JP4190941B2 - Production method and resin composition thereof - Google Patents

Description

【００６１】
【表２】

【００６２】
【表３】

【００６３】
【発明の効果】
以上説明したように、本発明の難燃ポリフェニレンエーテル樹脂組成物の製造方法は生産性に優れ、得られた樹脂組成物は優れた物性及び着色性を有する。
【図面の簡単な説明】
【図１】本発明の一例に係る難燃ポリフェニレンエーテル樹脂組成物の製造方法に関する概略を示す説明図である。
【符号の説明】
１． ポリフェニレンエーテル粉体のフレコンバッケージ
２． ポリフェニレンエーテル粉体ストックホッパー
３． 遮断弁
４． ポリフェニレンエーテル粉体用重量式フィーダー
５． ポリスチレン系樹脂用ストックホッパー
６． 遮断弁
７． ポリスチレン系樹脂用重量式フィーダー
８． ガス抜き配管
９． 第一工程用押出機第一供給口ホッパー
１０． 第一工程用二軸同方向回転押出機
１１． 真空ベント
１２． スクリーンチェンジャー
１３． ダイ部
１４． ストランドバス
１５． ストランドカッター
１６． 篩い
１７． 中間原料輸送用コンテナ
２０． 中間原料用ストックホッパー
２１． 遮断弁
２２． 中間原料用重量式フィーダー
２３． ポリスチレン系重量式フィーダー
２４． 第二工程押出機第一供給口ホッパー
２５． 第二工程用二軸同方向回転押出機
２６． 真空ベント
２７． ダイ部
２８． ストランドバス
２９． ストランドカッター
３０． 篩い
３１． 液状難燃剤添加ノズル
３２． 重量式液状添加難燃剤フィーダー（ギアポンプ）
３３． 重量式液状添加難燃剤フィーダー（タンクとロードセル）[0001]
BACKGROUND OF THE INVENTION
The polyphenylene ether resin composition has a lot size ranging from a small one to a large one, and has a large number of grades and various colors. Moreover, since the polyphenylene ether resin is a powder and difficult to handle, a special powder supply facility is required for each extruder in order to melt and knead the polyphenylene ether powder with an extruder.
The present invention relates to a method for producing a flame retardant polyphenylene ether resin composition having excellent productivity, physical properties and colorability .
[0002]
[Prior art]
The prior art for making a conventional polyphenylene ether resin intermediate (intermediate raw material) pellet and making a polyphenylene ether resin composition is:
(1) A technique for producing a polyphenylene ether resin composition by producing an intermediate (intermediate raw material pellet) of a polyphenylene ether powder resin and a polystyrene resin, and melt-kneading the intermediate raw material and the polystyrene resin is disclosed. Yes. (For example, refer to Patent Document 1.)
(2) Polyphenylene ether powder resin and flame retardant are melt-kneaded to produce a flame-retardant polyphenylene ether intermediate raw material pellet of about 2 to 5 mm, and the intermediate raw material and polystyrene resin are melt-kneaded to obtain a flame-retardant polyphenylene ether resin. Techniques for producing the composition are disclosed. (For example, see Patent Document 2.)
The conventional technology for extruding with high production and high quality under conditions of high concentration of conventional polyphenylene ether resin powder is as follows: (3) 70 parts by weight of polyphenylene ether powder resin and 30 parts by weight of polystyrene resin under stable and high production conditions Techniques for extruding and producing high quality pellets are disclosed. (For example, see Patent Documents 3, 4, 5 and 6.)
[0003]
[Patent Document 1]
Japanese Patent Laid-Open No. 04-117444 [Patent Document 2]
Japanese Patent Laid-Open No. 07-216100 [Patent Document 3]
Japanese Patent Laid-Open No. 09-070872 [Patent Document 4]
Japanese Patent Laid-Open No. 10-024483 [Patent Document 5]
JP-A-10-180840 [Patent Document 6]
JP-A-10-180842 [0004]
[Problems to be solved by the invention]
When producing a polyphenylene ether resin composition from polyphenylene ether powder, there are at least five problems.
(1) The polyphenylene ether resin composition has a wide variety and lot sizes of various sizes. In order to produce these various kinds of compositions, many extruders are required from a small size to a large size.
[0005]
(2) Since polyphenylene ether is a powder and is a resin that is particularly difficult to handle, each extruder requires a special powder transport device and a device (bug filter, dust collection duct) that prevents the powder from flowing out. It is necessary to install.
For example,
a. Since the bulk density of the powder is lower than that of the pellet, the amount of extrusion is reduced.
b. When supplying polyphenylene ether powder to the extruder feed hopper, if the polyphenylene ether powder does not separate the entrained gas well, it will cause poor powder biting in the extruder and reduce the amount of powder extruded. As a result, variations in physical properties occur.
[0006]
(3) The melting point of the polyphenylene ether powder is 290 ° C., and since the melt viscosity of the polyphenylene ether is high, the extrusion processing temperature becomes high. Therefore, the deterioration of the rubber in high impact polystyrene and the fluidity fall by gelation of polyphenylene ether resin are caused.
(4) Polyphenylene ether resin has a high melt viscosity, so in order to increase productivity, especially when the barrel temperature in the extruder transport zone is raised, the polyphenylene ether powder adheres to the barrel wall surface and screw bottom surface, resulting in thermal degradation. Wake up. The heat-degraded polyphenylene ether reacts with the flame retardant and causes coloring failure when colored. In addition, the thermal stabilizer is decomposed and the rubber is deteriorated.
[0007]
(5) If there are many kinds of polyphenylene ether intermediate raw materials, in the first step, there is an increase in product type switching loss, resulting in reduced productivity, a complicated production plan, and increased labor.
It is required to solve the problems of these polyphenylene ether powders.
However, the prior art is not sufficient for these problems.
An object of this invention is to establish the manufacturing method of the flame-retardant polyphenylene ether resin composition excellent in productivity, a physical property, and coloring property .
[0008]
[Means for Solving the Problems]
As a result of intensive investigations to achieve the above object, a method for producing a flame-retardant polyphenylene ether resin composition having excellent productivity, physical properties and colorability and the resin composition have been achieved.
That is, the present invention includes the following (a) to (a), wherein 70 to 99 parts by weight of polyphenylene ether powder and 1 to 30 parts by weight of a polystyrene resin and / or a flame retardant are melt-kneaded using an extruder to produce intermediate raw material pellets. c) Using the first step consisting of step c) and an extruder, the intermediate raw material pellets 10 to 90 parts by weight, the polystyrene resin 90 to 10 parts by weight, and the resin part 100 parts by weight, the flame retardant 5 to 30 parts by weight. A method for producing a flame-retardant polyphenylene ether resin composition comprising a second step of melt-kneading a part.
[0009]
a) A polyphenylene ether powder is supplied in the order of a powder stock hopper, a gravimetric feeder for powder, and an extruder first supply port hopper.
b) The polyphenylene ether powder supply pipe and the gas vent pipe are arranged in the order of the polyphenylene ether powder feed pipe and the gas vent pipe from above the first supply port hopper and from the gear box side toward the die. .
c) The polyphenylene ether powder is passed through the powder supply pipe, and supplied to the first supply port of the extruder along the first supply port hopper wall surface at a gear box side wall angle of 60 to 85 degrees. Remove the contained gas from the vent piping.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to the drawings.
First, the drawings will be described.
FIG. 1 shows a schematic diagram for producing a flame retardant polyphenylene ether resin composition by making intermediate raw material pellets from polyphenylene ether powder according to an example of the present invention.
In FIG. 1, 1 is a flexible container pack containing polyphenylene ether powder. 2 is a polyphenylene ether powder stock hopper. The flexible container is hung on 2, and the bottom of the flexible container is opened and supplied to the stock hopper. 3 is a weight type feeder hopper cutoff valve 4. The mechanism of this 3 shut-off valve sets the raw material weight lower limit value and the upper limit value in the hopper of the 4 weight type feeder, and when the raw material falls below the lower limit value, the 3 shut-off valve opens, When the raw material is fed from the stock hopper to the 4 weight feeder hopper and reaches the upper limit, the shut-off valve is throttled. 4 is a weight type feeder for polyphenylene ether powder. Reference numeral 5 denotes a polystyrene-based resin stock hopper. 6 is a shut-off valve. Reference numeral 7 denotes a polystyrene-based weight feeder. Reference numeral 8 denotes a vent pipe for extracting gas from the polyphenylene ether powder. 9 is the 1st supply port hopper of a 1st process extruder. Reference numeral 10 denotes a biaxial co-rotating extruder for the first process.
[0011]
11 is a vacuum vent. Reference numeral 12 denotes a screen changer. Reference numeral 13 denotes a die part. 14 and 28 are strand buses. 15 and 29 are strand cutters. 16 and 30 are sieves. Reference numeral 17 denotes an intermediate raw material transport container. Reference numeral 20 denotes an intermediate raw material stock hopper. 21 is a shut-off valve that is opened when the feeder 22 is REFIL. 23 is a weight type feeder for polystyrene resin. Reference numeral 24 denotes a first supply port hopper of the second process extruder. 25 is a biaxial co-rotating extruder for the second step. 26 is a vacuum vent. Reference numeral 27 denotes a die portion. 31 is a liquid flame retardant addition nozzle. 32 and 33 are liquid flame retardant weight type feeders, and 32 is a gear pump. Reference numeral 33 denotes a tank and a load cell.
[0012]
Next, the present invention will be described with reference to the drawings described above.
A preferred range of the polyphenylene ether powder of the present invention is 70 to 99 parts by weight, and a more preferred range is 80 to 99 parts by weight. A preferable range of the polystyrene-based resin is 30 to 1 part by weight, and a more preferable range is 20 to 1 part by weight. The polystyrene resins used in the first and second steps are general purpose polystyrene resins, high impact polystyrene resins, styrene / acrylic copolymer resins, styrene / acrylic / butadiene copolymer resins, and the like. Particularly preferred polystyrene resins are general purpose polystyrene and high impact polystyrene. The rubber average particle size of the high impact polystyrene is preferably around 1.0 to 2.0 μm, and the preferable rubber concentration is 8 to 15% by weight. The high impact polystyrene rubber is preferably a high cis butadiene rubber or a partially hydrogenated butadiene rubber. The partially hydrogenated butadiene rubber is hydrogenated in an amount of 5 to 70% by weight of the total double bonds, and the 1,2-vinyl bond amount and 1,4-bond amount are 3% by weight or less and 30% by weight, respectively. That is necessary.
[0013]
The polyphenylene ether of the present invention has a reduced viscosity (unit: g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.25 to 0.6, more preferably in the range of 0.35 to 0.55. Polymers and / or copolymers. Specific examples of the PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl). -6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,6- 3,6-trimethylphenol and 2-methyl-6-butylphenol) are preferred, among which poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol and 2,3 , 6-trimethylphenol copolymer is preferred, and poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred.
[0014]
The polyphenylene ether powder of the present invention is preferably supplied in a flexible container pack as shown in FIG. 1- (a) First Process Outline, or supplied to a stock hopper together with an inert gas using a pneumatic. However, when using a pneumatic, a filter that separates gas and polyphenylene ether powder is required for the stock hopper of 2. The inert gas flow rate for transporting the polyphenylene ether powder is preferably 1 to 100 Nm ³ for transporting 1 kg of the polyphenylene ether powder per hour. Further, the filter area is preferably 0.1 to 10 m ² in order to allow an inert gas amount of 1 Nm ³ to pass through per hour. The filter is preferably a bag filter or the like, and more preferably an automatic backwash device.
[0015]
In addition, the polyphenylene ether powder of the present invention is preferably supplied in the order of the powder stock hopper, the powder-type weight feeder, and the extruder first supply port hopper from the top to the bottom.
The polyphenylene ether powder stock hopper of the present invention preferably uses an inert gas (such as nitrogen gas, carbon dioxide gas, and argon gas) to lower the oxygen concentration to 18 wt% or less. More preferably, it is 15 wt% or less.
[0016]
The shut-off valve 3 used in the present invention is preferably a plate valve type or a rotary valve type.
The first and second process weight type feeder of the present invention is a device for measuring a decrease in weight of raw materials over time with a load cell or the like and adjusting it to a predetermined supply amount, manufactured by K-TRON, Switzerland, Brabender, USA Acryson And feeders of Kubota, Japan. The screw type of the weight type feeder of polyphenylene ether powder is preferably a biaxial fully meshing screw, an auger type biaxial, or a single screw. The polystyrene resin feeder screw can be either biaxial or uniaxial, but if the pellet is not very slippery and hard, a uniaxial screw is preferred. A belt-type heavyweight feeder can also be used.
[0017]
The extruder first feed port hopper of the present invention is preferably mounted on the barrel of the extruder. An inert gas (nitrogen gas, carbon dioxide gas, argon gas, etc.) is injected into the hopper, and the oxygen concentration in the hopper is preferably less than 10 wt%, more preferably less than 5 wt%, still more Preferably it is less than 2 wt%.
[0018]
A preferable angle of the wall surface of the hopper is 60 to 85 degrees. The polyphenylene ether powder is preferably dropped on the wall surface. In addition, the wall surface angle of the hopper referred to in the present invention is an angle (usually an acute angle) formed by the horizontal plane and the hopper. The piping layout of the hopper is preferably arranged in order from the gearbox side to the polyphenylene ether powder supply piping and the gas vent piping. When the positions of the powder supply pipe and the vent pipe are reversed, the bulk density of the powder is reduced and the gas venting is poor, and the amount of extrusion is greatly reduced. The polystyrene resin supply pipe is preferably installed on the downstream side of the vent pipe or at the lower part of the hopper. That is, the gas and fine powder accompanying the polyphenylene ether are present in the upper part of the hopper. For example, if the installation positions of the vent gas pipe and the polystyrene resin supply pipe are reversed, the gas venting is reduced. At the same time, the fine powder flows back to the polystyrene piping or the gravimetric feeder, the powder accumulates, and the flow rate of polyphenylene ether becomes unstable.
[0019]
Examples of the first and two-step twin-screw co-rotating extruders used in the present invention include ZSK series manufactured by Coperion, Germany, Toshiba Machine TEM series, and TEX series manufactured by Nippon Steel Works. Among them, the ZSK mega compounder, TEMSS series, and TEXαII series of high torque type extruders are preferable.
The screw major axis D of the extruder of the present invention is preferably D = 43 to 180 mm, more preferably D = 70 to 180 mm. The long axis of the extruder screw is preferably 43 mm or more in consideration of productivity, and is preferably 180 mm or less in consideration of suppression of heat generation and excessively low rotation speed and reduction in productivity.
[0020]
The screw configuration of the extruder plasticization zone of the present invention combines kneading disc light (abbreviated KR) and kneading disc neutral (abbreviated KN) because of the high concentration of polyphenylene ether powder. For example, a configuration in which KR, KR, KR, and KN are arranged in this order is preferable.
Since the operating conditions of the extruder of the present invention are high in polyphenylene ether powder concentration, it is necessary to control the resin temperature at the die outlet to less than 370 ° C. When the die outlet resin temperature of the polyphenylene ether resin is 370 ° C. or higher, the polyphenylene ether starts to undergo a crosslinking reaction, the molecular weight is increased, and the fluidity is greatly lowered. Therefore, the die outlet resin temperature needs to be lower than 370 ° C. The die exit resin temperature is preferably less than 370 ° C, more preferably less than 360 ° C.
[0021]
Among the operating conditions of the extruder according to the present invention, the relationship between the extruder screw major axis and the screw rotation speed can be obtained from the following formula (1).
2000 × D− ^0.57 <N <5000 × D− ^0.57 Formula (1)
N: Screw rotation speed rpm
The screw rotation speed N is preferably 2000 × D ^−0.57 rpm or more in consideration of generation of unmelted polyphenylene ether powder. In consideration of the die outlet resin temperature exceeding 370 ° C., it is preferably 5000 × D− ^0.57 rpm or less.
[0022]
Among the operating conditions of the extruder of the present invention, the extrusion amount is determined from the following formulas (2) and (3).
7 × 10 ⁻³ <DLQ <18 × 10 ⁻³ formula (2)
DLQ: dimensionless extrusion (-)
DLQ = Q / (60 × ρ × 2 × 3.14 × N × D ³ ) Formula (3)
Q: Extrusion amount kg / H
ρ: Density Here, 1000 kg / m ³
60: kg / H / rpm → kg / s / rps
The dimensionless extrusion amount DLQ is preferably 7 × 10 ⁻³ or more in view of the resin temperature, and is preferably 18 × 10 ⁻³ or less in consideration of the torque being excessively increased and the operation being impossible.
[0023]
The barrel set temperature of the extruder of the present invention is set to 150 to 300 ° C in the powder conveyance zone, and the barrel set temperature in the plasticizing zone is set to 250 to 300 ° C. The barrel temperature in the powder conveyance zone is 150 considering that the amount of gas entrained with the polyphenylene ether increases, the gas expands in the plasticization zone, hardly flows downstream, and the polyphenylene ether conveyance capability decreases. It is preferable that the temperature is at least ° C. Further, considering that the amount of powder adhering and staying on the wall of the barrel increases and the staying powder causes thermal deterioration and causes foreign matters, the temperature is preferably 300 ° C. or lower. The barrel set temperature of the plasticizing zone is preferably 250 ° C. or higher in consideration of melting of polyphenylene ether. Further, considering that the concentration of polyphenylene ether becomes high and the resin temperature at the die exit becomes too high, the temperature is preferably 300 ° C. or lower.
The vacuum vent of the extruder of the present invention is preferably degassed under reduced pressure (50 mmHg to 750 mmHg).
[0024]
The screen changer of the present invention is preferably one that can be switched one by one while continuously operating extrusion, or one that can be switched within one second in the plate method. The screen changer is preferably switched in continuous operation from the viewpoint of productivity. The effective filtration area of the breaker plate attached to the screen changer is preferably 1 to 50 mm ^{2 and} more preferably ² to 40 mm ² with respect to 1 kg of extrusion amount per hour. The filtration area is preferably 1 mm ² or more in consideration of the frequency of switching the screen changer due to foreign matter in the resin and the increase in the resin temperature due to the increase in the die pressure. In addition, the filtration area should be 50 mm ² or less considering that the breaker plate becomes larger, the retention area increases, the resin accumulated in the retention area is thermally deteriorated, peels off, becomes a foreign matter, and causes quality problems. Is preferred.
[0025]
The die part of the present invention is preferably a strand cutting die, a hot cutting die, or an underwater cutting die. The die hole diameter is preferably 1 to 8 mm. Considering that the pellet becomes too small and cannot be separated by a sieve, the die hole diameter is preferably 1 mm or more. Moreover, in the case of a strand, it is preferable that the die hole diameter is 8 mm or less considering that the take-up speed becomes too fast and it can be cut with a cutter.
[0026]
In the case of the strand cut method, the pellets of the first and second steps of the present invention are cooled by a strand bath containing cooling water controlled at 30 to 80 ° C. or cooled by a belt conveyor on which fountain is applied, or Germany It is preferable to cool with WS WET CUT SYSTEM of the country's SCHEER, and cut into a cylindrical shape having a diameter of 1 to 6 mm and a length of 1 to 6 mm with a pelletizer. Moreover, in the case of a hot cut system and an underwater system, it is preferable to cut the resin that has come out of the die hole into a spherical shape of 1 to 5 mm with a rotary blade.
[0027]
The size of the pellet of the present invention is preferably a columnar length of 1 to 6 mm, a diameter of 1 to 6 mm, a spherical shape and a diameter of 1 to 6 mm. The pellet is preferably 1 mm or more in consideration of an increase in fine powder called cutting powder. In view of insufficient plasticization, the pellet is preferably 6 mm or less. The pellet size distribution is preferably matched to the pellet size distribution of the polystyrene resin. The reason is that when blending polyphenylene ether intermediate raw material pellets and polystyrene pellets (including pellet blending with an extruder screw), classification is eliminated if the particle size distribution is made uniform. According to the common sense of resin manufacturers, it is common sense to cut the pellet size (length) distribution with a target of 3 mm.
[0028]
In the first and second steps of the present invention, a sieve is used. The sieve is a device that removes pellets that are too long or short. , Pellet chips) are also removed. In particular, it is common knowledge that chips of a cutter of 75 μm or less, called swarf, adhere to the hopper wall surface and the conveyance wall surface and become difficult to clean.
The average particle size of the polyphenylene ether powder of the present invention is in the range of 30 to 800 μm. The method for measuring the average particle size of the polyphenylene ether powder of the present invention is a value measured by a Cole counter measuring machine, a laser diffraction type particle size meter or the like.
[0029]
Moreover, the preferable molecular weight distribution (Mw / Mn) of the polyphenylene ether of the present invention is 1.5 to 3.5, and the particularly preferable molecular weight distribution (Mw / Mn) is 2.3 to 3.5. Mw is a weight average molecular weight, Mn is a number average molecular weight, and the molecular weight of polyphenylene ether is measured by gel permeation chromatography (hereinafter referred to as GPC) and is a polystyrene equivalent amount. Considering the balance of fluidity, Mw / Mn is preferably 1.5 or more, and considering that the low molecular weight portion is increased and impact resistance is lowered, Mw / Mn is preferably 3.5 or less.
[0030]
Furthermore, zinc oxide, zinc sulfide, phosphorus-based stabilizers (for example, MARK 2112, PEP36, PEP45, etc. manufactured by Asahi Denka), hindered phenol-based stabilizers, etc. are added as heat stabilizers in the first step of the present invention. I can do it.
Next, the second step of the present invention will be described.
In the second step of the present invention, the flame retardant is 5 to 30 parts by weight with respect to 100 parts by weight of the resin part composed of 10 to 90 parts by weight of the polyphenylene ether intermediate raw material pellets obtained in the first step and 90 to 10 parts by weight of the polystyrene resin. Is kneaded with an extruder to produce a polyphenylene ether resin composition.
[0031]
The flame retardant of the present invention may be either solid or liquid. In the case of a solid, it is preferably supplied from the first supply port hopper of the extruder, and in the case of a liquid, it is preferably added after melt-kneading the resin. Examples of the flame retardant include triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl-bis (3,5,5'-tri-methyl-hexyl phosphate), ethyl diphenyl phosphate, 2-ethyl -Hexyl di (p-tolyl) phosphate, bis- (2-ethylhexyl) p-tolyl phosphate, tolyl phosphate, bis- (2-ethylhexyl) phenyl phosphate, tri- (nonylphenyl) phosphate, di (dodecyl) p-tolyl Examples include phosphate and tricresyl phosphate.
[0032]
Dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate and 2-ethylhexyl diphenyl phosphate, 2,2-bis- {4- [bis (phenoxy) phosphoryl Oxy] phenyl} propane, 2,2-bis- {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, phosphoric acid- (3-hydroxyphenyl) diphenyl, resorcin / bis (diphenylphosphate), 2-naphthyl Examples thereof include phosphoric acid ester flame retardants such as diphenyl phosphate, 1-naphthyl diphenyl phosphate, and di (2-naphthyl) phenyl phosphate.
[0033]
The extruder of the present invention is preferably a single-screw extruder or a twin-screw co-rotating extruder. The single-screw extruder is preferably an extruder such as a kneader from Coperion (formerly Buss). The length L of the extruder is preferably about L = 20 to 48, and it is preferable that the reinforcement can be side-fed and the equipment can be added with a liquid flame retardant. The vacuum vent is preferably installed for removing moisture and decomposition products. When the flame retardant is liquid, a liquid addition device for supplying the liquid flame retardant is necessary. The liquid addition device is a device that supplies a liquid flame retardant from the injection nozzle to the side of the extruder using a gear pump, plunger pump, etc., and the flow rate is controlled by a device or unit that adjusts the valve opening. A weight type feeder that measures weight loss per hour and controls the number of rotations of the pump is preferable, and a weight type feeder is particularly preferable. The weight-type liquid addition feeder is often used in recent years because of its low price and high flow accuracy.
[0034]
In the extruder used in the present invention, it is desirable to remove foreign substances by attaching a metal mesh of No. 10 to No. 200 to the breaker plate. The filtration area of the breaker plate is preferably the same as in the first step. However, it is necessary to remove the mesh when building a reinforcement grade.
Moreover, a glass fiber and / or a reinforcing material can be added to the flame-retardant polyphenylene ether resin of the present invention as necessary. The addition amount is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the resin part obtained in the second step.
[0035]
The filler which is a reinforcing material of the present invention includes heavy calcium carbonate, colloidal calcium carbonate, soft calcium carbonate, silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, alumina, magnesium hydroxide, talc, mica, glass flakes , Hydrotalcite, acicular filler (wollastonite, potassium titanate, basic magnesium sulfate, seplite, zonotolite, aluminum borate), glass beads, silica beads, alumina beads, carbon beads, glass balloons, metallic conductive Fillers, non-metallic conductive fillers, carbon, magnetic fillers, piezoelectric / pyroelectric fillers, slidable fillers, fillers for sealing materials, UV absorbing fillers, damping fillers, conductive fillers (Ketjen black, acetylene black ) Etc., fiber , Glass fiber, carbon fiber, metal fiber and the like.
[0036]
In order to improve the impact resistance of the present invention, an additive may be further added to the flame retardant polyphenylene ether resin described above. The additive is a polyolefin resin (high density polyethylene, low density polyethylene, medium density polyethylene, linear low density polyethylene, ethylene / propylene copolymer, ethylene / octene copolymer, and the amount added is 100 weight of the polyphenylene ether resin. The amount is preferably 0.1 to 5 parts by weight, and preferably 0 to 5 parts by weight of styrene / ethylene / butylene / styrene block copolymer and / or styrene / isoprene block copolymer.
[0037]
【Example】
The present invention will be described based on examples.
First, the first process will be described.
Intermediate raw material production example (first step)
The operating conditions of the extruder used in the first step of the present invention are as shown below. (Hereinafter, polyphenylene ether may be abbreviated as PPE and polystyrene as PS.)
[0038]
(A) Raw material PPE resin A: Average particle diameter: 500 μm Mw / Mn: 2.8 Reduced viscosity: 0.51
PPE resin B: Average particle size 250 μm Mw / Mn: 2.5 Reduced viscosity: 0.45
(B) Extruder Extruder: A twin-screw co-rotating extruder TEM-136SS (extruder length 7 barrels approximately L / D = 28) manufactured by Toshiba Machine Co., Ltd. was used.
[0039]
Screw configuration and barrel configuration No. 1 barrel: Supply zone no. 2-No. 4 barrels: transport zone no. 5 barrels: Plasticizing zone no. 6 barrels: vacuum vent barrel (vacuum venting was performed at an absolute pressure of 100 mmHg.)
Barrel temperature No. 1 barrel 70 ℃
No. 2-No. 4 barrels: 250 ° C
No. 5 barrels: 290 ° C
No. 6 barrels: 270 ° C
[0040]
Screw rotation speed: 450rpm
Screen changer: Plate type screen changer Breaker plate effective filtration area of screen changer: 500cm ² Metal mesh: Metal mesh combining 20/60/20 (Attach to breaker plate)
Die plate: 4,5mmΦ hole diameter 150 holes
Strand bath length: 5m
Strand water temperature: 40 ° C
The strand was immersed in strand water for 2 m, then air-cooled, and water attached to the strand surface was blown off with an air wiper.
Strand pelletizer inlet temperature: 140 ° C
Pellet size (length): 3 mm target (separate granulated pellets and long pellets with a sieve to produce cylindrical pellets with 99 wt% of 2.5 to 3.5 mm.)
[0042]
First supply port hopper: Oxygen concentration in the rectangular first supply port hopper with a slope of 70 degrees: 2.5 wt%
Piping layout of the first supply hopper: (in order from the gearbox to the downstream)
1. 1. Polyphenylene ether supply pipe 2. Vent gas piping Polystyrene feed pipe weight feeder: K-Tron weight feeder (for polyphenylene ether powder and polystyrene pellet)
[0043]
Setting of each weight type feeder PPE feeder: 85 parts by weight PS feeder: 15 parts by weight (A & M general purpose polystyrene 685 / A & M high impact polystyrene H9405 = 5 parts by weight / 10 parts by weight)
Feeder for PS: 1 part by weight / stabilizer (685 / zinc oxide / Adeka phosphorus stabilizer PEP36 = 50/25/25) (masterbatch)
Confirmation of foreign matter The number of foreign matters in the pellets was determined by counting the number of carbides of a molded product compression-molded at 250 ° C. with a press mold having an inner size of 160 × 160 mm and a thickness of 1 mm. 100 μm or more was defined as 1 point / piece.
[0044]
[Manufacturing 1]
From a flexible container, 5 tons of polyphenylene ether powder was charged into a 20 m ³ stock hopper, and a REFIL amount of 400 kg was charged from the stock hopper to the feeder hopper.
The stock hopper, feeder hopper, and first supply port hopper were purged with nitrogen.
The rotation speed of the extruder in the first step was 300 rpm. The flow rate of the weight type feeder for polyphenylene ether powder was set to 2550 kg / H, and the flow rate of the weight type feeder for polystyrene system was set to 480 kg / H. The average diameter of the pellet size was 3.1 mm. The obtained composition was designated as intermediate raw material species a. Details are shown in Table 1.
[0045]
[Manufacturing 2]
Manufactured in the same manner as in Manufacture 1 except that the amount of extrusion was 1500 kg / H. Since the die outlet resin temperature exceeded 380 ° C., there were many foreign substances and the strands became gelled and hardened. The obtained composition was designated as intermediate raw material species b. Details are shown in Table 1.
[Manufacturing 3]
Manufactured in the same manner as in Manufacture 1 except that the screw rotation speed was changed to 500 rpm. Since the resin temperature exceeded 380 ° C., there were many foreign substances and the strands became gelled and hardened. The resulting composition was designated as intermediate raw material species c. Details are shown in Table 1.
[0046]
[Manufacturing 4]
Manufactured in the same manner as in Manufacture 1 except that the vent pipe and the polyphenylene ether powder supply pipe were replaced. Due to poor degassing in the polyphenylene ether powder, it was stored in the first supply hopper. Stable extrusion operation was not possible. Details are shown in Table 1.
[Manufacturing 5]
Manufactured in the same manner as Manufacture 1 except that the first supply hopper wall angle was changed to 40 degrees. Since the polyphenylene ether powder is stored on the hopper wall surface, the extrusion amount is reduced, and the stored polyphenylene ether powder is instantaneously supplied. Details are shown in Table 1.
[0047]
[Manufacturing 6]
Manufactured in the same manner as in Manufacture 1 except that the polyphenylene ether powder was sent from the flexible container to the weight-type hopper using a pneumatic. However, since polyphenylene ether powder is transported by pneumatic, a bag filter is installed at the end of the degassing pipe of the heavy hopper so that the gas and polyphenylene ether powder can be separated. Since the bulk density of the polyphenylene ether powder decreased when transported by pneumatic, the powder feeder phenomenon caused the powder flushing phenomenon (bulk density decreases and liquefaction occurs when the powder contains gas), and the first supply hopper The polyphenylene ether powder flowed all at once, and the extruder stopped due to torque over. Details are shown in Table 1.
[0048]
[Manufacturing 7]
Manufactured in the same manner as Manufacture 1 except that the nitrogen purge was stopped. Due to the high oxygen concentration, there were many foreign substances. The resulting composition was designated as intermediate raw material seed d. Details are shown in Table 1.
[0049]
[Manufacturing 9]
Manufactured in the same manner as in Manufacture 1 except that a polyphenylene ether powder having a molecular weight distribution Mw / Mn of 2.0 was used. The obtained composition was designated as intermediate raw material seed f. Details are shown in Table 2.
[Manufacturing 10]
Manufactured in the same manner as in Manufacture 1 except that the polyphenylene ether powder / PS resin was changed to 60 parts by weight / 40 parts by weight. The resin temperature was as low as 325 ° C., and productivity was increased. The obtained composition was designated as intermediate raw material seed g. Details are shown in Table 2.
Hereinafter, the present invention will be further described by examples and comparative examples.
[0050]
[Second step]
(C) Extruder Extruder: TEM58SS (10 barrels) manufactured by Toshiba Machine was used.
Screw configuration and barrel configuration No. 1 barrel: supply zone no. 2 to 4 barrels: transfer zone no. 5 barrels: plasticization zone no. 6 Barrel: Reinforcement side feed barrel No. 6 7 barrel: Barrel No. for reinforcing material kneading 8 Barrel: Vacuum vent barrel no. 9 barrel: Liquid additive injection barrel No. 9 10 barrels: Closed barrel
Barrel temperature No. 1 barrel: 50 ° C
No. 2-No. 4 barrels: 250 ° C
No. 5 barrels: 290 ° C
No. 6-No. 10 barrels: 270 ° C
Screw rotation speed: 600rpm
No. The 8-barrel vacuum vent was depressurized with an absolute pressure of 100 mmHg.
[0052]
The gravimetric feeder is used for polyphenylene ether intermediate raw material pellets and polystyrene resins (flame retardants, impact modifiers, colorants and other additives are blended with polystyrene resins) and liquid flame retardants for gravimetric liquid additions. Three were prepared. As the flame retardant, trade name CR741 manufactured by Daihachi Chemical was used, and the flame retardant feed tank and piping were heated to 70 to 100 ° C.
The plasticizing zone screw configuration (No. 5) was 2 kneading disc lights, 1 kneading disc neutral, 1 kneading disc left, and 1 kneading disc light.
[0053]
The reinforcing material kneading zone (No. 8) was 2 kneading disclites, 1 kneading disc neutral, 1 kneading disc left, and 1 kneading disc light.
The screw configuration of the liquefaction zone was 1 kneading disc light and 1 kneading disc left.
[0054]
Extrusion amount: 500 kg / H
Metal mesh: A metal mesh combining No. 20 / No. 60 / No. 20/100 was pasted on a breaker plate.
Die plate: 4mmφ hole diameter 25 holes Strand bath length: 5m
Strand water: 40 ° C
The strand was immersed in strand water for 2 m, then air-cooled, and water attached to the strand surface was blown off with an air wiper.
Strand pelletizer inlet temperature: 140 ° C
[0055]
Pellet size (length): 3 mm target (separate pellets and long pellets with a sieve to produce cylindrical pellets with 99 wt% of 2.5 to 3.5 mm).
The pellets were molded by an injection molding machine (cylinder temperature setting of 240 to 300 ° C., mold temperature setting of 50 to 85 ° C.), and Izod (ASTM D258 1/4 inch wide molded piece with notch 23 ° C.), HDT (ASTM D648 18.6 kg load 1/4 inch wide molded piece), MFR (ASTM D1238 10 kg load 250 ° C.) was measured. The colorability was visually determined by press-molding a pellet of 160 mm × 160 mm × thickness 0.5 mm with a press molding machine at 250 ° C. and pellets.
[0057]
[Example 1]
76.5 parts by weight of the intermediate raw material a obtained in the first step, 11.5 parts by weight of H9302 of A & Mumi high cis rubber, and 2 parts by weight of titanium oxide are uniformly mixed and supplied from a gravimetric feeder. Made in a gravimetric flame retardant feeder and added in 12 parts by weight. The amount of extrusion was set to 500 kg / H. The colorability was also good and the physical properties were good.
[0058]
[Example 2]
The same procedure as in Example 1 was performed except that the intermediate raw material obtained in the first step was changed to b.
[0059]
Examples 3 to 5
The same procedure as in Example 1 was performed except that the intermediate raw material a or b obtained in the first step was used and blended at a composition ratio as shown in Table 3.
[0060]
[Table 1]

[0061]
[Table 2]

[0062]
[Table 3]

[0063]
【The invention's effect】
As described above, the method for producing a flame-retardant polyphenylene ether resin composition of the present invention is excellent in productivity, and the obtained resin composition has excellent physical properties and colorability .
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an explanatory diagram showing an outline of a method for producing a flame-retardant polyphenylene ether resin composition according to an example of the present invention.
[Explanation of symbols]
1. 1. Flexible container package of polyphenylene ether powder 2. Polyphenylene ether powder stock hopper 3. Shut-off valve 4. Weight type feeder for polyphenylene ether powder 5. Stock hopper for polystyrene resin Shut-off valve 7. 7. Weight type feeder for polystyrene resin 8. Gas vent piping First feed extruder first supply port hopper 10. 10. Biaxial co-rotating extruder for the first process Vacuum vent 12. Screen changer 13. Die part 14. Strand bath 15. Strand cutter 16. Sieve 17. Intermediate raw material transport container 20. Stock hopper for intermediate materials 21. Shut-off valve 22. Weight type feeder for intermediate raw materials 23. Polystyrene weight type feeder 24. Second process extruder first supply port hopper 25. 26. A biaxial co-rotating extruder for the second process Vacuum vent 27. Die part 28. Strand bus 29. Strand cutter 30. Sieve 31. Liquid flame retardant addition nozzle 32. Heavy liquid additive flame retardant feeder (gear pump)
33. Weight liquid additive flame retardant feeder (tank and load cell)

Claims (19)

70 to 99 parts by weight of polyphenylene ether powder, 1 to 30 parts by weight of polystyrene-based resin, and if necessary, a flame retardant is melt-kneaded using an extruder to produce intermediate raw material pellets of the following (a) and (c) Extruding 5 to 30 parts by weight of a flame retardant for the first step including the step and the arrangement of (b) and 10 to 90 parts by weight of the intermediate raw material pellets, 90 to 10 parts by weight of the polystyrene resin and 100 parts by weight of the resin part A method for producing a flame-retardant polyphenylene ether resin composition comprising a second step of melt-kneading using a machine.
(A) The polyphenylene ether powder is supplied in the order of a powder stock hopper, a powder weight feeder, and an extruder first supply port hopper from top to bottom.
(B) The polyphenylene ether powder supply pipe and the gas vent pipe are arranged in the order of the polyphenylene ether powder feed pipe and the gas vent pipe in the order from the gear box side to the die direction on the first supply port hopper. To do.
(C) The polyphenylene ether powder is passed through the powder supply pipe and supplied to the first supply port along the first supply port hopper wall surface with a wall surface angle of 60 to 85 degrees on the gear box side. Degas the contained gas from the vent pipe. The method for producing a flame-retardant polyphenylene ether resin composition according to claim 1, wherein in the first step, the polyphenylene ether resin in the flexible container is supplied to a stock hopper. The first step is characterized in that in the first step, the polyphenylene ether powder is supplied to a stock hopper together with an inert gas, and is supplied to the first supply port hopper via a powder weight feeder. Of producing a flame-retardant polyphenylene ether resin composition. The flame-retardant polyphenylene ether resin composition according to any one of claims 1 to 3, wherein in the first step, a polystyrene-based resin is supplied to the downstream side of the vent vent pipe of the first supply port hopper. Production method. The method for producing a flame-retardant polyphenylene ether resin composition according to any one of claims 1 to 4, wherein in the first step, a polystyrene-based resin is supplied to a lower portion of the first supply port hopper. The method for producing a flame-retardant polyphenylene ether resin composition according to any one of claims 1 to 5, wherein in the first step, the oxygen concentration in the first supply port hopper is less than 10 wt%. The process for producing a flame-retardant polyphenylene ether resin composition according to any one of claims 1 to 6, wherein in the first step, the screw diameter D of the extruder is 43 to 180 mm. In the extruder of a 1st process, it melt-kneads on the conditions of following (1)-(3), The manufacturing method of the flame-retardant polyphenylene ether resin composition in any one of Claims 1-7 characterized by the above-mentioned.

In the extruder in the first step, the powder conveying zone barrel temperature is set to 150 to 300 ° C, and the barrel setting temperature of the plasticizing zone is set to 250 to 300 ° C. The manufacturing method of the flame-retardant polyphenylene ether resin composition in any one. The flame-retardant polyphenylene ether according to any one of claims 1 to 9, wherein in the extruder of the first step, at least one vacuum vent is provided on the downstream side of the plasticizing zone, and the gas component is degassed under reduced pressure. A method for producing a resin composition. In the extruder of a 1st process, a screen changer is a plate type screen changer, The manufacturing method of the flame-retardant polyphenylene ether resin composition in any one of Claims 1-10 characterized by the above-mentioned. In the extruder in the first step, the effective filtration area of the plate is 1 to 50 mm per kg of extrusion amount. ² It sets to, The manufacturing method of the flame-retardant polyphenylene ether resin composition of Claim 11 characterized by the above-mentioned. In an extruder of the first step, the pellets of the cutting method is a strand cut method, a flame retardant polyphenylene according to any one of claims 1 to 12, characterized in that a one selected from hot cut system and an under water cut method A method for producing an ether resin composition. The method for producing a flame-retardant polyphenylene ether resin composition according to any one of claims 1 to 13, wherein the size of the intermediate raw material pellet is cut into a spherical or cylindrical shape of 1 to 6 mm. The method for producing a flame-retardant polyphenylene ether resin composition according to any one of claims 1 to 14, wherein the molecular weight distribution (Mw / Mn) of the polyphenylene ether is 2.3 to 3.5. The extruder in the second step is a single-screw extruder with a liquid addition device, wherein the extruder barrel temperature is set to 150 to 290 ° C and the screw rotation speed is set to 100 to 800 rpm, and melt kneading is performed. Item 16. A method for producing a flame-retardant polyphenylene ether resin composition according to any one of Items 1 to 15. The extruder in the second step is a biaxial co-rotating extruder with a liquid addition device, and is set at a barrel set temperature of 150 to 290 ° C. and a screw rotation speed of 200 to 1500 rpm, and melt kneaded. The manufacturing method of the flame-retardant polyphenylene ether resin composition in any one of Claims 1-15. In the extruder of a 2nd process, a flame retardant supply apparatus is a weight type liquid addition feeder, The manufacturing method of the flame-retardant polyphenylene ether resin composition in any one of Claims 1-17 characterized by the above-mentioned. In the extruder in the second step, 100 parts by weight of a resin composition obtained by feeding intermediate raw material pellets, polystyrene resin and, if necessary, additives to the first supply port, and melt-kneading with a twin screw extruder The method for producing a flame retardant polyphenylene ether resin composition according to claim 1, wherein 5 to 60 parts by weight of a fiber and / or a reinforcing material are side-feeded.

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