can be stably produced with good toughness with less contamination of impurities derived from polyphenylene ether, while remarkably suppressing the generation of a polyphenylene ether resin deteriorated product and the generation of a material deposit around a die nozzle during extrusion, and with improved extrusion productivity, by extruding the resin composition by a specific extrusion method using an extruder, thereby completing the present invention.
Namely, the present invention is as follows.
[1]
A method for producing a resin composition by using an extruder, wherein,
the resin composition contains polyphenylene ether (A) in an amount of 10 mass% or more based on the total amount (100 mass%) of the resin composition,
the extruder is a twin-screw extruder having a solid-conveying zone, a melt-kneading zone, and a melt-conveying zone, the solid-conveying zone having a barrel provided with a first supply port,
when the length of the entire barrel of the extruder is 100%, 30 to 60% of the upstream side of the extruder is the solid-conveying zone, and the remaining 40 to 70% are the melt-kneading zone and the melt-conveying zone,
in the case where the length of the cylinder other than the cylinder provided with the first supply port is 100% of the cylinder constituting the solid matter transfer zone, the set temperature of 75% or more of the cylinders is in the range of 50 to 190 ℃,
the set temperature of the cylinder constituting the melt-kneading zone and the cylinder constituting the melt-transporting zone is in the range of 250 ℃ to 320 ℃,
the oxygen concentration in the collection hopper provided above the first supply port is set to 3 vol% or less.
[2]
The method for producing a resin composition as described in [1], wherein when a length of a cylinder other than the cylinder provided with the first supply port in the cylinder constituting the solid matter transfer zone is 100%, a set temperature of 100% of the cylinder is in a range of 50 ℃ to 190 ℃.
[3]
The method for producing a resin composition as described in [1] or [2], wherein the melt-transporting zone has a cylinder provided with an opening, and a vent provided with a nitrogen injection line and a gas discharge portion is provided above the opening.
[4]
The method for producing a resin composition according to any one of [1] to [3], wherein all of the extrusion raw material is supplied from the first supply port.
[5]
The method for producing a resin composition according to any one of [1] to [4], wherein the resin composition further contains 5 to 80 mass% of a styrene-based resin (B) based on the total amount (100 mass%) of the resin composition.
[6]
The method for producing a resin composition according to any one of [1] to [5], wherein the resin composition further contains 0.1 to 25 mass% of a styrene-based thermoplastic elastomer (C) based on the total amount (100 mass%) of the resin composition.
[7]
The method for producing a resin composition according to any one of [1] to [6], wherein the resin composition further contains 0.001 to 3 mass% of an antioxidant (D) based on the total amount (100 mass%) of the resin composition.
[8]
The method for producing a resin composition according to any one of [1] to [7], wherein the content of the polyolefin resin component in the resin composition is 5% by mass or less based on the total amount (100% by mass) of the resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The production method of the present invention can significantly suppress the generation of a deteriorated polyphenylene ether resin and the generation of a build-up around a die nozzle, which are generally generated in the barrel of an extruder during extrusion, and can stably obtain a resin composition having good toughness with reduced inclusion of impurities derived from polyphenylene ether, while improving extrusion productivity.
Detailed Description
Embodiments of the present invention (hereinafter referred to as "the present embodiment") will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
The method for producing a polyphenylene ether resin composition according to the present embodiment is a method for producing a resin composition using an extruder, wherein the polyphenylene ether (a) is contained in the resin composition in an amount of 10 mass% or more based on the total amount (100 mass%) of the resin composition; the extruder is a twin-screw extruder having a solid conveying zone, a melt-kneading zone, and a melt-conveying zone, the solid conveying zone having a barrel provided with a first supply port; when the length of the whole cylinder of the extruder is set as 100%, 30-60% of the upstream side of the extruder is a solid conveying zone, and the rest 40-70% of the upstream side of the extruder is a melting and mixing zone and a melting and conveying zone; in the case where the length of the cylinder other than the cylinder provided with the first supply port is 100% among the cylinders constituting the solid transfer zone, the set temperature of 75% or more of the cylinders is in the range of 50 ℃ to 190 ℃; the set temperature of the cylinder forming the melting and mixing zone and the cylinder forming the melting and conveying zone is within the range of 250-320 ℃; the oxygen concentration in a collection hopper provided above the first supply port is set to 3 vol% or less.
< resin composition > <
The resin composition according to the present embodiment contains polyphenylene ether (a) in an amount of 10 mass% or more based on the total amount (100 mass%) of the resin composition.
The polyphenylene ether resin composition according to the present embodiment is produced by melt-kneading the component (a), the optional components (B) to (D), and other components added as needed, according to the production method according to the present embodiment described below.
The present inventors have found that when the above resin composition is extruded by a specific extrusion method, the formation of an oxidized crosslinked product of a polyphenylene ether resin and the generation of a build-up around a die nozzle, which occur in a cylinder of an extruder, are significantly suppressed, the extrusion productivity is improved, and the incorporation of impurities derived from a polyphenylene ether is reduced. The respective constituent components of the resin composition will be described in detail below.
< polyphenylene Ether (A) >
The polyphenylene ether (A) is preferably a homopolymer or a copolymer having a repeating structural unit comprising a general formula (1) [ a ] and/or a general formula (1) [ b ].
[ solution 1]
Figure BDA0002430682300000051
[ solution 2]
Figure BDA0002430682300000052
The above formula (1) [ a]、(1)[b]In, R1、R2、R3、R4、R5And R6Preferably, each is independently a monovalent residue selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom and a hydrogen atom.
However, in this case, R is not included5And R6And also in the case of hydrogen.
Further, the alkyl group preferably has 1 to 3 carbon atoms, the aryl group preferably has 6 to 8 carbon atoms, and the monovalent residue is more preferably hydrogen.
The number of repeating units in the above-mentioned (1) [ a ] and (1) [ b ] is not particularly limited, since it varies depending on the molecular weight distribution of the polyphenylene ether (A).
Examples of the homopolymer of polyphenylene ether include, but are not limited to, poly (2, 6-dimethyl-1, 4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2, 6-diethyl-1, 4-phenylene) ether, poly (2-ethyl-6-n-propyl-1, 4-phenylene) ether, poly (2, 6-di-n-propyl-1, 4-phenylene) ether, poly (2-methyl-6-n-butyl-1, 4-phenylene) ether, poly (2-ethyl-6-isopropyl-1, 4-phenylene) ether, poly (2-methyl-6-chloroethyl-1, 4-phenylene) ether, poly (2-ethyl-6-n-, Poly (2-methyl-6-hydroxyethyl-1, 4-phenylene) ether and poly (2-methyl-6-chloroethyl-1, 4-phenylene) ether, and the like.
Further, examples of the copolymer of polyphenylene ether include, but are not limited to, copolymers mainly composed of polyphenylene ether structure, such as a copolymer of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol, a copolymer of 2, 6-dimethylphenol and o-cresol, and a copolymer of 2,3, 6-trimethylphenol and o-cresol.
Among polyphenylene ethers, poly (2, 6-dimethyl-1, 4-phenylene) ether is preferably used.
The polyphenylene ether (A) may be used alone or in combination of 2 or more.
Further, polyphenylene ether (A) may contain various phenylene ether units other than those represented by formulas (1) [ a ] and (1) [ b ] as partial structures.
Examples of the phenylene ether unit include, but are not limited to, a 2- (dialkylaminomethyl) -6-methylphenylene ether unit, a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like described in, for example, Japanese patent application laid-open Nos. H01-297428 and 63-301222.
Further, polyphenylene ether (A) may contain a structural unit other than the phenylene ether unit in the main chain.
Examples of such a structural unit include a unit derived from diphenoquinone. In particular, the polyphenylene ether (a) is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, based on 100% by mass of the polyphenylene ether (a), and the structural units other than the phenylene ether units contained in the main chain.
In addition, in polyphenylene ether (A), a functionalized polyphenylene ether can be produced by reacting (modifying) a part or the whole of polyphenylene ether with a functionalizing agent containing 1 or more species selected from the group consisting of carboxylic acid, acid anhydride, amide, imide, amine, orthoester, hydroxyl group, and ammonium salt of carboxylic acid.
The reduced viscosity of the polyphenylene ether (A) used in the present embodiment is preferably in the range of 0.25 to 0.60dL/g, more preferably 0.30 to 0.55dL/g, and still more preferably 0.35 to 0.50 dL/g. It is preferably 0.25dL/g or more in view of sufficient mechanical properties, and 0.55dL/g or less in view of molding processability and the feeling of brightness of the molded article.
The reduced viscosity in the present embodiment is a value measured using a chloroform solvent, a concentration of 0.50g/dL, and a Ubbelohde viscometer at 30 ℃.
The ratio (Mw/Mn value) of the weight average molecular weight Mw to the number average molecular weight Mn (in the form of a polymer powder) of the polyphenylene ether (A) used in the present embodiment is preferably 1.2 to 3.0, more preferably 1.5 to 2.5, and still more preferably 1.8 to 2.3 before heat processing by extrusion or the like. The Mw/Mn value is preferably 1.2 or more in view of molding processability of the resin composition, and is preferably 3.0 or less in view of maintaining mechanical properties, particularly tensile strength, of the resin composition.
The weight average molecular weight Mw and the number average molecular weight Mn are values obtained by measuring molecular weights in terms of polystyrene by GPC (gel permeation chromatography).
In the polyphenylene ether resin composition of the present embodiment, the content of polyphenylene ether (a) is 10 mass% or more of the entire resin composition. Preferably, the content is 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more. From the viewpoint of sufficiently exhibiting the effects obtained by the production method of the present embodiment, it is important to include 10 mass% or more.
< styrene resin component (B) >
The styrene resin (B) may be blended in the resin composition of the present embodiment mainly for the purpose of improving molding flowability.
In the present embodiment, the styrene-based resin (B) refers to a homopolymer of a styrene-based compound, a copolymer of a styrene-based compound and a compound copolymerizable with the styrene-based compound (excluding a conjugated diene compound). The component (B) does not include those included in the component (C) described later.
Specific examples of the styrene resin (B) include styrene, α -methylstyrene, 2, 4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene.
Examples of the compound copolymerizable with the styrene compound include methacrylates such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; anhydrides such as maleic anhydride; and so on.
The styrene-based resin (B) can be obtained by polymerizing a styrene-based compound, or a styrene-based compound and a compound copolymerizable with the styrene-based compound, in the presence or absence of a rubber polymer.
Examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, a hydrogenated product thereof, and an ethylene-propylene copolymer rubber.
In the present embodiment, as the styrene-based resin (B), polystyrene or high impact polystyrene reinforced with a rubber polymer is preferable, and polystyrene is more preferable.
The styrene resin (B) content in the resin composition used in the present embodiment is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, even more preferably 20 to 60% by mass, and particularly preferably 25 to 45% by mass, based on 100% by mass of the resin composition. The compounding amount is preferably 5% by mass or more from the viewpoint of imparting sufficient molding flowability, and the compounding amount is preferably 80% by mass or less from the viewpoint of maintaining sufficient heat resistance.
< styrene-based thermoplastic elastomer (C) >
The styrene-based thermoplastic elastomer (C) used in the present embodiment is a block copolymer having a styrene block and a conjugated diene compound block.
In the conjugated diene compound block, it is preferable that the hydrogenation is carried out at a hydrogenation ratio of at least 50% from the viewpoint of thermal stability. The hydrogenation rate is more preferably 80% or more, and still more preferably 95% or more.
Examples of the conjugated diene compound block include, but are not limited to, polybutadiene, polyisoprene, poly (ethylene-butylene), poly (ethylene-propylene) and vinyl-polyisoprene. The conjugated diene compound block may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The arrangement of the repeating units constituting the block copolymer may be linear or radial. Further, the block structure composed of the polystyrene block and the rubber mid block may be any of two types, three types and four types. Among these, a three-type linear block copolymer having a polystyrene-poly (ethylene-butylene) -polystyrene structure is preferable in that the effects desired in the present embodiment can be sufficiently exhibited. In the conjugated diene compound block, a butadiene unit may be contained in a range of not more than 30% by mass.
In the composition of the present embodiment, a functionalized styrene-based thermoplastic elastomer obtained by introducing a functional group such as a carbonyl group or an amino group can be used as the styrene-based thermoplastic elastomer.
The styrene-based thermoplastic elastomer (C) according to the present embodiment has a bound styrene content selected from the range of 20 to 90 mass%, preferably 55 to 80 mass%, and more preferably 60to 70 mass%. The content of the component (a) is preferably 20% by mass or more in view of miscibility with the component (a) and the component (B), and is preferably 90% by mass or less in view of imparting sufficient impact resistance.
The number average molecular weight Mn of the styrene-based thermoplastic elastomer (C) according to the present embodiment is preferably in the range of 30,000 to 500,000, more preferably 40,000 to 300,000, and still more preferably 45,000 to 250,000. The range of 30,000 to 500,000 is preferable from the viewpoint of providing sufficient toughness to the molded article.
The Mw/Mn value of the component (C) determined from the weight average molecular weight Mw and the number average molecular weight Mn obtained from polystyrene equivalent molecular weight is preferably in the range of 1.0 to 3.0, more preferably 1.0 to 2.0, and even more preferably 1.0 to 1.5. From the viewpoint of mechanical properties, the range of 1.0 to 3.0 is preferable.
The content of the styrene-based thermoplastic elastomer (C) according to the present embodiment is preferably 0.1 to 25 mass%, more preferably 0.5 to 20 mass%, and still more preferably 1 to 20 mass% of 100 mass% of the resin composition. The content is preferably 0.1 mass% or more in terms of improving toughness, and 25 mass% or less in terms of mechanical properties of the molded article.
< antioxidant (D) >
The resin composition according to the present embodiment may further contain an antioxidant (D).
As the antioxidant (D), any of a primary antioxidant that functions as a radical chain inhibitor and a secondary antioxidant having an effect of decomposing a peroxide can be used. That is, by using an antioxidant, when a polyphenylene ether is exposed to high temperatures for a long period of time, it is possible to capture a radical (primary antioxidant) which may be generated at a terminal methyl group or a side chain methyl group, or to decompose a peroxide (secondary antioxidant) which is generated at a terminal methyl group or a side chain methyl group due to the action of the radical, and therefore, it is possible to prevent oxidative crosslinking of a polyphenylene ether.
As the primary antioxidant, hindered phenol-based antioxidants are mainly used, and specific examples thereof include 2, 6-di-t-butyl-4-methylphenol, pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], n-octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2' -methylenebis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-di-t-pentylphenyl) ethyl ] -4, 6-di-tert-amylphenyl acrylate, 4' -butylidenebis (3-methyl-6-tert-butylphenol), alkylated bisphenols, tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, 3, 9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy ] -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane, and the like.
As the secondary antioxidant, a phosphorus-based antioxidant can be mainly used. Specific examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite, triphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 3, 9-bis (2, 6-di-t-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5,5] undecane, and the like.
Further, as other antioxidants, metal oxides such as zinc oxide and magnesium oxide, and metal sulfides such as zinc sulfide may be used in combination with the above-mentioned antioxidants.
Among these, in order to improve the toughness of the molded article and the mechanical properties after long-term exposure to high temperature, a phosphorus-based antioxidant is preferable as the secondary antioxidant, a phosphite-based antioxidant is more preferable, and a phosphite-based antioxidant having a structure of the following chemical formula (2) in a molecule is particularly preferable.
[ solution 3]
Figure BDA0002430682300000091
The content of the antioxidant (D) is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, even more preferably 0.1 to 1% by mass, and particularly preferably 0.1 to 0.5% by mass, based on 100% by mass of the resin composition. The amount of the additive is preferably 0.001 mass% or more in view of suppressing oxidative deterioration of the resin during extrusion molding, and preferably 3 mass% or less in view of maintaining the surface appearance of the molded article.
< other ingredients >
When the resin composition according to the present embodiment is colored, it is preferable that a colorant made of carbon black, titanium oxide, other inorganic or organic known dyes, pigments, or the like is contained in an amount of 0.001 to 5% by mass based on 100% by mass of the resin composition. The colorant is preferably contained in an amount of 0.001% by mass or more in terms of sufficient coloring, and 5% by mass or less in terms of sufficient mechanical strength and appearance retention of the molded article.
In the resin composition according to the present embodiment, the content of the polyolefin resin component is preferably 5% by mass or less based on 100% by mass of the resin composition.
Examples of the polyolefin resin component include polyolefin resins such as polyethylene and polypropylene, and polyolefin copolymers such as ethylene-propylene copolymers, ethylene-octene copolymers, ethylene-ethyl acrylate copolymers, and ethylene-ethyl methacrylate copolymers.
In the resin composition according to the present embodiment, the content of the polyolefin resin component is more preferably 3% by mass or less, and still more preferably 1% by mass or less. The content of the polyolefin resin component is preferably 5% by mass or less in order to suppress a decrease in physical properties and appearance due to, for example, peeling of the surface layer of the molded article.
The resin composition according to the present embodiment preferably does not contain an inorganic filler as a reinforcing agent from the viewpoints of toughness of a molded article and molded appearance. The inorganic filler as a reinforcing agent is generally used for reinforcing a thermoplastic resin, and examples thereof include glass fibers, carbon fibers, glass flakes, talc, mica, and the like. The term "not containing an inorganic filler" as used herein means that the content of the inorganic filler in 100% by mass of the resin composition is 1% by mass or less. The content is preferably 0.5% by mass or less, more preferably 0.1% by mass or less.
The resin composition according to the present embodiment may further contain an ultraviolet absorber, a release agent, a lubricant, and the like as necessary within a range that does not significantly reduce the effects of the present embodiment.
< method for producing resin composition >)
As described below, the resin composition according to the present embodiment is produced by melt-kneading the component (a) and, if necessary, the components (B) to (D) of the present application, and other components added as needed.
The present inventors have found that in the production method, when the resin composition is extruded by a specific extrusion method, the production of a polyphenylene ether resin-deteriorated product and the production of a deposit around a die nozzle, which are generated in a cylinder of an extruder, are significantly suppressed, the extrusion productivity is improved, and a polyphenylene ether resin composition having good toughness and containing less impurities derived from polyphenylene ether can be stably mass-produced.
The method for producing the resin composition will be described in detail below.
The polyphenylene ether resin composition of the present embodiment is produced by melt-kneading the component (a), the components (B) to (D) if necessary, and other components added as needed in a twin-screw extruder having a solid-conveying zone, a melt-kneading zone, and a melt-conveying zone in a barrel.
In this case, when the length of the entire barrel of the extruder is 100%, 30 to 60% of the upstream side of the extruder is a solid conveying zone, and the remaining 40 to 70% are a melt kneading zone and a melt conveying zone; further, when the length of the cylinder other than the cylinder provided with the first supply port is 100% among the cylinders constituting the solid transfer zone, the resin composition can be produced by setting the set temperature of the cylinder to 75% or more to a range of 50 to 190 ℃, the set temperature of the cylinders in the melt-kneading zone and the melt-transfer zone to a range of 250 to 320 ℃, and adjusting the oxygen concentration in the collecting hopper provided above the first supply port to 3 vol% or less.
In order to stably obtain a large amount of the resin composition which can sufficiently exhibit the effects desired in the present embodiment in the production of the resin composition, a twin-screw extruder having a screw diameter of 40 to 90mm is suitably used as the twin-screw extruder used.
As a suitable example, the following method can be mentioned: when a TEM58SS twin-screw extruder (13 barrels (including a barrel under a first supply port hopper), 58mm in screw diameter, 53 in L/D; screw mode having 2 kneading disks L, 12 kneading disks R and 4 kneading disks N, manufactured by Toshiba mechanical Co., Ltd.) was used, the barrel length of the solid conveying zone was set to 45%, the barrel lengths of the remaining melt-kneading zone and melt-conveying zone were set to 55%, the barrel set temperature of the solid conveying zone (the barrel under the first supply port hopper, which is not included because of water cooling) was set to 100 to 180 ℃, the barrel set temperatures of the melt-kneading zone and melt-conveying zone were set to 270 to 310 ℃, and the oxygen concentration in the collective hopper above the first supply port was set to 0.3 to 2.0 vol%, (the barrel under the first supply port hopper, the barrel length of the entire extruder was set to 100%, (the barrel including the barrel under the first supply port hopper, which was not included in the hopper) was set to 100 to 180 ℃., (the, The screw rotation speed is 350-600 rpm, and the extrusion speed is 350-600 kg/h.
In the production of the above resin composition, the solid conveying zone in the barrel of the twin-screw extruder means a zone in which the extrusion raw material component is not completely melted and only conveyed by the single-flight and/or double-flight right-flight feed screw element structure in a completely unmelted or semi-melted state in which unmelted component is present in the extrusion raw material component.
The length of the solid transfer zone in the extruder is selected from the range of 30 to 60% when the length of the entire barrel of the extruder is 100%. Preferably 35 to 60%, more preferably 40 to 55%, and still more preferably 45 to 55%. The content of the polyphenylene ether resin is required to be 30% or more in order to sufficiently suppress thermal deterioration of the polyphenylene ether resin, and 60% or less in order to sufficiently melt-knead the extrusion raw material components and to achieve production stability.
The melt-kneading zone in the barrel of the twin-screw extruder is a zone in which the extrusion raw material component in a completely unmelted or semi-melted state conveyed from the solid conveying zone is melt-kneaded as described in the text, and it means a zone formed by a screw structure including a plurality of kneading screw elements such as a kneading disc R, a kneading disc N, and a kneading disc L.
The melt-conveying zone in the barrel of the twin-screw extruder is a zone for conveying the extrusion raw material component conveyed from the melt-kneading zone to the resin discharge port (die nozzle) of the extruder, and means a zone for conveying the molten extrusion raw material component by using only the single-flight and/or double-flight right-flight feed screw element structure.
The total length of the melt kneading zone and the melt conveying zone in the extruder is selected from the range of 70 to 40% when the length of the barrel of the entire extruder is 100%. Preferably 60to 40%, more preferably 57 to 40%, and still more preferably 57 to 45%. The polyphenylene ether resin needs to be 70% or less in view of sufficiently suppressing thermal deterioration, and 40% or more in view of sufficiently melt-kneading the extrusion raw material components.
When the length of the entire barrel of the extruder is 100%, the length of the melt-kneading zone in the extruder is preferably in the range of 15 to 40%. More preferably 20 to 40%, and still more preferably 22 to 35%. The content of the polyphenylene ether resin is preferably 15% or more in view of sufficient melt kneading of the extruded resin component, and preferably 40% or less in view of suppressing thermal deterioration of the polyphenylene ether resin.
Regarding the barrel set temperature of the solid transfer zone in the extruder, when the length of the barrel other than the barrel provided with the first supply port among the barrels constituting the solid transfer zone is set to 100%, the set temperature of 75% or more (preferably 80% or more, more preferably 90% or more, and further preferably 100%) of the barrels is selected from the range of 50 to 190 ℃. The set temperature is preferably in the range of 70 to 190 ℃, more preferably in the range of 100 to 180 ℃, and even more preferably in the range of 130 to 170 ℃. From the viewpoint of production stability, it is required to be 50 ℃ or higher, and from the viewpoint of suppressing thermal deterioration of polyphenylene ether resin, it is required to be 190 ℃ or lower.
The barrel setting temperature of the melting and mixing zone and the melting and conveying zone in the extruder is selected from the range of 250-320 ℃. Preferably in the range of 260-320 ℃, more preferably in the range of 270-310 ℃. From the viewpoint of sufficient melt kneading of the extruded resin components and production stability, it is necessary to be 250 ℃ or higher, and from the viewpoint of suppressing thermal deterioration of the polyphenylene ether resin and production stability, it is necessary to be 320 ℃ or lower.
The set temperature of the resin discharge part (die head) in the extruder is preferably in the range of 270 to 320 ℃. More preferably 290 to 315 ℃, and still more preferably 300 to 310 ℃. From the viewpoint of production stability, it is preferably 270 ℃ or higher, and from the viewpoint of suppressing thermal deterioration of the polyphenylene ether resin, it is preferably 320 ℃ or lower.
When the resin composition of the present embodiment is produced using a twin-screw extruder, attention is paid to the fact that the gel or carbide generated by oxidative deterioration of the polyphenylene ether as the component (a) is incorporated into extruded resin pellets, and causes deterioration in physical properties such as surface appearance and toughness of a molded article.
Therefore, it is important to charge the component (a) from the raw material inlet at the most upstream side (top feed inlet) and set the oxygen concentration inside the collective hopper at the most upstream inlet to 3 vol% or less. The oxygen concentration in the collecting hopper is preferably 2 vol% or less, more preferably 1 vol% or less, and still more preferably 0.5 vol% or less.
The oxygen concentration can be adjusted by sufficiently replacing nitrogen gas in the raw material storage hopper, sealing the raw material inlet from the raw material storage hopper to the extruder so that air does not enter and exit the raw material storage hopper through the feed pipe line, and then adjusting the nitrogen feed amount and the opening degree of the gas outlet.
In the production of the resin composition of the present embodiment, it is preferable that all of the extrusion materials are supplied from the first supply port (top feed port) from the viewpoint of sufficiently reducing the oxygen concentration in the collecting hopper at the most upstream feed port, and this is also preferable from the viewpoint of suppressing the oxidative deterioration of the component (a) and sufficiently exhibiting the effects required for the application of the present invention.
The oxygen concentration inside the collection hopper is measured using an oxygen concentration meter, and the sensor portion of the oxygen concentration meter is disposed so as to be positioned in the middle portion inside the collection hopper, whereby the oxygen concentration can be measured at all times during extrusion.
Further, when the molten resin extruded from the die nozzle of the extruder is brought into contact with air, the molten resin adhering to the edge of the nozzle is deteriorated by oxidative crosslinking, which may cause generation and growth of deposits. It is also possible that the resin grows at the edge of the nozzle with the progress of long-term production, and finally gets mixed into the resin, which causes poor appearance and deterioration of physical properties. For the blowing of the nitrogen gas, a known deposit removing device may be used, and a nitrogen gas line may be connected to the blowing.
The blowing amount of nitrogen gas to the die nozzle is preferably in the range of 1 to 50L/min, more preferably in the range of 5 to 30L/min, and even more preferably in the range of 10 to 25L/min. The amount of the nitrogen-containing gas is preferably 1L/min or more from the viewpoint of sufficient contact between the resin and the nitrogen gas, and preferably 50L/min or less from the viewpoint of consideration of the surrounding environment.
In general, in order to remove residual volatile components in the raw material components at the time of extrusion, it is originally preferable to perform vacuum devolatilization using a vacuum vent, but in this case, outside air may be sucked from a minute gap between the vacuum vent and the inside of the cylinder around the vacuum vent, and the deterioration of the resin may be promoted by oxidative crosslinking of the molten resin. In this case, a mode of performing extrusion without intentionally performing reduced pressure devolatilization using a vacuum vent is also preferable in some cases. When the vacuum vent is removed and the plug is attached to the upper portion of the cylinder, the internal pressure of the cylinder rises due to the gas generated from the molten resin during extrusion, the discharge of the molten resin from the die nozzle becomes unstable, and strand drawing may be difficult during extrusion, and therefore, it is preferable to provide a vent having a nitrogen injection line and a gas discharge portion at the opening portion of the upper portion of the cylinder, inject nitrogen into the vent from the nitrogen injection line and blow the nitrogen into the molten resin at the opening portion of the vent, and perform extrusion while discharging the gas component generated from the molten resin and the nitrogen gas from the gas discharge portion.
The flow rate of the nitrogen gas injected into the exhaust port is preferably in the range of 1 to 50L/min, more preferably in the range of 5 to 30L/min, and even more preferably in the range of 10 to 25L/min. The amount of nitrogen gas is preferably 1L/min or more from the viewpoint of sufficient contact between the resin and nitrogen gas, and preferably 50L/min or less from the viewpoint of the environment.
In the production of the resin composition of the present embodiment, the screw rotation speed of the twin-screw extruder is preferably in the range of 250 to 700 rpm. More preferably 300 to 600rpm, even more preferably 350 to 600rpm, and particularly even more preferably 400 to 500 rpm. The resin composition is preferably 250rpm or more in view of sufficient melt kneading, and is preferably 700rpm or less in view of suppressing thermal deterioration due to heat generation by shearing of the resin composition.
In the production of the resin composition of the present embodiment, the extrusion rate of the twin-screw extruder is preferably in the range of 250 to 700 kg/h. More preferably 300 to 600kg/h, still more preferably 350 to 500kg/h, and particularly still more preferably 350 to 450 kg/h. From the viewpoint of sufficient mass productivity, it is preferably 250kg/h or more, and from the viewpoint of production stability, it is preferably 700kg/h or less.
[ molded article ]
The molded article made of the polyphenylene ether resin composition according to the present embodiment can be obtained by molding the resin composition obtained by the above-described production method.
The molding method of the resin composition includes, but is not limited to, injection molding, extrusion molding, vacuum molding, and pneumatic molding, and particularly, injection molding is more preferably used from the viewpoint of molding appearance.
The molding temperature at the time of molding the resin composition is preferably within a range in which the maximum temperature of the cylinder is set to 250 to 340 ℃, more preferably 270 to 330 ℃, and still more preferably 280 to 320 ℃. The molding temperature is preferably 250 ℃ or higher from the viewpoint of sufficient molding processability, and is preferably 340 ℃ or lower from the viewpoint of suppressing thermal deterioration of the resin and maintaining physical properties.
The resin composition is preferably molded at a mold temperature of 40 to 150 ℃, more preferably 80 to 140 ℃, and still more preferably 80 to 120 ℃. The mold temperature is preferably 40 ℃ or higher in view of sufficiently maintaining the appearance of the molded article, and is preferably 150 ℃ or lower in view of molding stability.
For this reason, the production method of the present embodiment can be used as a suitable molded article in the present embodiment, and examples of the molded article include home electric and office appliance OA equipment parts, motor electronic equipment, automobile applications, various industrial products, and the like, because the production of a deteriorated polyphenylene ether resin and the generation of a material deposit around a die nozzle, which are generated in the barrel of an extruder during extrusion, are significantly suppressed, the extrusion productivity is improved, and a polyphenylene ether resin composition having excellent toughness and containing less contamination of impurities derived from polyphenylene ether can be stably mass-produced.
Examples
The present embodiment will be described in more detail below with reference to examples and comparative examples, but the present embodiment is not limited to these examples.
The evaluation and measurement methods and materials of physical properties used in examples and comparative examples are as follows.
[ production stability ]
1. Accumulating material
When the resin compositions of the following examples and comparative examples were produced by melt-kneading under the extrusion conditions described below using a TEM58SS twin-screw extruder (manufactured by toshiba machinery, 12 barrels (not including the lower barrel of the first supply port hopper), a screw diameter of 58mm, and an L/D of 53), the presence or absence of build-up (the molten resin adhered to the edge of the die nozzle and grown in a needle shape) was confirmed.
The evaluation was "good" (excellent) "when no occurrence of the buildup was visually observed after 2 hours of continuous operation, and the evaluation was" poor "(poor)" when occurrence of the buildup was visually observed after 2 hours of operation. When the evaluation criterion is "o", the production method of the present application is suitable.
2. Stability of wire traction
In the extrusion of the resin composition in the above "1. buildup", a case where the strands were stably pulled up after 2 hours of continuous operation was judged to be "good", a case where strand breakage occurred within 2 times in 2 hours of operation was judged to be "Δ (good)", and a case where strand breakage occurred 3 times or more in 2 hours of operation was judged to be "x (bad)". When the evaluation criterion is "o", the production method of the present application is suitable.
[ evaluation of physical Properties ]
3. Toughness (tensile Strength, tensile elongation)
Pellets of the resin compositions of examples and comparative examples obtained by extrusion in the above "1. build-up" were dried in a hot air dryer at 100 ℃ for 2 hours. The dried resin composition was molded into a dumbbell type ISO3167 or multipurpose test piece type A into a dumbbell type A molded piece by an injection molding machine (IS-80EPN, manufactured by Toshiba machine Co.) equipped with an ISO physical property test piece mold under conditions of a cylinder temperature of 320 ℃, a mold temperature of 80 ℃, an injection pressure of 50MPa (gauge pressure), an injection speed of 200mm/sec, and an injection time/cooling time of 20sec/20 sec. The resulting dumbbell-shaped molded pieces were left at 23 ℃ for 24 hours, and then the tensile strength and tensile elongation (tensile nominal strain) of each of 5 pieces were measured at 23 ℃ under the condition of a tensile test speed of 5mm/min in accordance with ISO527, and the average values thereof were determined. As evaluation criteria, it was judged that the higher the value of the tensile strength, the better the mechanical strength, the higher the tensile elongation, the better the toughness, and the less the oxidation deterioration of the resin composition and the incorporation of impurities.
4. Heat stability (tensile Strength Retention after aging)
The ISO dumbbell-shaped molded pieces of the resin compositions of examples 1 to 12 and comparative examples 1 to 6 molded in the above-mentioned "3-toughness (tensile strength, tensile elongation)" were aged in a hot air oven set at 140 ℃ for 1000 hours, then left at 23 ℃ for 24 hours, and then the tensile strength of 5 pieces was measured at 23 ℃ under a condition of a tensile test speed of 5mm/min according to ISO527, and the average value was obtained, and the retention rate of the tensile strength value after aging was calculated, assuming that the tensile strength before aging was 100%. The higher the retention of tensile strength after aging, the more suppressed the oxidative deterioration of the resin composition inside the extruder barrel and the less the contamination of impurities.
[ raw materials ]
< polyphenylene Ether (A) >
(A-1)
Poly (2, 6-dimethyl-1, 4-phenylene) ether having a reduced viscosity of 0.50dL/g (0.5g/dL in chloroform, 30 ℃ C., as measured by an Ubbelohde viscometer).
< styrene resin (B) >
(B-1)
General-purpose polystyrene (trade name: polystyrene 685[ registered trademark ], manufactured by PSJ corporation). It is a polystyrene containing no rubber component, that is, a polystyrene which is not rubber-reinforced.
< styrene-based thermoplastic elastomer (C) >
(C-1)
A triblock copolymer having a polystyrene block-poly (styrene-butadiene) random block-polystyrene block structure and containing 62 mass% of bound styrene was obtained. The hydrogenation rate was 98%. Mn is 48000, Mw is 55000, and Mw/Mn is 1.146.
< antioxidant (D) >
(D-1)
Phosphorus antioxidant (chemical name: 3, 9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5,5] undecane, trade name: ADKSTABPEP-36[ registered trademark ], manufactured by ADEKA Co.).
< other ingredients >
(coloring agent)
Carbon black having an average primary particle diameter of 16 nm.
(polyolefin resin component)
Ethylene-propylene copolymer (trade name: TAFMER P0680J (registered trademark), manufactured by Mitsui chemical Co., Ltd.).
[ example 1]
100% by mass was fed (A-1) from the most upstream part (top feed port) of a TEM58SS twin-screw extruder (manufactured by Toshiba machinery, Inc., barrel number 13 (including the lower barrel of the first feed port hopper), screw diameter 58mm, L/D53; screw mode having 2 kneading disks L, 12 kneading disks R, and 4 kneading disks N), and when the barrel length of the entire extruder (including the lower barrel of the first feed port hopper) was set to 100%, the barrel length of the solid conveying zone (including the lower barrel of the first feed port hopper) was set to 38.5%, the barrel lengths of the remaining melt-kneading zone and melt-conveying zone were set to 61.5% (wherein the barrel length of the melt-kneading zone was 38.5%), the temperature setting for the solid conveying zone (the lower barrel C0 of the first feed port hopper was not included because of water cooling) C1 to C4 were all set to 180 ℃, the barrel set temperatures C5 to C9 in the melt-kneading zone were all set to 290 ℃, C10 among the barrel set temperatures C10 to C12 in the melt-conveying zone was set to 290 ℃, C11 was set to 300 ℃, C12 was set to 320 ℃, the die part was set to 320 ℃, nitrogen was blown at a flow rate of 20L/min to the die nozzle, a vent having a nitrogen injection line and a gas discharge part was provided at the upper opening of the C11 barrel, and nitrogen was blown at a flow rate of 20L/min from the nitrogen injection line during extrusion. Further, the resin composition was obtained by melt-kneading the resin composition with the screw speed of 500rpm and the extrusion speed of 400kg/h, with the oxygen concentration in the collecting hopper above the first supply port set to 0.5 vol%. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 2]
Extrusion was carried out by feeding (A-1)70 mass% and (B-1)30 mass% from the most upstream portion using the twin-screw extruder described in example 1 above. In this case, assuming that the barrel length of the entire extruder (including the lower barrel of the first feed port hopper) is set to 100%, the barrel length of the solid conveying zone (including the lower barrel of the first feed port hopper) is 46.2%, the barrel lengths of the remaining melt-kneading zone and melt-conveying zone are 53.8% (wherein the barrel length of the melt-kneading zone is 30.8%), the barrel set temperatures of the solid conveying zone (the lower barrel of the first feed port hopper C0 is not included because of water cooling) C1 to C5 are all set to 180%, the barrel set temperatures of the melt-kneading zone C6 to C9 are all set to 290%, the barrel set temperatures of the melt-conveying zone C10 to C12 are C10, C11 is set to 300 ℃, C12 is set to 310 ℃, nitrogen blowing to the die nozzle is not performed, and a vent connected to a vent vacuum line is provided in the upper opening portion of the C11, a resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 1, except that the degree of vacuum in the vent was 7.998kPa (60 Torr). The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 3]
Extrusion was carried out by feeding (A-1)50 mass%, (B-1)30 mass%, and (C-1)20 mass% from the most upstream portion using the twin-screw extruder described in example 1. In this case, when the barrel length of the entire extruder (including the lower barrel of the first supply port hopper) was set to 100%, the barrel length of the solid conveying zone (including the lower barrel of the first supply port hopper) was set to 53.8%, and the barrel lengths of the remaining melting and kneading zone and the melting and conveying zone were set to 46.2% (wherein the barrel length of the melting and kneading zone was set to 30.8%), the barrel set temperatures of the solid conveying zone (the lower barrel of the first supply port hopper C0 was not included because of water cooling) C1 among C1 to C6 were set to 50 ℃, C2 to C5 were set to 100 ℃, C5 and C6 were set to 140 ℃, the barrel set temperatures of the melting and kneading zone C7 to C10 were all set to 280 ℃, the barrel set temperatures of the melting and conveying zone C11 to C12 were set to 280 ℃, the barrel head was set to 300 ℃, nitrogen blowing was not performed to the die nozzle, and a vent port to which a vent vacuum line was connected to the upper opening portion of C11 was provided, a resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 1, except that the degree of vacuum of the vent port was 7.998kPa (60Torr) and the oxygen concentration in the collecting hopper above the first supply port was changed to 1.0 vol%. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 4]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 3, except that nitrogen was blown into the die nozzle at a flow rate of 20L/min. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 5]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 4, except that a vent having a nitrogen injection line and a gas discharge portion was provided at the upper opening of the C11 cylinder, and nitrogen was blown into the vent at a flow rate of 20L/min from the nitrogen injection line during extrusion. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 6]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 3, except that the oxygen concentration in the collecting hopper above the first supply port was changed to 1.5 vol% for 30% by mass of (A-1), 50% by mass of (B-1) and 20% by mass of (C-1). The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 7]
When the barrel length of the entire extruder (including the barrel under the first supply port hopper) was set to 100% for 15 mass% (a-1), 65 mass% (B-1) and 20 mass% (C-1), the barrel length of the solid transfer zone (including the barrel under the first supply port hopper) was set to 38.5%, and the barrel lengths of the remaining melt-kneading zone and melt-transfer zone were set to 61.5% (wherein the barrel length of the melt-kneading zone was 23.1%), the barrel set temperatures of the solid transfer zone (barrel C0 under the first supply port hopper, which was not included because of water cooling) C1 to C4 were set to 50 ℃, C2 to C3 ℃, C4 was set to 130 ℃, the barrel set temperatures of the melt-kneading zone C5 to C2 were set to 270 ℃, the barrel set temperatures of the melt-transfer zone C8 to C12 ℃ were set to 270 ℃, and the die head was set to 280 ℃, a resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 6, except that a vent port connected to a vent port vacuum line was provided at the upper opening of a cylinder of C11, the degree of vacuum of the vent port was 7.998kPa (60Torr), and the oxygen concentration in the collecting hopper at the upper part of the first supply port was 1.8 vol% without blowing nitrogen into the die nozzle. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 8]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 3 except that the barrel set temperature of the solid transfer zone (the barrel C0 was not included under the first supply port hopper because of water cooling) was set to 150 ℃ for all of C1 to C6 and the oxygen concentration in the collective hopper above the first supply port was set to 2.7 vol% for (A-1)50 wt%, (B-1)29.5 wt%, (C-1)20 wt%, and (D-1)0.5 wt%. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 9]
The extrusion was carried out by feeding 65 mass% of (A-1), 20 mass% of (B-1), 14 mass% of (C-1), 0.5 mass% of (D-1) and 0.5 mass% of carbon black from the most upstream portion using the twin-screw extruder described in example 1. In this case, assuming that the length of the barrel of the entire extruder (including the lower barrel of the first supply port hopper) is 100%, the length of the barrel of the solid conveying zone (including the lower barrel of the first supply port hopper) is 46.2%, and the lengths of the remaining melting and kneading zones and the melting and kneading zone are 53.8% (wherein the length of the barrel of the melting and kneading zone is 38.5%), C1, C2 to C4, and C5 in C1 to C5 are set to 120%, C2 to C4 are set to 150%, C5 is set to 180%, the barrel set temperatures C6 to C10 in the melting and kneading zone are all set to 280%, C11, C12, and the die head is set to 310 ℃, nitrogen is not blown to the die head nozzle, and a vent port connected to a vent vacuum line is provided at the upper opening of the barrel of C11, a resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 1, except that the degree of vacuum of the vent port was 7.998kPa (60Torr) and the oxygen concentration in the collecting hopper above the first supply port was changed to 2.0 vol%. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 10]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 9, except that 4% by mass of 14% by mass of (C-1) was replaced with the polyolefin resin component TAFMER P0680J. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 11]
Melt-kneading and extrusion were carried out under the same conditions as in example 3 except that C6 in the barrel setting temperature of the solid transfer zone was set to 230 ℃. The evaluation results of the obtained resin composition are shown in table 1 below.
[ example 12]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 9, except that C5 at the barrel setting temperature in the solid transfer zone was set to 250 ℃. The evaluation results of the obtained resin composition are shown in table 1 below.
Comparative example 1
Assuming that the barrel length of the entire extruder (including the lower barrel of the first supply port hopper) was 100%, the barrel length of the solid transfer zone (including the lower barrel of the first supply port hopper) was 23.1%, and the barrel lengths of the remaining melt-kneading zone and melt-transfer zone were 76.9% (wherein the barrel length of the melt-kneading zone was 38.5%), C1 and C2 in C1 to C2 at the barrel set temperature of the solid transfer zone (the lower barrel C0 of the first supply port hopper was not included because of water cooling) were set to 120 ℃, C2 was set to 180 ℃, and all the barrel set temperatures C3 to C7 in the melt-kneading zone were set to 280 ℃, C8 to C11 and C12 in the barrel set temperatures C8 to C12 in the melt-transfer zone were set to 280 ℃, and extrusion was performed under the same conditions as in example 9, thereby obtaining a resin composition. The evaluation results of the obtained resin composition are shown in table 1 below.
Comparative example 2
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 9 except that C1, C2 to C4, C5 and the oxygen concentration in the collective hopper above the first supply port were set to 230 ℃, 250 ℃ and 280 ℃ among C1 to C5, respectively, at the barrel set temperature in the solid transfer zone (barrel C0 under the first supply port hopper was not included because of water cooling), and the oxygen concentration in the collective hopper above the first supply port was set to 0.5 vol%. The evaluation results of the obtained resin composition are shown in table 1 below.
Comparative example 3
When the barrel length of the entire extruder (including the lower barrel of the first supply port hopper) was set to 100%, the barrel length of the solid transfer zone (including the lower barrel of the first supply port hopper) was set to 61.5%, and the barrel lengths of the remaining melt-kneading zone and melt-transfer zone were set to 38.5% (wherein the barrel length of the melt-kneading zone was 15.4%), C1 to C3 in C1 to C7 at the set temperature of the barrel of the solid transfer zone (the lower barrel C0 of the first supply port hopper was not included because of water cooling), C4 to C6 were set to 150 ℃, C7 was set to 180 ℃, all the set temperatures C8 to C9 in the melt-kneading zone were set to 280 ℃, C10, C11, C12 and C12 in the set temperatures C10 to C12 in the melt-transfer zone were set to 280 ℃, and the oxygen concentration in the upper set to 0.5 vol% of the hopper in the same conditions as in example 9, the extrusion was carried out to obtain a resin composition. The evaluation results of the obtained resin composition are shown in table 1 below.
Comparative example 4
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 9, except that the oxygen concentration in the collecting hopper above the first supply port was set to 4.5 vol%. The evaluation results of the obtained resin composition are shown in table 1 below.
Comparative example 5
A resin composition was obtained by melt kneading and extrusion under the same conditions as in comparative example 2, except that nitrogen was blown at a flow rate of 20L/min to a die nozzle, a vent having a nitrogen injection line and a gas discharge portion was provided in the upper opening of the cylinder C11, and nitrogen was blown at a flow rate of 20L/min from the nitrogen injection line during extrusion. The evaluation results of the obtained resin composition are shown in table 1 below.
Comparative example 6
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in example 9, except that C4 and C5 in the barrel setting temperature of the solid transfer zone were set to 250 ℃. The evaluation results of the obtained resin composition are shown in table 1 below.
Figure BDA0002430682300000221
As shown in table 1, the resin compositions of examples 1 to 12 were produced by the production methods described in the scope of claims of the present application, and no occurrence of strand deposition was observed in the die nozzle, and strand pulling stability was good, and no strand breakage was observed in the extrusion production for 2 hours.
In example 4, the portion of the nozzle part of the die from which the resin was discharged through the holes was subjected to nitrogen gas blowing, and the tensile elongation and the retention of tensile strength after aging tended to be excellent as compared with example 3 in which nitrogen gas blowing was not performed.
In example 5, nitrogen gas was further blown into the exhaust port, and the tensile elongation and the retention of tensile strength after aging tended to be more excellent than in example 4.
In example 8, in addition to the production method of the present application, the antioxidant component (C) was blended in the resin composition, whereby oxidation deterioration of the resin was further suppressed at the time of extrusion, and further, the tensile elongation and the retention of tensile strength after aging tended to be excellent.
In example 9, even when a coloring agent (carbon black) was added to the resin composition, the production stability and resin properties were not affected by the production method of the present invention, and a resin composition having good properties was obtained.
In example 10, it was observed that when the content is 5% by mass or less, even if the polyolefin resin component is compounded, the tensile elongation and the retention of tensile strength after aging tend to be excellent without being affected by the production stability and the deterioration of physical properties.
In examples 11 and 12, the cylinder length and the set temperature of the solid transfer zone were within the scope of claims of the present application, and the physical properties were also good, and in the cylinder length of the solid transfer zone other than the cylinder provided with the first supply port, when the cylinder length at the set temperature of 50 to 190 ℃ was set to a range of 75% or more and less than 100%, the toughness and the thermal stability of the molded article tended to be slightly lowered as compared with the case where the length was set to 100%.
On the other hand, in comparative examples 1 to 6, the resin compositions were produced by the production methods other than the claimed range of the production method of the present application, and therefore, the production stability and the physical properties were not sufficient.
In comparative example 1, since the length of the solid transfer zone was short and in comparative example 2, the barrel setting temperature of the solid transfer zone was high, which were outside the scope of the claims of the present application, generation and growth of the buildup were observed during production, and production stability and physical properties were not sufficient.
In comparative example 3, the length of the solid-conveying zone was too long to be outside the scope of claims of the present application, and no melt was observed in the resin composition, and the strand pulling stability and physical properties were insufficient.
In comparative example 4, the oxygen concentration in the collection hopper was high, and was outside the range claimed in the production method of the present application, and generation and growth of the deposit were observed during production, and the production stability and physical properties were insufficient.
In comparative example 5, as in comparative example 2, the cylinder setting temperature of the solid transfer zone was high and outside the scope of the claims of the present application, and nitrogen blowing to the die nozzle and nitrogen blowing to the vent were performed, so that the growth of the buildup was suppressed and strand pulling was stabilized to the end, but the occurrence of buildup was confirmed during production and the physical properties were insufficient.
In comparative example 6, the set temperature of the solid transfer zone was outside the range of claims of the present application, and therefore, although strand pulling was stabilized to the end, generation of the build-up was confirmed at the time of production. In addition, the physical properties are also insufficient.
Industrial applicability
According to the production method of the present invention, the production of a polyphenylene ether resin degradation product and the generation of a build-up around a die nozzle, which occur in the barrel of an extruder during extrusion, are significantly suppressed, the extrusion production stability is improved, and the polyphenylene ether resin composition having good toughness can be stably mass-produced because the incorporation of impurities is small, and the obtained resin composition can be favorably used in parts of home electronics OA equipment, motor electronics, automobile applications, various industrial products, and the like.

Claims (8)

1. A method for producing a resin composition by using an extruder, wherein,
the resin composition contains polyphenylene ether (A) in an amount of 10 mass% or more based on 100 mass% of the total resin composition,
the extruder is a twin screw extruder having a solids conveying zone, a melt mixing zone, and a melt conveying zone, the solids conveying zone having a barrel with a first feed port,
when the length of the entire barrel of the extruder is 100%, 30 to 60% of the upstream side of the extruder is the solid transfer zone, and the remaining 40 to 70% are the melt-kneading zone and the melt-transfer zone,
in the case where the length of the cylinder other than the cylinder provided with the first supply port is 100% of the cylinders constituting the solid matter transfer zone, the set temperature of 75% or more of the cylinders is in the range of 50 ℃ to 190 ℃,
the set temperature of the barrel constituting the melt-kneading zone and the barrel constituting the melt-conveying zone is in the range of 250 ℃ to 320 ℃,
the oxygen concentration in a collection hopper provided above the first supply port is set to 3 vol% or less.
2. The method for producing a resin composition according to claim 1, wherein, in a case where a length of a cylinder other than the cylinder provided with the first supply port in the cylinder constituting the solid transfer zone is set to 100%, a set temperature of the 100% cylinder is in a range of 50 ℃ to 190 ℃.
3. The method for producing a resin composition according to claim 1 or 2, wherein the melt-transporting zone has a cylinder provided with an opening, and a vent provided with a nitrogen injection line and a gas discharge portion is provided above the opening.
4. The method for producing a resin composition according to any one of claims 1 to 3, wherein all of the extrusion raw material is supplied from the first supply port.
5. The method for producing a resin composition according to any one of claims 1 to 4, wherein the resin composition further contains 5 to 80% by mass of a styrene-based resin (B) relative to 100% by mass of the total resin composition.
6. The method for producing a resin composition according to any one of claims 1 to 5, wherein the resin composition further contains a styrene-based thermoplastic elastomer (C) in an amount of 0.1 to 25% by mass based on 100% by mass of the total resin composition.
7. The method for producing a resin composition according to any one of claims 1 to 6, wherein the resin composition further contains 0.001 to 3% by mass of an antioxidant (D) based on 100% by mass of the total resin composition.
8. The method for producing a resin composition according to any one of claims 1 to 7, wherein the content of the polyolefin resin component in the resin composition is 5% by mass or less with respect to 100% by mass of the total resin composition.
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