JP7170566B2 - Method for producing resin composition - Google Patents

Description

The present invention relates to a method for producing a resin composition.

In general, a resin composite material containing a powdery reinforcing agent is prepared by mixing the powdery reinforcing agent with the resin using an extruder, granulating the mixture, and then producing a product using a molding machine. An extruder for producing this composite material is charged with a resin from an upstream feed port, melted in a first kneading zone, charged with a powdery reinforcing agent from a side feeder, and the reinforcing agent is added in a second kneading zone. Mixed with molten resin.

Since the powdery reinforcing agent entraps gas and is supplied into the extruder, the conveying capacity is likely to be insufficient when supplying it from the side feeder into the extruder. Therefore, the supply amount may exceed the ability to convey the powdery reinforcing agent, and the powdery reinforcing agent may accumulate in the hopper of the side feeder, making it impossible to supply.

Patent Literature 1 discloses a technique for improving the carrying capacity by attaching a special kneading disk to the side feeder screw.

JP 2015-030132 A

When manufacturing using a powdery polyphenylene ether resin as the resin, the powdery polyphenylene ether resin supplied from the upstream supply port also entrains gas and enters the extruder, so the powder from the side feeder The conveying capacity when supplying the reinforcing agent is further reduced, and stable supply becomes more difficult.

In this case, even if a side feeder as disclosed in Patent Document 1 is used, the supply stability of the powdery reinforcing agent is not necessarily sufficient, and when the amount of powdery reinforcing agent supplied is large, stable Supply was sometimes difficult.

Therefore, an object of the present invention is to provide a method for producing a polyphenylene ether-based resin composition that can stably supply a powdery reinforcing agent even when the supply amount of the powdery reinforcing agent is large. .

As a result of intensive studies to solve the above problems, an extruder having an upstream supply port and a downstream supply port connected to a side feeder is used, and a specific amount of powdery polyphenylene ether resin is supplied from the upstream supply port. , a method for producing a polyphenylene ether-based resin composition in which a specific amount of powdery reinforcing agent is supplied from a downstream supply port, and the side feeder screw of the side feeder has a specific shape, thereby achieving the above object. and completed the present invention.

That is, the present invention is as follows.
[1]
A method for producing a resin composition using an extruder,
The extruder has an upstream feed port and a downstream feed port connecting a side feeder, the side feeder having a side feeder screw and a side feeder cylinder,
(a) supplying a first feedstock containing a powdery polyphenylene ether-based resin from the upstream supply port;
supplying a second feedstock containing (b) a powdery reinforcing agent from the downstream supply port;
The supply amount of the first feedstock is 30 to 60% by mass with respect to the total amount of the raw material (100% by mass), and the (a) powdery polyphenylene ether-based resin is added to 50% by mass in 100% by mass of the first feedstock. Contains ~90% by mass,
The supply amount of the powdery reinforcing agent (b) supplied from one downstream supply port is 15 to 35% by mass with respect to the total amount of raw materials (100% by mass), and the powdery reinforcing agent (b) is supplied. The bulk density of 0.8 g / mL or less,
A method for producing a resin composition, wherein the side feeder screw is single and biaxial.
[2]
The method for producing a resin composition according to [1], wherein the ratio (Do/Di) of the major axis Do to the minor axis Di of the side feeder screw is 1.8 to 2.2.
[3]
The method for producing a resin composition according to [1] or [2], wherein the ratio (Ls/Do) of the lead Ls of the side feeder screw to the major diameter Do of the screw is 1.0 to 2.0.
[4]
[1] to [3], wherein the ratio (σ/Do) of the gap distance σ between the side feeder cylinder and the side feeder screw to the major diameter Do of the side feeder screw is 0.005 to 0.05. A method for producing a resin composition according to any one of the above.
[5]
The method for producing a resin composition according to any one of [1] to [4], wherein the component (a) has a bulk density of 0.8 g/mL or less.
[6]
The method for producing a resin composition according to any one of [1] to [5], wherein the component (b) is at least one member selected from the group consisting of mica, talc and wollastonite.
[9]
The method for producing a resin composition according to any one of [1] to [6], wherein the first raw material further contains (c) a polystyrene resin.
[8]
The method for producing a resin composition according to any one of [1] to [7], wherein (d) the condensed phosphate ester is further added using a liquid addition pump.

According to the present invention, it is possible to provide a method for producing a polyphenylene ether-based resin composition capable of stably supplying a powdery reinforcing agent even when the supply amount of the powdery reinforcing agent is large.

It is the schematic which shows an example of the side feeder 1 thread twin screw of this embodiment installed in the side feeder cylinder. (A) is a front view of a side feeder single thread twin screw, and (B) is a side view of a side feeder single thread twin screw. It is the schematic which shows an example of the side feeder 2-start twin screw installed in the side feeder cylinder. (A) is a front view of a side feeder two-start twin screw, and (B) is a side view of the side feeder two-start twin screw.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. Moreover, the present invention can be modified and implemented as appropriate within the scope of the gist thereof.
In this specification, the upstream side and the downstream side refer to the upstream side and the downstream side of the raw material flow in the extruder or the side feeder of the present embodiment.

<Method for producing resin composition>
The method for producing a resin composition of the present embodiment is a method for producing a resin composition using an extruder, the extruder having an upstream supply port and a downstream supply port connecting a side feeder, The feeder has a side feeder screw and a side feeder cylinder, supplies (a) a first feedstock containing a powdery polyphenylene ether-based resin from the upstream supply port, and (b) powdery from the downstream supply port A second feedstock containing a reinforcing agent is supplied, and the amount of the first feedstock supplied is 30 to 60% by mass with respect to the total amount of the raw material (100% by mass), and the (a) contains 50 to 90% by mass of a powdery polyphenylene ether resin, and the supply amount of the (b) powdery reinforcing agent supplied from one downstream supply port is the total amount of raw materials (100% by mass) 15 to 35% by mass, the (b) powdery reinforcing agent has a bulk density of 0.8 g/mL or less, and the side feeder screw is single and biaxial. It is a method for producing a resin composition.

(extruder)
The extruder used in the method for producing the resin composition of the present embodiment has an upstream supply port and a downstream supply port to which a side feeder is connected. There may be two or more downstream supply ports to which side feeders are connected.
The type of extruder used in this embodiment is not particularly limited, but a twin-screw co-rotating twin-screw extruder is preferred. Examples of extruders include the "ZSK" series manufactured by COPERION, Germany, the "TEM" series manufactured by Toshiba Machine Co., Ltd., the "TEX" series manufactured by Japan Steel Works, Ltd., and the like.
The standard and size of the extruder are not particularly limited, but the barrel diameter is preferably 40 to 200 mm. When the barrel diameter is 40 mm or more, productivity is improved, and when the barrel diameter is 200 mm or less, excessive heat generation during melt-kneading can be prevented.
Although the length of the extruder is not particularly limited, it is preferably 30 to 60 times the barrel diameter. When the length of the extruder is 30 times or more the diameter of the barrel, it becomes easier to sufficiently knead the raw materials supplied from the side feeder, and the length of the extruder is 60 times or less than the diameter of the barrel. This is preferable because the deflection of the screw shaft can be reduced.

((upstream supply port))
The upstream feed port of the extruder of the present embodiment is preferably located in the most upstream barrel (No. 1 barrel) of the extruder.
In the method for producing a resin composition of the present embodiment, (a) a first feedstock containing a powdery polyphenylene ether-based resin is supplied from an upstream supply port.

((downstream supply port))
The downstream supply port of the extruder of this embodiment is located downstream of the upstream supply port and is connected to a side feeder. The extruder of this embodiment may have a plurality of downstream supply ports.
In the method for producing a resin composition of the present embodiment, the second feedstock containing (b) the powdery reinforcing agent is supplied from the downstream supply port.
The position of the downstream supply port of the extruder of the present embodiment is preferably such that the ratio (L/D) of the length L to the downstream supply port and the barrel diameter D is 12 to 40, and 16 to 36. more preferred.

－Side Feeder－
The side feeder connected to the extruder of the present embodiment can be used as a resin composition manufacturing apparatus or the like by connecting to the lateral side or upper portion of the barrel of the extruder. The side feeders are connected to a side feeder barrel separate from the barrel with the upstream feed port, and there may be more than one.
In the method for producing a resin composition of the present embodiment, the second feedstock containing (b) the powdery reinforcing agent is supplied from the side feeder.
(b) When two or more types of powdery reinforcing agents are used, the extruder of the present embodiment may have two or more side feeders. Moreover, even if the (b) powdery reinforcing agent is of one kind, the (b) powdery reinforcing agent may be dividedly supplied from two or more side feeders.

The side feeder of this embodiment has a side feeder screw and a side feeder cylinder.

--Side feeder screw--
The side feeder screw of the side feeder of this embodiment is a single screw with one flight (major diameter portion) and has two shafts. If the screw has a single shaft, the carrying capacity will be low, and if it has three or more shafts, the mechanical structure will be complicated, which is not preferable. A single-start twin-screw is preferable from the viewpoint of transportability and structure.
FIG. 1 shows a schematic front view (A) and a schematic side view (B) of an example of the side feeder screw 1 of this embodiment.

The side feeder screw preferably has a ratio of major axis Do to minor axis Di (Do/Di) of 1.8 to 2.2, more preferably 1.86 to 2.2, and still more preferably 1.86. ~2.1. If Do/Di is less than 1.8, the conveying ability will be low. Moreover, when Do/Di exceeds 2.2, the minor diameter Di becomes small and the strength of the screw shaft decreases.

In addition, the side feeder screw preferably has a ratio (Ls/Do) of the lead Ls to the major diameter Do of 1.0 to 2.0, more preferably 1.0 to 1.7, still more preferably 1.0 to 1.0. 1 to 1.7. When Ls/Do is 1.0 or more, the conveying capacity can be further increased, and when it is 2.0 or less, the mechanical strength of the screw can be kept high.

The rotation speed of the side feeder screw is preferably 100-450 rpm, more preferably 150-400 rpm. When the screw rotation speed is within the above range, the raw material can be stably supplied into the extruder.

Here, FIG. 2 shows a schematic front view (A) and a schematic side view (B) of an example of a side feeder screw with two threads and two shafts. There are two flights (major diameter portions) in one lead, which are smaller than a single side feeder screw.

--Side feeder cylinder--
The side feeder cylinder of this embodiment has a biaxial shape according to the shape of the side feeder screw.
Moreover, the diameter Ds of the side feeder cylinder is equal to or less than the barrel diameter of the extruder to be connected.

The ratio of the gap distance σ between the side feeder cylinder and the side feeder screw to the major diameter Do of the side feeder screw (σ/Do) is preferably 0.005 to 0.05, more preferably 0.007 to 0.007. 0.05, more preferably 0.008 to 0.05. When σ/Do is 0.005 or more, the blade width of the single-thread screw is too wide, and (b) the powdery reinforcing agent clogs the gap, causing the screw to stop or the single-thread screw to fail. Wear of the flight portion can be suitably prevented. Further, when σ/Do is 0.05 or less, the amount of the powdery reinforcing agent (b) that passes through the gap can be reduced, and the conveying capacity can be further increased.
In the present disclosure, the gap distance σ between the side feeder cylinder and the side feeder screw is calculated by the following formula (1).
σ=(Ds−Do)/2 (1)

The side feeder of this embodiment can be connected with a hopper, a cylinder cooling device, etc., as required.

When a liquid raw material is supplied to the extruder, it can be kneaded by feeding the liquid raw material directly into the barrel of the extruder using a liquid addition pump or the like. The liquid-added pump is not particularly limited, and examples thereof include gear pumps and flange-type pumps. Among these, gear pumps are preferred. In addition, a heater is used to heat the tank that stores the liquid raw material used for the liquid addition pump, the pipe between the tank and the pump, and the pipe between the pump and the extruder cylinder, which is the flow path for the liquid raw material. is more preferable. Since this can reduce the viscosity of the liquid raw material, the load on the liquid addition pump can be reduced, which is preferable from the viewpoint of operability and the like.

In this embodiment, the configuration of the extruder is not particularly limited, but for example, an upstream supply port on the upstream side, a first kneading zone downstream from the upstream supply port, and a downstream supply from the first kneading zone A port is provided (if necessary, a second downstream supply port may be provided downstream of the downstream supply port), a second kneading zone downstream of the downstream supply port, and a second kneading zone downstream of the second kneading zone a liquid addition pump, a third kneading zone downstream of the liquid addition pump, and a vacuum vent downstream of the third kneading zone.

(Manufacture of resin composition)
In the method for producing the resin composition of the present embodiment, the above-described extruder is used to supply (a) the first feedstock containing the powdery polyphenylene ether-based resin from the upstream supply port, and the side feeder is connected to the downstream including feeding through the feed port a second feedstock comprising (b) a pulverulent strengthening agent.
In addition, in the method for producing the resin composition of the present embodiment, (d) the condensed phosphate may be further added using a liquid addition pump.

In the method for producing the resin composition of the present embodiment, the extrusion temperature is not particularly limited, and may be 100 to 370° C., and the screw rotation speed is not particularly limited, and may be 100 to 1,200 rpm.

((first feedstock))
In the method for producing a resin composition of the present embodiment, the first feedstock supplied from the upstream feed port contains (a) powdery polyphenylene ether-based resin. The first feedstock may also contain (c) a polystyrene-based resin.

The supply amount of the first feedstock is 30 to 60% by mass with respect to the total amount of the raw material (100% by mass). (b) The supply amount is preferably 60% by mass or less from the viewpoint of facilitating the supply of the second feedstock without excessively increasing the filling rate in the extruder before adding the powdery reinforcing agent. Moreover, from the viewpoint of not excessively lowering the filling rate in the extruder before adding the component (b), it is preferable that the supply amount is 30% by mass or more. The amount supplied is more preferably 35 to 55% by mass, more preferably 40 to 55% by mass.

-(a) powdery polyphenylene ether resin-
(a) powdery polyphenylene ether-based resin (in this specification, sometimes referred to as "PPE" or simply referred to as "(a) component") is a phenylene ether homopolymer (homopolymer) or a copolymer of phenylene ether and other monomers.
The component (a) may be used alone or in combination of two or more.

［式中、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～７の第１級のアルキル基、又は炭素数１～７の第２級のアルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及び少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群より選ばれる一価の基を表す。］ Examples of the component (a) include homopolymers and/or copolymers having a repeating unit structure (a unit structure derived from phenylene ether) represented by the following formula (1).

[In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, or a selected from the group consisting of secondary alkyl groups, phenyl groups, haloalkyl groups, aminoalkyl groups, hydrocarbonoxy groups, and halohydrocarbonoxy groups in which at least two carbon atoms separate the halogen and oxygen atoms; represents a monovalent group. ]

Examples of the component (a) include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl- 6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether) and other homopolymers; 2,6-dimethylphenol and other phenols (e.g., 2,3 , 6-trimethylphenol and 2-methyl-6-butylphenol). Among them, poly(2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1,4-phenylene ether) ) is more preferred.

A conventionally known method can be applied to the method for producing the component (a). As a method for producing the component (a), for example, a method of producing by oxidative polymerization of 2,6-xylenol or the like using a complex of a cuprous salt and an amine as a catalyst, disclosed in JP-A-50-150798. JP-A-50-051197, JP-A-63-152628, and the like.

The reduced viscosity of the component (a) (0.5 g/dL chloroform solution, measured at 30° C., measured with an Ubbelohde viscosity tube) is preferably 0.7 dL/g or less from the viewpoint of fluidity. It is more preferably 0.6 dL/g or less, more preferably 0.2 dL/g or more, more preferably 0.3 dL/g or more from the viewpoint of mechanical properties.

In addition, the above component (a) contains all or part of the structural units constituting the polyphenylene ether, an acyl functional group, a carboxyl group, an acid anhydride group, an acid amide group, an imide group, an amine group, an orthoester group, a hydroxy and a group derived from an ammonium carboxylate, by reacting (modifying) with a functionalizing agent containing one or more functional groups selected from the group consisting of a group derived from ammonium carboxylate, thereby replacing it with a functionalized polyphenylene ether. may

In the present embodiment, the shape of the component (a) that provides the effects of the present invention is powder.
The component (a) preferably has a bulk density of 0.8 g/mL or less, more preferably 0.7 g/mL or less, and even more preferably 0.6 g/mL or less. When the bulk density of the component (a) is 0.8 g / mL or less, the amount of gas entrapped when the component (a) is supplied into the extruder increases, and the powder (b) supplied from the side feeder The transportability of the body-strengthening agent is further reduced, and the effects of the present invention are exhibited more remarkably.
The bulk density of the component (a) can be measured by a powder property evaluation device (Powder Tester PT-X, manufactured by Hosokawa Micron Corporation).

The content of component (a) in 100% by mass of the first feedstock is 50 to 90% by mass. If the content is more than 90% by mass, the amount of entrained gas increases when the first feedstock is fed into the extruder. Therefore, the second raw material supplied from the side feeder becomes difficult to enter into the extruder, and the conveying capacity is lowered, so stable supply cannot be performed. Further, when the content is less than 50% by mass, the amount of gas entrapped when the component (a) is supplied into the extruder is small, and the second feedstock supplied from the side feeder is difficult to enter into the extruder. Therefore, the effect of the present invention is hardly exhibited. The content is more preferably 55 to 90% by mass, still more preferably 55 to 85% by mass.

-(c) polystyrene resin-
The first feedstock of the present embodiment contains (c) a polystyrene resin (in this specification, sometimes simply referred to as "(c) component") from the viewpoint of lowering the melt viscosity of the resin in the extruder. You may
The (c) polystyrene-based resin of the present embodiment is a polymer obtained by polymerizing a styrene-based compound or a compound copolymerizable with a styrene-based compound in the presence or absence of a rubbery polymer.

（式中、Ｒは水素、低級アルキル基又はハロゲンを示し、Ｚはビニル基、水素、ハロゲン及び低級アルキル基よりなる群から選択され、ｐは０～５の整数である。） (c) The styrene-based compound constituting the polystyrene-based resin means a compound represented by the following formula (2).

(Wherein, R represents hydrogen, a lower alkyl group or a halogen, Z is selected from the group consisting of a vinyl group, hydrogen, a halogen and a lower alkyl group, and p is an integer of 0 to 5.)

Specific examples of styrene compounds include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like.

Examples of compounds that can be copolymerized with styrene compounds include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; acid anhydrides such as maleic anhydride; and used with styrenic compounds.

Examples of rubbery polymers include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds or hydrogenated products thereof, ethylene-propylene copolymer rubbers, and the like.

(c) Polystyrene resins include polystyrene, rubber-reinforced polystyrene (high-impact polystyrene (HIPS)), styrene-acrylonitrile copolymer (AS resin), rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), and other styrenes. system copolymers, and the like.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of component (c) in 100% by mass of the first feedstock is 5 to 50% by mass from the viewpoint of lowering the melt viscosity of the first feedstock and stabilizing the supply of component (b) into the extruder. preferably 10 to 45% by mass, even more preferably 15 to 40% by mass.

In addition to components (a) and (c), the first feedstock of the present embodiment includes plasticizers, antioxidants, stabilizers such as ultraviolet absorbers, antistatic agents, release agents, dyes and pigments, and the like. additives, and resins other than components (a) and (c).
The content of the other components in 100% by mass of the first feedstock is preferably 3% by mass or less.

((second feedstock))
In the method for producing a resin composition of the present embodiment, the second raw material supplied from the downstream supply port connected to the side feeder contains (b) a powdery reinforcing agent.

The supply amount of the second feedstock is preferably 15 to 60% by mass, preferably 15 to 55% by mass, based on the total amount of the raw material (100% by mass) from the viewpoint of stabilizing the supply into the extruder. More preferably, 20 to 50% by mass is even more preferable.

-(b) powdery reinforcing agent-
(b) The powdery reinforcing agent (in this specification, sometimes referred to simply as "(b) component") includes, for example, ground calcium carbonate, colloidal calcium carbonate, soft calcium carbonate, silica, kaolin, Clay, barium sulfate, zinc oxide, alumina, magnesium hydroxide, talc, chlorite, mica, milled fiber, hydrotalcite, needle filler (wollastonite, potassium titanate, basic magnesium sulfate, cerite, xonotlite, boron acid aluminum), glass beads, silica beads, alumina beads, carbon beads, glass balloons, carbon, magnetic fillers, piezoelectric/pyroelectric fillers, slidable fillers, sealing fillers, ultraviolet absorbing fillers, damping fillers, Conductive fillers (ketjen black, acetylene black) can be mentioned. These may be used individually by 1 type, and may use 2 or more types together.

The bulk density of the component (b) is 0.8 g/mL or less, preferably 0.7 g/mL or less, more preferably 0.5 g/mL or less. If the bulk density of the component (b) is 0.8 g/mL or less, the conveying ability when supplied from the side feeder is lowered, and the effects of the present invention are exhibited.
The bulk density of the component (b) can be measured with a powder property evaluation device (Powder Tester PT-X, manufactured by Hosokawa Micron Corporation).

The amount of component (b) supplied from one downstream supply port is 15 to 35% by mass, preferably 15 to 30% by mass, relative to the total amount of raw material (100% by mass), and 15 to 25% by mass. % by mass is more preferred.
If the supply amount of the powdery reinforcing agent (b) supplied from one downstream supply port is 35% by mass or more with respect to the total amount of raw materials, the amount of entraining gas when the component (b) is supplied into the extruder increases, the component (b) becomes difficult to enter the extruder, and the conveying capacity is lowered, so that stable supply becomes impossible. Conversely, if the supply amount of the powdery reinforcing agent (b) supplied from one downstream supply port is less than 15% by mass with respect to the total amount of raw materials, the gas is generated when the component (b) is supplied into the extruder. Since the amount of entrapment is small and the problem of difficulty in entering the component (b) into the extruder is unlikely to occur, the effects of the present invention are difficult to achieve.
The total supply amount of component (b) is 15 to 50% by mass, preferably 15 to 45% by mass, more preferably 15 to 40% by mass, relative to the total amount of raw materials (100% by mass). preferable.

In addition to the component (b), the second feedstock of the present embodiment includes stabilizers such as plasticizers, antioxidants, and ultraviolet absorbers, additives such as antistatic agents, release agents, and dyes and pigments. It may contain other resins, glass fibers, glass flakes, and other reinforcing agents other than the component (b).
The content of the other components in 100% by mass of the second feedstock is preferably 55% by mass or less.

In the method for producing the resin composition of the present embodiment, (d) the condensed phosphate may be further added using a liquid addition pump.

-(d) condensed phosphate ester-
The raw material of the present embodiment is (d) a condensed phosphate ester flame retardant (in this specification, it may be simply referred to as "(d) component" for the purpose of imparting flame retardancy to the resulting resin composition. .) may be contained.

式（３）、（４）中、Ｑ¹、Ｑ²、Ｑ³、及びＱ⁴は、各々独立して、炭素数１～６のアルキル基を表し、Ｒ⁵及びＲ⁶は、メチル基を表し、Ｒ⁷、及びＲ⁸は、各々独立して、水素原子又はメチル基を表す。
ｎは、０以上の整数であり、ｎ¹、及びｎ²は、各々独立して０～２の整数であり、ｍ¹、ｍ²、ｍ³、及びｍ⁴は、各々独立して、０～３の整数である。
なお、式（３）及び（４）のｎは、０以上の整数であり、好ましくは１～３の整数である。 Component (d) contains, as a main component, at least one selected from the group consisting of condensed phosphate esters represented by the following formulas (3) and (4), among condensed phosphate ester-based flame retardants. things are preferred.
The "main component" as used herein means that the component is contained in component (d) in an amount of 90% by mass or more, preferably 95% by mass or more, and more preferably 100% by mass.

In formulas (3) and (4), Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ each represent a methyl group. and R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.
n is an integer of 0 or more, n ¹ and n ² are each independently an integer of 0 to 2, m ¹ , m ² , m ³ and m ⁴ are each independently 0 Integer from ~3.
In formulas (3) and (4), n is an integer of 0 or more, preferably an integer of 1-3.

Among them, R ⁷ and R ⁸ in formula (3) represent a methyl group, and m ¹ , m ² , m ³ , m ⁴ , n ¹ , and n ² are 0; Q ¹ , Q ² , Q ³ , Q ⁴ , R ⁷ and R ⁸ in (3) represent a methyl group, n ¹ and n ² are 0, m ¹ , m ² , m ³ and m Condensed phosphoric acid esters in which ⁴ is an integer of 1 to 3, wherein n is an integer of 1 to 3, particularly phosphoric acid esters in which n is 1, in a total amount of 50% by mass or more. preferable.
By using these condensed phosphates, the volatility of the resin composition during molding can be further reduced.

The amount of component (d) supplied is preferably 2 to 25% by mass with respect to the total amount of raw materials (100% by mass) from the viewpoint of reducing the melt viscosity in the extruder and suppressing the torque increase of the main screw of the extruder. It is more preferably 3 to 20% by mass, even more preferably 5 to 15% by mass.

―Other raw materials―
In order to further impart other properties to the resin composition obtained, the raw material of the present embodiment includes, for example, a plasticizer, an antioxidant, a stabilizer such as an ultraviolet absorber, an antistatic agent, a mold release agent, and a dye or pigment. , and other additives such as resins other than those mentioned above can be further added.
The additives described above may be included in the first feedstock and/or the second feedstock, as described above, or may You may supply from a supply port.

Further, in order to further improve the mechanical properties, a reinforcing agent other than the component (b) can be used in combination, and examples thereof include glass fibers and glass flakes.
The reinforcing agent other than the above component (b) may be contained in the second feedstock as described above, or may can be supplied from

The amount of other raw materials supplied may be 30% by mass or less with respect to the total amount of raw materials (100% by mass).

<Resin composition>
The resin composition of the present embodiment is produced by the method for producing a resin composition of the present embodiment, and is produced by melt-kneading raw materials of the resin composition using the extruder described above.
The resin composition produced by the method for producing a resin composition of the present embodiment contains (a) a powdery polyphenylene ether resin and (b) a powdery reinforcing agent, and if necessary, (c) Polystyrene resin, (d) condensed phosphate, and other raw materials may be included.

EXAMPLES The present invention will be described in more detail below with reference to Examples, Comparative Examples, and Reference Examples, but the present invention is not limited to these Examples.

Raw materials used in Examples, Comparative Examples, and Reference Examples are shown below.
―Raw materials used―
(a) powdery polyphenylene ether resin (PPE)
Product name “S201A”, manufactured by Asahi Kasei Corporation, bulk density: 0.6 g / mL
(b) Powdery Strengthening Agent (b-1) Mica Product name “BHT Mica 200D”, manufactured by Beijing Huxin Trading Co., Ltd., bulk density: 0.2 g / mL
(b-2) Talc Product name “Crown Talc PK-MMB” manufactured by Matsumura Sangyo Co., Ltd., bulk density: 0.6 g / mL
(c) polystyrene resin (PS)
Product name “685”, (d) condensed phosphate ester manufactured by PS Japan Co., Ltd. Product name “E890”, manufactured by Daihachi Chemical Industry Co., Ltd. (other raw materials)
・PPE/PS Masterbatch (MB)
Masterbatch pellets and stabilizers obtained by melt-kneading 60 parts by mass of S201A (manufactured by Asahi Kasei Corporation) and 40 parts by mass of 685 (manufactured by PS Japan Co., Ltd.) Trade name "PEP36", trade name "Irganox 1010" manufactured by ADEKA Co., Ltd. , BASF Co., Ltd. Glass flake Product name “Microglass-Fleca REFG-315” Nippon Sheet Glass Glass fiber Product name “ECS03T-249” Nippon Electric Glass Co., Ltd.

Methods for evaluating the production of resin compositions in Examples, Comparative Examples, and Reference Examples are shown below.
-Evaluation method-
During the production of the resin composition, it was confirmed whether the component (b) could be supplied. The case where component (b) could be supplied from the side feeder without any problem was evaluated as ◯, and the case where component (b) was accumulated in the hopper of the side feeder and could not be supplied was evaluated as x.

[Examples 1 to 8, Comparative Examples 1 to 4, Reference Examples 1 and 2]
A twin-screw extruder (trade name “TEM58SS”, manufactured by Toshiba Machine Co., Ltd.) was used as an extruder used for producing the resin composition of each example. The number of barrels of the twin-screw extruder is 12 blocks, and regarding the flow direction of the raw material, the upstream supply port is at the first barrel from the upstream, the downstream supply port is at the sixth barrel, the downstream supply port is at the ninth barrel, and the downstream supply port is at the ninth barrel. A liquid addition pump was provided at the eye and a vacuum vent was provided at the eleventh barrel. In addition, the material was supplied to the downstream supply port 1 and the downstream supply port 2 by using side feeders, and the screw rotation speed of each side feeder was 300 rpm.
The side feeder screws used are shown in Table 1. Both screws are biaxial.
To the twin-screw extruder set as above, each raw material was supplied from each supply port and liquid addition pump as shown in Table 2, and the extrusion temperature was 220 to 320 ° C., the screw rotation speed was 500 rpm, and the discharge rate was 500 kg / hour. The mixture was melt-kneaded under the conditions to produce a resin composition.
Table 2 shows the results of evaluating each example by the above evaluation method.

Examples 1 to 8 were excellent in supplying performance of the powdery reinforcing agent, and it was shown that the production method of the resin composition according to the present embodiment was excellent in supplying performance of the powdery reinforcing agent.

INDUSTRIAL APPLICABILITY According to the present invention, the present invention has industrial applicability as a technology for manufacturing resin compositions used for home appliances, OA equipment, automobile parts, electrical parts, optical parts, battery cases, battery cells, and the like.

Claims (8)

A method for producing a resin composition using an extruder,
The extruder has an upstream feed port and a downstream feed port connecting a side feeder, the side feeder having a side feeder screw and a side feeder cylinder,
(a) supplying a first feedstock containing a powdery polyphenylene ether-based resin from the upstream supply port;
supplying a second feedstock containing (b) a powdery reinforcing agent from the downstream supply port;
The supply amount of the first feedstock is 30 to 60% by mass with respect to the total amount of the raw material (100% by mass), and the (a) powdery polyphenylene ether-based resin is added to 50% by mass in 100% by mass of the first feedstock. Contains ~90% by mass,
The supply amount of the powdery reinforcing agent (b) supplied from one downstream supply port is 15 to 35% by mass with respect to the total amount of raw materials (100% by mass), and the powdery reinforcing agent (b) is supplied. The bulk density of 0.8 g / mL or less,
A method for producing a resin composition, wherein the side feeder screw is single and biaxial. 2. The method for producing a resin composition according to claim 1, wherein the ratio (Do/Di) of the major axis Do of the side feeder screw to the minor axis Di is 1.8 to 2.2. 3. The method for producing a resin composition according to claim 1, wherein the ratio (Ls/Do) of the lead Ls of the side feeder screw to the major diameter Do of the screw is 1.0 to 2.0. The ratio (σ/Do) of the gap distance σ between the side feeder cylinder and the side feeder screw to the major diameter Do of the side feeder screw is 0.005 to 0.05. A method for producing the resin composition according to item 1. The method for producing a resin composition according to any one of claims 1 to 4, wherein the component (a) has a bulk density of 0.8 g/mL or less. The method for producing a resin composition according to any one of claims 1 to 5, wherein the component (b) is at least one member selected from the group consisting of mica, talc and wollastonite. The method for producing a resin composition according to any one of claims 1 to 6, wherein the first feedstock further contains (c) a polystyrene resin. The method for producing a resin composition according to any one of claims 1 to 7, wherein (d) the condensed phosphate ester is further added using a liquid addition pump.

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