JP2016043654A - Method of manufacturing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which suppresses decomposition of a thermoplastic resin and has satisfactory thermal stability, in a method of manufacturing the resin composition by kneading the thermoplastic resin and a vinyl polymer.SOLUTION: A method of manufacturing a resin composition uses an extruder. In a cylinder 6 of the extruder, a raw material supply port 1, a vent port 2, a side feed port 3 for supplying a vinyl polymer (B) obtained by an emulsion polymerization method or a suspension polymerization, and a discharge port 5 are provided separately from one another in this order respectively in a cylinder axis direction. In the extruder, a screw element having kneading capability is included in a cylinder inner region between a downstream side end of the raw material supply port 1 and an upstream side end of the vent port 2, a screw element having a resin-damming operation is included in a cylinder inner region between a downstream side end of the vent port 2 and an upstream side end of the side feed port 3, and a screw element having kneading capability is included in a cylinder inner region between a downstream side end of the side feed port 3 and an upstream side end of the discharge port 5. In the method of manufacturing the resin composition, a vinyl polymer (B) is subjected to side feed and melted and kneaded after a thermoplastic resin is melted.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a resin composition by kneading a thermoplastic resin and a vinyl polymer with an extruder.

  In recent years, the performance and quality required for thermoplastic resins have only increased, and it is often required to satisfy different properties and functions simultaneously. In addition, these requirements vary greatly depending on the industrial field and type of industry, and it is very difficult to use a thermoplastic resin alone in order to respond to each.

  As a solution to this problem, a technique of kneading other resins and additives into a thermoplastic resin is often used. In particular, a resin composition having characteristic performance is produced by a kneading method using an extruder. On the other hand, the thermoplastic resin and additives used as the matrix are often different in various physical property values, and when mixing those with large viscosity differences or those that are susceptible to thermal decomposition, in order to eliminate the viscosity difference and suppress thermal decomposition A method of obtaining a resin composition by side-feeding additives and other resins is known (Patent Document 1).

  Patent Documents 2 and 3 describe methods for obtaining a thermoplastic resin composition by melt-kneading a thermoplastic resin and a reinforcing material such as reinforcing fibers and / or granular fillers.

JP 2002-144400 A JP 2008-238626 A JP 59-143608 A

  However, even after the matrix resin is melted, even if other resins and additives are side-feeded and kneaded, the desired function of the resin composition may not be exhibited.

  As a result of intensive studies, the inventors have side-feeded additives and other resins when the outgas such as water generated when the matrix resin melts is not discharged out of the extruder system. When mixing and kneading, the matrix resin or the side-feed resin is decomposed due to the influence of outgas such as water and the metal salt contained in the side-feed resin. It was found that the function of In particular, it has been found that the thermoplastic resin may be decomposed to impair the residence heat stability.

  An object of the present invention is to provide a method for producing a resin composition with good residence heat stability by suppressing the decomposition of the thermoplastic resin in a method for producing a resin composition by kneading a thermoplastic resin and a vinyl polymer. There is to do.

According to the present invention,
A method for producing a resin composition, wherein an extruder is used to knead a thermoplastic resin (A) and a vinyl polymer (B) to produce a resin composition,
The vinyl polymer (B) is a polymer obtained by an emulsion polymerization method or a suspension polymerization method,
To the cylinder of the extruder,
A raw material supply port which is an opening for supplying the thermoplastic resin (A);
A vent opening which is a vent opening;
A side feed port which is an opening for supplying the vinyl polymer (B);
An outlet that is an opening for discharging the resin composition,
Are provided in this order in the cylinder axial direction and spaced apart from each other,
In the cylinder inner region located between the downstream end of the raw material supply port and the upstream end of the vent port in the cylinder axial direction, a screw element having kneading ability is included,
In the cylinder axial direction, a screw element having an action of clogging resin is included in the cylinder inner region located between the downstream end of the vent port and the upstream end of the side feed port,
In the cylinder axial direction, an extruder including a screw element having kneading ability is used in a cylinder inner region located between the downstream end of the side feed port and the upstream end of the discharge port. The flow direction of the thermoplastic resin (A),
Provided is a method for producing a resin composition in which after the thermoplastic resin (A) is melted, the vinyl polymer (B) is side-feeded and melt-kneaded.

  The above method is particularly effective when the vinyl polymer (B) contains at least one metal component selected from the group consisting of Na, K, Ca, Mg and Fe in a total concentration of 5 ppm or more.

  The above method is particularly effective when the thermoplastic resin (A) is a resin having a load deflection temperature at 1.80 MPa of 120 ° C. or higher and obtained by condensation polymerization.

The vinyl polymer (B) has the following formula 2.0> (MFR [g / 10 min] at 180 ° C. of the vinyl polymer (B)) / (MFR [g / 10 min] at 320 ° C. of the thermoplastic resin (A)). )> 0.15
The above method is particularly effective when the polymer satisfies the above.

  The above method is particularly effective when the vinyl polymer (B) is a polymer containing 10% by mass to 95% by mass of a (meth) acrylic acid ester monomer unit.

  According to the present invention, in a method for producing a resin composition by kneading a thermoplastic resin and a vinyl polymer, it is possible to suppress the decomposition of the thermoplastic resin and obtain a resin composition with good residence heat stability. It becomes.

It is a schematic diagram of the extruder used in the Example.

  Hereinafter, the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

  The present invention relates to a production method for producing a resin composition by kneading a thermoplastic resin (A) and a vinyl polymer (B) using an extruder.

  The vinyl polymer (B) is a polymer obtained by an emulsion polymerization method or a suspension polymerization method, particularly an emulsion polymerization method using a metal salt such as an emulsifier in the polymerization process, or a metal salt as a dispersion aid in the polymerization process. It is a polymer obtained by the suspension polymerization method used. The present invention is extremely useful when such a polymer is used as the vinyl polymer (B).

  In the present invention, kneading is performed using an extruder having the following configuration.

  As shown in FIG. 1, a raw material supply port 1 and a vent port 2 (hereinafter referred to as a “first vent port” in order to distinguish from a second vent port 4 to be described later) are provided in a cylinder of the extruder. The side feed port 3 and the discharge port 5 are provided in this order from the upstream side to the downstream side in the cylinder axial direction and spaced apart from each other. In addition, the upstream and downstream are about the flow direction of the thermoplastic resin (A) used as a raw material. A second vent port 4 may be provided between the side feed port and the discharge port so as to be separated from these.

Here, the raw material supply port 1 is an opening for supplying the thermoplastic resin (A),
The first vent port 2 is a vent opening (first vent opening),
The side feed port 3 is an opening for supplying the vinyl polymer (B),
The second vent port 4 is a vent opening (second vent opening),
The discharge port 5 is an opening for discharging the resin composition.

  In a cylinder inner region 12 (sometimes referred to as a “first kneading section” in the present specification) located between the downstream end of the raw material supply port 1 and the upstream end of the first vent port 2 in the cylinder axial direction. , Screw elements having kneading ability are included. The first kneading part 12 is a part existing between the downstream end of the raw material supply port and the upstream end of the first vent port in the cylinder axial direction in the cylinder inner region.

  In a cylinder inner region 14 (sometimes referred to as a “resin blocking portion” in this specification) located between the downstream end of the first vent port 2 and the upstream end of the side feed port 3 in the cylinder axial direction, A screw element having a function of clogging the resin is included. The resin damming portion 14 is a portion existing between the downstream end of the first vent port and the upstream end of the side feed port in the cylinder axial direction in the cylinder inner region.

  Kneading in a cylinder inner region 16 (sometimes referred to as “second kneading section” in this specification) located between the downstream end of the side feed port 3 and the upstream end of the discharge port 5 in the cylinder axial direction. A screw element with the capability is included. The second kneading portion is a portion existing between the downstream end of the side feed port and the upstream end of the discharge port in the cylinder inner region.

  The raw material supply port, the first vent port, the side feed port, the second vent port, and the discharge port may each consist of a single opening or a plurality of openings. For example, when the raw material supply port has a single opening, “the downstream end of the raw material supply port” means the downstream end of the single opening. When the raw material supply port is composed of a plurality of openings, the “downstream end of the raw material supply port” means the end on the most downstream side with respect to the plurality of openings. Further, when the first vent port is composed of a single opening, “the upstream end of the first vent port” means the upstream end of the single opening. When the first vent port is composed of a plurality of openings, the “upstream end of the first vent port” means the end on the most upstream side with respect to the plurality of openings. That is, when one of the raw material supply port, the first vent port, the side feed port, the second vent port, and the discharge port has a plurality of openings, each of the upstream end or the downstream end has a plurality of the plurality of openings. It means the most upstream or downstream end of the opening.

  A screw element having kneading ability refers to a screw capable of kneading a material by a shearing action. Examples of screw elements having kneading ability include forward kneading discs, forward mixing screws, forward rotor screws, reverse kneading discs, neutral kneading discs, reverse mixing screws or reverse Directional rotor screw.

  The screw element having a function of clogging resin refers to a screw that can fill the resin inside the upstream extruder by the clogging action of the material. Examples of the screw element having a capping action include a seal ring, a reverse full flight screw, a reverse kneading disk, a neutral kneading disk, a reverse mixing screw, or a reverse rotor screw.

  In addition, the screw element which has a kneading | mixing capability and the effect | action which dampens resin refers to the screw element which has a kneading | mixing capability and has the effect | action which dampens resin. Examples of the screw element having the kneading ability and the function of clogging the resin include a reverse kneading disk, a neutral kneading disk, a reverse mixing screw, and a reverse rotor screw.

  In the present invention, the above-described configuration is arranged in an extruder, and after melting the thermoplastic resin (A), the vinyl polymer (B) is side-feeded and melt-kneaded.

  Most or all of the thermoplastic resin (A) supplied from the raw material supply port can be melted in the first kneading section.

  According to the present invention, since the outgas such as water generated when the thermoplastic resin (A) is melted can be efficiently discharged out of the extruder, a trace amount of emulsifier and metal salt contained in the vinyl polymer (B) It is possible to suppress the decomposition of the thermoplastic resin (A) due to the action of the polymer, and it is possible to suppress the decomposition of the polymer (B) due to the influence of outgas such as water generated when the thermoplastic resin (A) melts. Therefore, a resin composition with good residence heat stability can be obtained.

  This production method is particularly useful when the vinyl polymer (B) contains at least one metal component selected from the group consisting of Na, K, Ca, Mg, and Fe in a total concentration of 5 ppm (mass basis) or more.

  This production method is particularly effective when the thermoplastic resin (A) has a load deflection temperature at 1.80 MPa (hereinafter sometimes referred to as HDT) of 120 ° C. or higher and is obtained by condensation polymerization. Have. The load deflection temperature (HDT) at 1.80 MPa here is a temperature measured by the ASTM D648 method.

Moreover, this production method has a particularly great effect when the vinyl polymer (B) is a polymer satisfying the following formula:
2.0> (MFR [g / 10 min] of vinyl polymer (B) at 180 ° C.) / (MFR [g / 10 min] of 320 ° C. of thermoplastic resin (A))> 0.15,
Here, MFR is a melt flow index.

  In addition, this production method has a particularly large effect when the polymer (B) is a polymer containing 10% by mass to 95% by mass of a (meth) acrylic acid ester monomer unit.

<Thermoplastic resin (A)>
The thermoplastic resin (A) that can be used in the present invention is not particularly limited, and examples thereof include polypropylene, polystyrene, polyvinyl chloride, ABS, acrylic resin, polycarbonate, polyarylate, polybutylene terephthalate, and the like. May be used alone, or two or more may be used in combination.

  When the softening temperature of the thermoplastic resin (A), that is, the HDT at 1.80 MPa is high, the extruder cylinder set temperature during extrusion is increased. For the thermoplastic resin (A) having an HDT of 120 ° C. or higher at 1.80 MPa, it is desirable that the cylinder set temperature during extrusion be 200 ° C. or higher. Further, when the thermoplastic resin (A) is a resin obtained by condensation polymerization, a high temperature atmosphere of 200 ° C. or higher, an outgas such as a small amount of water, and an emulsifier or a metal salt contained in the vinyl polymer (B). The thermoplastic resin (A) may be decomposed due to the influence. The present invention can be kneaded with the vinyl polymer (B) without damaging the properties of the thermoplastic resin (A) even under such conditions. In the thermoplastic resin (A) having an HDT of 140 ° C. or higher at 1.80 MPa, the cylinder setting temperature of the extruder is desired to be further increased, so that the present invention works more suitably. Examples of the resin (A) having an HDT at 1.80 MPa of 120 ° C. or higher and obtained by condensation polymerization include polycarbonate, polyarylate, polybutylene terephthalate, and the like, particularly when polycarbonate is used. Is preferred.

<Vinyl polymer (B)>
The vinyl polymer (B) is a polymer obtained by polymerizing a vinyl monomer. The vinyl monomer to be used is not particularly limited as long as a polymer can be obtained by an emulsion polymerization method or a suspension polymerization method, but an aromatic vinyl monomer or a (meth) acrylic acid ester unit is not particularly limited. It is preferable to use a monomer or the like. Examples of the aromatic vinyl monomer include α-methylstyrene and styrene. Examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, and 4-t- (meth) acrylate. Butylphenyl, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate , (Meth) acrylic acid trichlorophenyl and the like. However, (meth) acrylic acid means acrylic acid or methacrylic acid. These monomers may be used individually by 1 type, and may use 2 or more types together.

  The vinyl polymer (B) has a (meth) acrylic acid ester monomer unit of 10% by mass to 95% by mass (content ratio of monomer unit when the vinyl polymer (B) is 100% by mass). Some polymers are preferred. The content ratio of the (meth) acrylic acid ester monomer unit in the vinyl polymer (B) is more preferably 25% by mass or more and 90% by mass or less. When the (meth) acrylic acid ester monomer unit is 10% by mass or more, the compatibility of the vinyl polymer (B) and the thermoplastic resin (A) can be easily matched, which is preferable. On the other hand, when the (meth) acrylic acid ester monomer unit is 95% by mass or less, it is easy to match the refractive index with the thermoplastic resin (A) using an aromatic vinyl monomer, which is preferable.

  The mass average molecular weight of the vinyl polymer (B) is preferably 5,000 to 200,000. If the mass average molecular weight of the polymer is 5000 or more, the heat resistance and mechanical properties of the resulting resin composition are not lowered. The weight average molecular weight of the vinyl polymer (B) is more preferably 10,000 or more, and further preferably 30,000 or more. If the mass average molecular weight of the vinyl polymer (B) is 200,000 or less, it is easy to modify because it is easily compatible with the thermoplastic resin (A). The mass average molecular weight of the vinyl polymer (B) is more preferably 150,000 or less, and even more preferably 100,000 or less.

  The shape of the vinyl polymer (B) is not particularly limited, and examples thereof include powder, flakes, and pellets. Especially, the powder in which the vinyl polymer (B) supplied from the side feed part is easy to disperse | distribute to a thermoplastic resin (A) is preferable.

  As a polymerization method of the vinyl polymer (B), an emulsion polymerization method or a suspension polymerization method is used. The polymer latex of the obtained vinyl polymer (B) can be pulverized by a known method to obtain the vinyl polymer (B).

  The vinyl polymer (B) obtained by the emulsion polymerization method contains a trace amount of an emulsifier and a metal salt used at the time of polymerization. When the total concentration of metal components (at least one selected from the group consisting of Na, K, Ca, Mg and Fe) in the vinyl polymer (B) is 5 ppm or more, a thermoplastic resin (A ) Easily occurs, and the present invention preferably works. When the total concentration of the metal components (Na, K, Ca, Mg, Fe) in the vinyl polymer (B) is 20 ppm or more, the thermoplastic resin (A) is more easily decomposed by the catalytic action of the metal components. Therefore, the present invention works more suitably. The total concentration of the metal components is preferably 2000 ppm or less.

  The method for analyzing the metal component (Na, K, Ca, Mg, Fe) in the vinyl polymer (B) is not particularly limited as long as the metal component can be quantified. For example, the vinyl polymer (B) Dry ashing by a known method, heated to a specified concentration with hydrochloric acid and distilled water equivalent to JISK0557A3, measured with an ICP emission spectrometer, etc., and quantified by comparison with a calibration curve prepared with a solution of known concentration I can do it. A value obtained by summing the measured concentrations of each component (Na, K, Ca, Mg, Fe) is defined as a total concentration.

  When kneading the thermoplastic resin (A) and such a vinyl polymer (B), an outgas such as water contained in a trace amount of the thermoplastic resin (A) and a trace amount of emulsifier contained in the vinyl polymer (B). The thermoplastic resin (A) and the vinyl polymer (B) may be decomposed due to the influence of metal salt or metal salt. According to the method of the present invention, since these decompositions can be suppressed, the vinyl polymer (B) obtained by the emulsion polymerization method can be suitably used. Similarly, the vinyl polymer (B) obtained by the suspension polymerization method contains a trace amount of a metal salt as a dispersion aid used at the time of polymerization, such as water contained in a trace amount of the thermoplastic resin (A). The thermoplastic resin (A) and the vinyl polymer (B) may be decomposed during kneading due to the influence of the outgas and the metal salt. According to the present invention, since such decomposition can be suppressed, the vinyl polymer (B) obtained by the suspension polymerization method can be suitably used.

<Resin composition>
The resin composition produced by the present invention is obtained by kneading a thermoplastic resin (A) and a vinyl polymer (B). In order to modify various physical properties of the thermoplastic resin (A) without deteriorating the excellent properties of the thermoplastic resin (A), these blending ratios are 70 to 99.5 mass of the thermoplastic resin (A). %, Vinyl polymer (B) 0.5-30% by mass, additives 0-5% by mass (the total of the thermoplastic resin (A), vinyl polymer (B) and additives is 100% by mass). Is preferred. It is preferable for the blending ratio of the vinyl polymer (B) to be 0.5% by mass or more because the blending effect of the vinyl polymer (B) can be satisfactorily obtained. It is preferable for the blending ratio of the vinyl polymer (B) to be 30% by mass or less because it is easy to modify without deteriorating the excellent properties of the thermoplastic resin (A). The blending ratio of the vinyl polymer (B) is more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more. On the other hand, the blending ratio of the vinyl polymer (B) is more preferably 25% by mass or less, and further preferably 20% by mass or less. Moreover, since the modification effect of a vinyl polymer (B) is hard to receive the influence of an additive as the compounding ratio of an additive is 5 mass% or less, it is preferable. The blending ratio of the additive is more preferably 2% by mass or less, and further preferably 0.5% by mass or less.

  The resin composition produced by the production method of the present invention may contain various stabilizers, reinforcing agents, inorganic fillers, mold release agents, antistatic agents, bluing agents, flame retardants, fluoroolefins and the like as necessary. May be blended. Examples of various stabilizers include known ultraviolet absorbers, light stabilizers, antioxidants, heat stabilizers, and the like. Examples of the reinforcing agent include glass fiber, carbon fiber, and potassium titanate fiber. Examples of the inorganic filler include talc, mica, and calcium carbonate. Examples of the fluoroolefin include polyethylene terephthalate.

<Extruder>
In the present invention, kneading can be performed using an extruder as shown below.

  As the extruder, a single screw extruder, a twin screw extruder, a multi-screw extruder, or the like can be used. Among these, a twin screw extruder is preferable because of its high kneading effect. If it is a twin screw extruder, the rotation direction and combination of a screw can use any of a same direction rotation type / different direction rotation type, a meshing type / non-meshing type. Among them, the same direction rotation complete meshing type is preferable because of its high internal self-cleaning property. What is necessary is just to select suitably the magnitude | size of an extruder, ie, a screw diameter and length, by the quantity to process. The screw diameter is preferably about 15 mm to 200 mm, but is not limited. Further, the total length of the cylinder or the total length of the screw is preferably about 20 to 100 times the screw diameter, but is not limited.

  An external heater, an external jacket, an internal jacket, or the like can be used for controlling the temperature of the cylinder (for example, the cylinder walls of the first kneading section 12, the resin damming section 14, and the second kneading section 16 in particular). . As the external heater, a band heater, an aluminum cast heater, a brass cast heater, or the like can be used. In the case of an outer jacket or an inner jacket, the temperature can be controlled by flowing hot / cold water or a heating medium. There is no problem in using these in combination. In order to enable finer temperature control, these heaters and jackets should be provided for each divided section as a combination of cylinders divided into blocks whose length is about 2 to 6 times the screw diameter. More preferred.

<Raw material supply port 1>
The raw material supply port 1 refers to an opening for supplying the thermoplastic resin (A) into the extruder cylinder. The thermoplastic resin (A) can be supplied from the raw material supply port into the extruder cylinder using a known method. A thermoplastic resin (A) can be quantitatively supplied to the trapezoidal hopper 101 using a known quantitative feeder (not shown), and the supplied thermoplastic resin (A) is trapped in a trapezoidal shape by a natural drop due to gravity. To the inside of the extruder cylinder.

<First vent port 2>
The first vent port 2 is an opening for discharging outgas such as water out of the extruder. Even if the vinyl polymer (B) is added by reducing the outgas such as moisture contained in the thermoplastic resin (A), the thermoplastic resin (A) and further the vinyl polymer (B) are added. Is difficult to disassemble.

  The first vent port can be constituted by at least one opening existing on the downstream side of the first kneading section. When a plurality of such openings are provided, all the openings are regarded as the first vent port.

  When the MFR at 320 ° C. of the thermoplastic resin (A) is large, or when the thermoplastic resin (A) contains a lot of outgas such as water, the thermoplastic resin (A) comes out of the extruder from the first vent port. Since “vent up” may occur, an open vent is preferable as the first vent port. When the MFR of the thermoplastic resin (A) at 320 ° C. is small, and the thermoplastic resin (A) contains almost no outgas such as water, the first vent port has a low possibility of vent-up. Is preferred.

<Side feed port 3>
The side feed port 3 is an opening for supplying the vinyl polymer (B) into the extruder cylinder. When there are a plurality of such openings, all the openings are regarded as side feed openings.

  When the vinyl polymer (B) is side-fed, the vinyl polymer (B) can receive a shearing force only on the downstream side of the side feed port. Therefore, side feed is suitable as a method for adding the vinyl polymer (B) when the vinyl polymer (B) is easily thermally decomposed.

<Discharge port 5>
The discharge port 5 is an opening through which the resin composition is discharged from the extruder. The outlet can be constituted by one or a plurality of openings. The processing method of the resin composition discharged from the extruder is not particularly limited. After discharging in a fixed shape, it may be cooled and pulverized, or a general pellet forming means may be employed. When used as a masterbatch, it is preferably formed into a pellet. Although it does not specifically limit as a method of shape | molding in a pellet form, It is good to extrude a resin composition from a die | dye to a strand form, and to cut it to suitable length.

<Second vent 4>
A second vent port 4 can be provided in the extruder. Thereby, gas components, such as a water | moisture content and decomposition product from a vinyl polymer (B), can be removed from a 2nd vent port. The second vent port can be constituted by at least one opening. When a plurality of such openings are provided, all the openings are regarded as the second vent port. The second vent port is not particularly limited as long as outgas such as water can be discharged out of the extruder, but a vacuum vent that can efficiently remove a small amount of outgas such as water is preferable.

  The second vent port 4 can be provided between the side feed port 3 and the discharge port 5 separately from these. That is, the second vent port is configured by one or a plurality of openings provided in a cylinder wall in a partial region of the second kneading unit 16. In the present specification, a region where the second vent port is provided in the cylinder axial direction inside the cylinder, that is, the cylinder internal region 16b from the upstream end to the downstream end of the second vent port in the cylinder axial direction is referred to as “second”. It may be referred to as a “vent part”. In the case where the second vent port is provided, the second kneading part 16 includes, in addition to the second vent part 16b, a portion 16a upstream from the second vent part (from the side feed port downstream end to the second vent port upstream end). And a portion 16c downstream of the second vent portion (cylinder internal region from the second vent port downstream end to the discharge port upstream end).

<Raw material supply unit 11>
The cylinder inner region of the portion where the raw material supply port 1 is provided in the extruder cylinder axial direction, that is, the cylinder inner region 11 from the upstream end to the downstream end of the raw material supply port in the cylinder axial direction (in this specification, this (In some cases, the region is referred to as a “raw material supply unit”), and when there is a cylinder internal region upstream of the raw material supply unit, the screw configuration is not particularly limited in the cylinder internal region. A screw element may or may not be present. Transport the thermoplastic resin (A) from the viewpoint of transporting the thermoplastic resin (A) to the first kneading part, particularly from the viewpoint of preventing the “feed neck phenomenon” where the thermoplastic resin (A) does not enter the extruder. It is preferable to dispose the screw element that can be formed in the above-described region (raw material supply unit, and further, the cylinder internal region on the upstream side thereof). For example, since the transportation capability is high, it is preferable to provide a full flight screw in the forward direction, a kneading disk in the forward direction, and in particular, a full flight screw in the forward direction. When the said area | region is not the screw structure which can transport a thermoplastic resin (A), it can send in a pressure to a thermoplastic resin (A).

<First kneading part 12>
By using a screw element having kneading ability in the first kneading part, shear heat generation can be obtained, and the thermoplastic resin (A) can be efficiently melted. Furthermore, the thermoplastic resin (A) can be melted by setting the temperature.

  A screw element having a kneading ability is arranged on a part or the whole of the first kneading part in the cylinder axial direction. In the former case, there may be a portion where the screw element is not arranged in the portion of the first kneading portion where the screw element having the kneading ability in the cylinder axial direction is not arranged, and a screw having no kneading ability (for example, , A full flight screw in the forward direction or the reverse direction) may be included.

  When the thermoplastic resin (A) is melted in the first kneading section, outgas such as water having a boiling point lower than the extruder cylinder set temperature is generated. The outgas here is a gaseous substance at the melting temperature and normal pressure of the thermoplastic resin (A) including water contained in a trace amount in the thermoplastic resin (A). Examples of the other outgas include a decomposition product of the thermoplastic resin (A), an additive previously added to the thermoplastic resin (A), and a decomposition product thereof.

<First vent part 13>
A region 13 where the first vent port is provided in the cylinder axial direction inside the cylinder, that is, a cylinder internal region from the upstream end to the downstream end of the first vent port in the cylinder axial direction (in this specification, this region is The screw configuration is not particularly limited, and some screw elements may or may not exist in the first vent portion. From the viewpoint of transporting the thermoplastic resin (A) to the first kneading part, in particular, from the viewpoint of preventing “venting up” in which part of the thermoplastic resin (A) flows out from the vent port, the thermoplastic resin (A) is used. It is preferable to arrange a screw element that can be transported in the first vent portion. For example, it is preferable to provide a positive full flight screw or a positive kneading disk having a high transportation capacity, and in particular, a positive full flight screw.

  The type of the first vent port is not particularly limited as long as outgas such as water can be discharged out of the extruder. However, when the resin viscosity in the first vent is low, or the thermoplastic resin (A) contains a lot of outgas such as water. In this case, an open vent is preferable from the viewpoint of preventing “venting up” of the thermoplastic resin (A) coming out of the extruder from the first vent port. The first vent port in the case where the resin viscosity up to the first vent port is high and the thermoplastic resin (A) contains almost no outgas such as water is preferably a vacuum vent because the possibility of vent-up is low.

<Resin damming part 14>
The resin damming portion 14 is a portion that dampens the thermoplastic resin (A) by the screw element. By using a screw element having a resin damming action in the resin damming portion, the thermoplastic resin (A) can be retained, and the outgas such as moisture contained in the thermoplastic resin (A) can be effectively removed. Can be removed (from the first vent).

  A screw element having a function of blocking the resin is provided on a part or the whole of the resin blocking portion in the cylinder axial direction. In the former case, there may be a portion where the screw element is not arranged in the portion of the resin blocking portion where the screw element having the resin blocking action in the cylinder axial direction is not arranged, and a screw having no resin blocking action ( For example, a full flight screw in the positive direction) may be included.

  The thermoplastic resin (A) exists in the first kneading part and the resin damping part, but the vinyl polymer (B) to be mixed does not exist. By melting the thermoplastic resin (A) in the first kneading part, the outgas can be extracted from the first vent port, so that it is not necessary to further apply shear in the resin damming part thereafter, and in the resin damming part. This is because it is preferable to suppress more thermal decomposition of the thermoplastic resin (A) due to further shearing.

  Although an element having a resin damming action but not having a kneading ability can be arranged in the resin damming portion, it is preferable to provide a screw element having a kneading ability and a resin damming action. The reason for this is that a higher damming effect can be obtained by having kneading ability and resin damming action. An example of an element having a resin damming action but no kneading ability is a full flight screw in the reverse direction.

  When the vinyl polymer (B) is added from the side feed port and kneaded with the thermoplastic resin (A), due to the influence of outgas such as water and the influence of the emulsifier and metal salt contained in the vinyl polymer (B). The thermoplastic resin (A) and the vinyl polymer (B) may be decomposed. Therefore, it is desired that the outgas such as water contained in the thermoplastic resin (A) is efficiently discharged from the first vent. Therefore, a thermoplastic resin (A) is provided by disposing a screw element having a resin blocking action between the first vent part and the side feed part and lengthening the residence time of the thermoplastic resin (A) in the first vent part. Outgas such as water generated during melting can be efficiently discharged out of the system.

  The ratio (L / D) of the length (cylinder axial direction) of the screw element used in the resin damming portion and having a damming action to the diameter of the screw element arranged in the resin damming portion is 0.75 or more and 3 or less. Is preferred. If L / D is 0.75 or more, the damming effect of the thermoplastic resin (A) is good, and if L / D is 3 or less, it is easy to suppress decomposition of the thermoplastic resin (A). Therefore, it is preferable. More preferably, 1 ≦ L / D ≦ 2.

<Side feed section 15>
In the cylinder axial direction, in the cylinder inner region 15 between the upstream side end of the side feed port and the downstream side end of the side feed port (in this specification, this region may be referred to as a “side feed part”) The screw configuration is not particularly limited, and some screw elements may or may not exist. From the viewpoint of transporting the thermoplastic resin (A), particularly from the viewpoint of preventing the “feed neck phenomenon” in which the vinyl polymer (B) does not enter the extruder, a screw element that can transport the thermoplastic resin (A) is side-mounted. It is preferable to arrange in the feed part. For example, since the transportation capability is high, it is preferable to provide a full flight screw in the forward direction, a kneading disk in the forward direction, and in particular, a full flight screw in the forward direction.

  Although there is no restriction | limiting in particular about the supply method in the extruder of a vinyl polymer (B), Connect the side feeder and especially the side feeder which supplies a vinyl polymer (B) into a cylinder quantitatively to a side feed port. Can do. The side feeder may be any device that can feed the vinyl polymer into the extruder even when the resin is flowing into the extruder.

  The side feed port is located at the upstream end of the side feed port when the position of the upstream end of the screw element disposed at the most upstream in the extruder cylinder flow direction is 0 and the downstream end position of the discharge port is 1. It is preferable that the position is arranged in a range of 0.3 to 0.9. If it is 0.3 or more, the thermoplastic resin (A) previously charged in the extruder can be melted well, which is preferable. Moreover, if it is 0.9 or less, the second kneading part (including the second vent part in some cases) for kneading the side-feed vinyl polymer (B) and the thermoplastic resin (A) can be easily provided. preferable. More preferably, it is 0.4 to 0.8.

<Second kneading part 16>
In the second kneading section (between the downstream end on the side feed port and the upstream end on the discharge port) 16, the thermoplastic resin (A) previously supplied to the extruder and the side-feed vinyl polymer (B) are It can be kneaded.

  A screw element having a kneading ability is disposed in part or all of the second kneading part in the cylinder axial direction. In the case of the former, there may be a portion where the screw element is not arranged in the portion of the second kneading portion where the screw element having the kneading ability in the cylinder axial direction is not arranged, and a screw having no kneading ability (for example, , A full flight screw in the forward direction or the reverse direction) may be included.

  In the second kneading part, about 20 to 60% of screw elements having kneading ability (the length of the screw element having kneading ability provided in the second kneading part relative to the length of the second kneading part in the cylinder axial direction) It is preferable to deploy. If this ratio is 20% or more, the thermoplastic resin (A) and the vinyl polymer (B) can be effectively kneaded. If this ratio is 60% or less, thermal decomposition of the vinyl polymer due to shearing heat generation can be easily suppressed.

<When providing a second vent port>
In the case of providing the second vent port, the second kneading part 16 includes a second vent part 16b, and further includes a part 16a upstream from the second vent part and a part 16c downstream from the second vent part.

  In this case, a screw element having a kneading ability is arranged on a part or all of the portion 16a upstream of the second vent portion. In the former case, a portion where the screw element having the kneading ability in the cylinder axial direction is not provided in the portion 16a may be a portion where the screw element is not provided, and a screw having no kneading ability (for example, a normal screw). Direction or reverse full flight screw).

  In the 2nd vent part 16b, a screw structure is not specifically limited, Even if a certain screw element exists in a 2nd vent part, it does not need to exist. From the viewpoint of transporting the thermoplastic resin (A) and the vinyl polymer (B), in particular, from the viewpoint of preventing “vent up” in which a part of the thermoplastic resin (A) vinyl polymer (B) flows out from the vent. It is preferable to arrange a screw element capable of transporting the thermoplastic resin (A) and the vinyl polymer (B) in the second vent portion. For example, it is preferable to provide a positive full flight screw or a positive kneading disk having a high transportation capacity, and in particular, a positive full flight screw.

  In the portion 16c downstream of the second vent portion of the second kneading portion, the screw configuration is not particularly limited, and some screw elements may or may not exist.

  Preferably, the screw elements having the kneading ability provided in the second kneading part 16 are all provided in the part 16a, and the screw elements having the kneading ability are not provided in the second vent part 16b and the downstream part 16c. As a preferable screw element in the portion 16c on the downstream side of the second vent portion, a full flight screw in the positive direction can be cited.

  The temperature and rotation speed of the extruder can be appropriately set according to the thermoplastic resin (A) and vinyl polymer (B) to be handled.

<About MFR (Melt Flow Rate)>
For the MFR ratio defined as follows, 2.0> MFR ratio> 0.15 is preferable.
MFR ratio = (MFR [g / 10 min] of vinyl polymer (B) at 180 ° C.) / (MFR [g / 10 min] of 320 ° C. of thermoplastic resin (A)).

  According to the present invention, after the thermoplastic resin (A) is melted, outgas such as moisture is removed at the first vent port, and then the vinyl polymer (B) is side-feeded to thermoplastic resin (A). And vinyl polymer (B) can be kneaded. The vinyl polymer (B) is added to the molten thermoplastic resin (A). The viscosity of the molten thermoplastic resin (A) (MFR [g / 10 min] at 320 ° C.) is close to the viscosity of the vinyl polymer (B) (MFR [g / 10 min] of the vinyl polymer (B) at 180 ° C.). This is preferable because the kneading length after the side feed (the length of the screw element having the kneading ability) can be shortened, and the decomposition of the thermoplastic resin (A) can be further suppressed, so 2.0> MFR ratio> 0.15. Is preferable, and 1.5> MFR ratio> 0.5 is more preferable.

  MFR is based on JISK7210, and can measure the thermoplastic resin (A) based on the amount of polymer flowing out for 10 minutes under the conditions of a measurement temperature of 320 ° C. and a load of 2.16 kg. The measurement method of the vinyl polymer (B) can also be measured under the same measurement conditions as the thermoplastic resin (A) except that the measurement temperature is 180 ° C.

  Examples of the present invention are shown below, but the present invention is not limited thereto. Unless otherwise specified, “part” means part by mass, and “%” means mass%.

<Production of vinyl polymer (B) by emulsion polymerization method>
The following emulsifier mixture was put into a separable flask equipped with a thermometer, a nitrogen introducing tube, a cooling tube, and a stirring device and stirred, and the internal temperature of the separable flask was raised to 60 ° C. in a nitrogen atmosphere.

Emulsifier mixture:
Emar 20C (trade name, manufactured by Kao Corporation, anionic emulsifier) 5.0 parts,
-300 parts of ion exchange water.

The following reducing agent mixture was then added into the separable flask.
Reducing agent mixture:
・ 0.0001 part of ferrous sulfate,
-Ethylenediaminetetraacetic acid disodium salt 0.0003 parts,
・ Longarit 0.3 parts,
・ Ion exchange water 5 parts.

  Next, the following monomer mixture (1) was dropped into the separable flask over 180 minutes, and stirred for 15 minutes after the completion of the dropping.

Monomer mixture (1):
Α-methylstyrene 10.0 parts,
・ Styrene 30.0 parts,
-Phenyl methacrylate 10.0 parts,
-0.25 parts of n-octyl mercaptan,
-0.1 part of t-butyl hydroperoxide.

  Next, the following monomer mixture (2) was dropped into the separable flask over 240 minutes. After completion of the dropping, the internal temperature was raised to 80 ° C. and stirred for 60 minutes to complete the polymerization.

Monomer mixture (2):
・ Styrene 20.0 parts,
-30.0 parts of phenyl methacrylate,
-0.25 parts of n-octyl mercaptan,
-0.1 part of t-butyl hydroperoxide.

  Cool the internal temperature of the separable flask to 50 ° C., add 0.8 part of Pelex SS-L (trade name, manufactured by Kao Corporation, anionic emulsifier), add 6 parts of dispersant (α), A latex of polymer (B) containing 40% of (meth) acrylic acid ester monomer units was obtained.

  In another separable flask, 625 parts of an aqueous solution in which 5 parts of calcium acetate was dissolved was heated to 91 ° C. and stirred. In this, the latex of the obtained polymer (B) was dripped gradually, after completion | finish of dripping, it heated at 95 degreeC and hold | maintained for 5 minutes, and the latex of the polymer (B) was coagulated.

  The obtained solidified product was subjected to solid-liquid separation, washed, and dried at 75 ° C. for 24 hours to obtain a polymer (B) powder.

  Mw (mass average molecular weight) of the polymer (B) was 45000, Mn (number average molecular weight) was 16500, and molecular weight distribution (Mw / Mn) was 2.6. The metal components in the polymer (B) were Ca, K, and Na, and the total concentration was 1,108 ppm. The MFR of the polymer (B) at 180 ° C. was 7.9 g / 10 min.

<Method for producing dispersant (α)>
The following compound (i) was put into a separable flask, and the internal temperature was heated to 60 ° C. and dissolved while stirring to obtain an aqueous solution.

  The following compound (ii) was slowly put into a separable flask containing this aqueous solution, and then homomixer (manufactured by Primics Co., Ltd., main body: TK Robotics (trade name), stirring unit: T.M. K. Homomixer MARK II 2.5 type (trade name)) was stirred at 12,000 rpm for 1 minute to obtain a dispersant (α).

Compound (i):
IRGASTAB MBS11 50.0 parts (trade name, manufactured by Ciba Japan Co., Ltd., 2,4-dimethyl-6- (1-methylpentadecyl) phenol, melting point: 25 ° C. or less, 80% and octadecyl-3- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], melting point: 50-55 ° C., 20% mixture)
IRGANOX 1076 50.0 parts (trade name, manufactured by Ciba Japan Co., Ltd.), octadecyl-3- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], melting point: 50 to 55 ° C),
9.3 parts oleic acid.

Compound (ii):
・ Ion exchange water 100.0 parts,
-2.2 parts of potassium hydroxide.

<Mass average molecular weight (Mw), number average molecular weight (Mn)>
Using gel permeation chromatography, Mw and Mn of the polymer were measured using a standard polystyrene calibration curve with the following equipment and measurement conditions.

Column: Tosoh Co., Ltd. TSK-GEL SUPER HZM-N,
Measurement temperature: 40 ° C.
Eluent: chloroform,
Eluent speed: 0.6 ml / min,
Detector: RI.

<Stability thermal stability>
The residence heat stability of the resin composition was evaluated by the following method.
After sufficiently drying the sampled pellets, a test piece of length 80 mm × width 10 mm × thickness 4 mm was molded using an injection molding machine “IS-100” (trade name, manufactured by Toshiba Machine Co., Ltd.). The obtained test piece was annealed at 150 ° C. for 2 hours, HDT was measured according to ISO 75-2, and the load was 1.82 MPa. The HDT at this time is called HDT _I.
Next, the pellets sampled in the cylinder when molding a test piece with an injection molding machine (IS-100 (trade name), manufactured by Toshiba Machine Co., Ltd.) are retained at 320 ° C. for 30 minutes, and then described above. Test pieces were prepared in the same manner as described above, and HDT was measured. The HDT at this time is called HDT _{30 min} . ΔHDT was determined from the following formula to evaluate the residence heat stability.
ΔHDT = HDT _I -HDT _30min
When ΔHDT is large, it means that the thermal stability after being retained at 320 ° C. for 30 minutes is greatly reduced. When ΔHDT is small, even if it is retained at 320 ° C. for 30 minutes, the thermal stability is greatly reduced. It means not.

<Example 1>
The extruder is a twin screw extruder “TEX-44” (trade name, manufactured by Nippon Steel, Ltd., screw diameter 47 mm, total screw length is approximately 52 times the screw diameter (L / D = 52), complete in the same direction. The meshing type) was used.

  Regarding the basic structure of the extruder, as shown in FIG. 1, from the upstream side which is the thermoplastic resin supply side, the raw material supply port 1, the first vent port 2, the side feed port 3, the second vent port 4, the exhaust An outlet 5 is provided in the cylinder 6. The cylinder inner region includes the raw material supply unit 11, the first kneading unit 12, the first vent unit 13, the resin damming unit 14, the side feed unit 15, and the second kneading unit 16 (the second vent unit 16b, upstream from the second vent unit). Side portion 16a, downstream portion 16c) of the second vent portion, and upstream portion of the raw material supply portion.

  A trapezoidal hopper 101 is connected to the raw material supply port 1, and the thermoplastic resin (A) is supplied into the cylinder from here by natural fall due to gravity. A trapezoidal hopper 103 is connected to the side feed port 3, and the vinyl polymer (B) is supplied from the inside to the inside of the cylinder by natural fall due to gravity. The first vent port 2 and the second vent port 4 are connected to cylindrical members 102 and 104 for connection to vacuum piping, respectively. A die 105 for forming into a pellet shape is connected to the discharge port 5.

  The details of the screw elements used are shown in Table 1.

  The total length of the raw material supply unit 11 and the length of the region upstream from the raw material supply unit 11 was L / D = 2.0.

  The length of the first kneading part 12 is L / D = 19.0, the position of L / D = 11.25 from the upstream end of the first kneading part, and L / D = 18.25 from the same end. A screw element (total L / D = 7.0) having a configuration of “R1, R1, R1, R1, and L” shown in Table 2 as a screw element having kneading ability was disposed in a region between the positions.

  The length of the 1st vent part 13 was L / D = 2.0.

  The length of the resin stopper 14 is L / D = 8.75, and the region between the position of L / D = 3.25 from the upstream end of the resin stopper and the position of 5.25 from the same end The screw elements (total L / D = 2.0) having the structure of “N · L” shown in Table 2 were arranged as screw elements having a resin damming action.

  The length of the side feed part 15 was L / D = 2.0.

  The length of the second kneading part 16 is L / D = 18.25, and the position of L / D = 3.25 from the upstream end of the second kneading part and L / D = 10.25 from the same end. A screw element (total L / D = 7.0) having a configuration of “R1, R1, R1, R1, and L” shown in Table 2 as a screw element having kneading ability was disposed in a region between the positions. The length of the portion 16a was L / D = 12.25, the length of the second vent portion 16b was L / D = 2.0, and the length of the portion 16c was L / D = 4.0.

  In addition to the portion where the screw element shown in Table 2 is arranged in the cylinder, a full flight screw (F) in the positive direction is arranged (in practice, L / D = 0.75, 1.00, 1.. 25, 1.50 positive full flight screws (F) were used as appropriate).

  As for the side feed port, when the upstream end position of the screw element arranged at the most upstream in the extruder cylinder flow direction is 0 and the downstream end position of the discharge port is 1, the upstream end position of the side feed port is 0.61.

  The ratio of screw elements having kneading ability in the second kneading part (length of screw element having kneading ability / length of second kneading part) is about 40% (7.0 / 18.25 = 4.3). ).

  Moreover, both the 1st vent and the 2nd vent were made into the vacuum vent, and it attracted | sucked at -0.076--0.080MPa (gauge pressure).

  The extruder controlled the cylinder set temperature from the raw material supply unit to the front of the side feed unit at 320 ° C., and the cylinder set temperature from the side feed unit to the discharge port at 280 ° C.

  As the thermoplastic resin (A), a polycarbonate resin “APEC1800” (trade name, manufactured by Bayer) of HDT159 ° C. at 1.80 MPa is used, and 122.4 [kg / h] (heat to the entire resin composition to be manufactured) It was supplied to the extruder from the raw material supply port at a speed of the blending ratio of the plastic resin (A): 85% by mass). “APEC1800” has an MFR at 320 ° C. of 9.1 g / min, and the MFR ratio (MFR [g / 10 min] at 180 ° C. of the vinyl polymer (B)) / (320 of the thermoplastic resin (A)). The MFR [g / 10 min] at 0.9 ° C. was 0.9.

  "Sumilizer GP" (trade name, manufactured by Sumitomo Chemical Co., Ltd.), "ADEKA STAB PEP-36" (trade name, manufactured by ADEKA) and "ADEKA STAB AO-80" (trade name, Co., Ltd.) ADEKA) was mixed at a ratio of 1/2 (mass ratio) to prepare a heat stabilizer (Y). 0.67 parts of heat stabilizer (Y) was previously mixed with 100 parts of vinyl polymer (B) to obtain a heat stabilizer (Y) / vinyl polymer (B) mixture. Using a side feeder, the heat stabilizer (Y) / vinyl polymer (B) mixture was placed in an extruder at 21.6 [kg / h] (the blending ratio of the vinyl polymer (B) with respect to the entire resin composition to be produced: (14.9% by mass) from the side feed section to the extruder and extruded at a screw speed of 400 rpm. The resin coming out from the outlet was cut by a pelletizer, the pellets were sampled, and the residence heat stability of the sampled pellets was measured. The results are shown in Table 3.

  In Table 3, the resin temperature is a temperature obtained by actually measuring the temperature of the resin composition immediately after being discharged from the discharge port with a thermometer. The specific power is a value obtained by dividing the net power of the extruder by the total throughput.

<Examples 2 and 3>
“APEC1800”, the supply amount of the vinyl polymer (B) and the heat stabilizer (Y) (the mixing ratio of the three components is the same as in Example 1), except that the screw rotation speed was changed as described in Table 3, The same test as in Example 1 was performed.

<Comparative Examples 1-3>
The length of the first kneading part 12 is kept at L / D = 19.0, and replaced with screw elements (total L / D = 7.0) having a configuration of “R1, R1, R1, R1, and L”. Screw elements (total L / D = 9.0) having the configuration of “R2, F, F, R2, N, F, N, and L” shown in Table 2 from the upstream end of the first kneading section. = 9.5 and the region between the same end and the position of L / D = 18.5.

  The length of the resin damming portion 14 was kept at L / D = 8.75, and full-flight screws (F) in the positive direction were all disposed in the resin damming portion. Here, for the sake of convenience, the name “resin damming portion” is used, but it should be noted that in the comparative example, no screw element having a resin damming action is arranged in this portion.

  In addition, in order to compensate for the decrease in the shearing action of the screw element on the thermoplastic resin (A) in the resin damping part (for comparison with the example), the screw configuration of the first kneading part was changed as described above. ing.

  Except for these, the extruder configuration was the same as in Example 1. In addition, the supply amount of “APEC1800”, the supply amount of the vinyl polymer (B) and the heat stabilizer (Y), and the screw rotation speed were set as shown in Table 3. Except for these, the same test as in Example 1 was performed.

  In the comparison between Example 1 and Comparative Example 1, the specific power showed almost the same value. Since the screw configuration of the second kneading part of Example 1 and Comparative Example 1 is the same, only the first kneading part of Comparative Example 1 is sheared to “APEC1800” in the first kneading part of Example 1 and the resin. It can be seen that it is almost the same as the shear at the damming part.

  As is apparent from the results in Table 3, ΔHDT (the temperature at which the load deflection temperature decreases at 1.82 MPa) of the example is as small as 2.6 ° C. to 3.3 ° C. Therefore, it was possible to obtain a resin composition modified with the vinyl polymer (B) while maintaining the residence thermal stability of the thermoplastic resin (A). In the comparative example, since no screw element having a resin damming action was provided in the resin damming portion, ΔHDT was large and the residence heat stability of the thermoplastic resin (A) was lowered.

1: Raw material supply port 2: First vent port 3: Side feed port 4: Second vent port 5: Discharge port 6: Cylinder 11: Raw material supply unit 12: First kneading unit 13: First vent unit 14: Resin clogging Part 15: Side feed part 16: Second kneading part 16a: Part upstream of the second vent part of the second kneading part 16b: Second vent part 16c: Part of the second kneading part downstream of the second vent part 101: thermoplastic resin (A) supply hopper 102: cylindrical member 103: vinyl polymer (B) supply hopper 104: cylindrical member 105: dice

Claims (5)

A method for producing a resin composition, wherein an extruder is used to knead a thermoplastic resin (A) and a vinyl polymer (B) to produce a resin composition,
The vinyl polymer (B) is a polymer obtained by an emulsion polymerization method or a suspension polymerization method,
To the cylinder of the extruder,
A raw material supply port which is an opening for supplying the thermoplastic resin (A);
A vent opening which is a vent opening;
A side feed port which is an opening for supplying the vinyl polymer (B);
An outlet that is an opening for discharging the resin composition,
Are provided in this order in the cylinder axial direction and spaced apart from each other,
In the cylinder inner region located between the downstream end of the raw material supply port and the upstream end of the vent port in the cylinder axial direction, a screw element having kneading ability is included,
In the cylinder axial direction, a screw element having an action of clogging resin is included in the cylinder inner region located between the downstream end of the vent port and the upstream end of the side feed port,
In the cylinder axial direction, an extruder including a screw element having kneading ability is used in a cylinder inner region located between the downstream end of the side feed port and the upstream end of the discharge port. The flow direction of the thermoplastic resin (A),
A method for producing a resin composition, comprising melting the thermoplastic resin (A), side-feeding the vinyl polymer (B), and melt-kneading.   2. The method according to claim 1, wherein the vinyl polymer (B) contains at least 5 ppm or more in total concentration of at least one metal component selected from the group consisting of Na, K, Ca, Mg and Fe.   The method according to claim 1 or 2, wherein the thermoplastic resin (A) is a resin having a load deflection temperature at 1.80 MPa of 120 ° C or higher and obtained by condensation polymerization. The vinyl polymer (B) has the following formula 2.0> (MFR [g / 10 min] at 180 ° C. of the vinyl polymer (B)) / (MFR [g / 10 min] at 320 ° C. of the thermoplastic resin (A)). )> 0.15
The method in any one of Claims 1-3 which is a polymer which satisfy | fills.   The method in any one of Claims 1-4 whose vinyl polymer (B) is a polymer containing 10 to 95 mass% of (meth) acrylic acid ester monomer units.

Images