JP2014025057A - Process for producing aqueous dispersion, process for producing graft polymer, and process for producing thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing an aqueous dispersion which can easily produce an aqueous dispersion having a small average particle diameter, a small amount of unemulsified material, a narrow particle diameter distribution, and excellent filterability.SOLUTION: Provided is a process for producing an aqueous dispersion by preparing a phase inversion material by dispersing an ethylenic polymer in an aqueous medium by a twin screw extruder (10) having two screws (12a) and (12b), arranged in a barrel (11) and by cooling the phase inversion material by using a cooling means (an extruder for cooling (20)). Here, the twin screw extruder (10) and the cooling means are connected through a connection pipe (30a) and a difference (T-T) between a temperature (T) of a barrel tip (11b) and a temperature (T) of the connection pipe (30a) is set in a range of 30 to 100°C.

Description

  The present invention relates to a method for producing an aqueous dispersion in which an ethylene polymer is dispersed in water. Moreover, it is related with the manufacturing method of a graft polymer, and the manufacturing method of a thermoplastic resin composition.

An aqueous dispersion in which an ethylene polymer is dispersed in water may be used as a raw material for a thermoplastic resin composition, an adhesive, a paint, or the like.
As a method for producing an aqueous dispersion, a polymerization method and a method utilizing a phase inversion phenomenon using an extruder or the like are known. Among these, the polymerization method is widely adopted as a method for obtaining an aqueous dispersion, but has problems such as complicated control of the polymerization reaction and complexity on the apparatus.
On the other hand, a method of utilizing the phase inversion phenomenon using an extruder or the like is to mix a molten thermoplastic resin and an aqueous medium with high shear in the presence of an emulsifier, etc., and disperse the thermoplastic resin in the aqueous medium. This is a method for continuously producing an aqueous dispersion.
Patent Documents 1 and 2 specifically disclose a method of obtaining an aqueous dispersion using an extruder, and the aqueous dispersion obtained using an extruder has a small average particle diameter and an unemulsified amount. It is described that a small amount can be manufactured stably.
In Patent Document 3, an aqueous dispersion is prepared by dispersing an ethylene / propylene / conjugated diene copolymer in water using an extruder, and a graft polymer is produced using the aqueous dispersion. It is disclosed that an AES resin is produced by blending a resin with the graft polymer.

Japanese Examined Patent Publication No. 7-96647 JP 2008-101156 A JP 2006-45466 A

  However, when an aqueous dispersion is produced by the methods described in Patent Documents 1 and 2, the resulting aqueous dispersion has a small average particle size and a wide particle size distribution despite a small amount of non-emulsified product. , Some large particles may be generated. In the paint field, filterability of about 300 mesh may be required to maintain the smoothness of the coating film surface, but when the particle size distribution is wide like the aqueous dispersions described in Patent Documents 1 and 2. However, the filterability was lowered, and the working efficiency was liable to be lowered.

By the way, since AES resin has excellent weather resistance and impact resistance, it is used as a vehicle exterior material in the automobile field. In recent years, in the automobile field, production costs have been reduced by unpainting vehicle exterior parts. When the coating is not applied, the surface state of the AES resin itself is reflected on the design surface of the vehicle exterior part. Therefore, an AES resin that increases the surface smoothness and surface gloss of the molded product is required.
However, even in the method described in Patent Document 3, the particle size distribution of the aqueous dispersion is wide, and the resulting AES resin tends to have insufficient surface smoothness and surface gloss of the molded product.

  An object of the present invention is to provide a method for producing an aqueous dispersion that can easily produce an aqueous dispersion having a small average particle size, a small amount of non-emulsified material, a narrow particle size distribution, and excellent filterability. Moreover, it aims at providing the manufacturing method of the graft copolymer which can manufacture easily the thermoplastic resin composition excellent in surface smoothness and surface glossiness. Moreover, it aims at providing the manufacturing method of the thermoplastic resin composition which can manufacture easily the thermoplastic resin composition excellent in surface smoothness and surface glossiness.

In one embodiment of the method for producing an aqueous dispersion of the present invention, a phase inversion body is prepared by dispersing an ethylene polymer in an aqueous medium by a twin screw extruder in which two screws are provided in a barrel. the phase body, a process for the preparation of an aqueous dispersion of cooling with a cooling means and the cooling means and the twin-screw extruder connected with connecting tube, connected to the temperature T ₁ of the twin screw extruder barrel tip the difference in temperature _{T 2} of the tubes _(T 1 -T _2), characterized in that in the range of 30 to 100 ° C..
In one embodiment of the method for producing a graft polymer of the present invention, an aqueous dispersion is produced by the method for producing an aqueous dispersion, and at least an aromatic vinyl monomer and a polymerization initiator are added to the aqueous dispersion. It is characterized by graft polymerization.
One aspect of the method for producing a thermoplastic resin composition of the present invention is to produce a graft polymer by the above-mentioned method for producing a graft polymer, and the graft polymer has a styrene type having at least an aromatic vinyl monomer unit. It is characterized by mixing a polymer.

According to the method for producing an aqueous dispersion of the present invention, an aqueous dispersion having a small average particle size, a small amount of non-emulsified material, a narrow particle size distribution, and excellent filterability can be easily produced.
According to the method for producing a graft copolymer of the present invention, a graft copolymer having excellent surface smoothness and surface gloss can be easily produced.
According to the method for producing a thermoplastic resin composition of the present invention, a thermoplastic resin composition having excellent surface smoothness and surface gloss can be easily produced.

It is a schematic diagram which shows the manufacturing apparatus used with one embodiment of the manufacturing method of the aqueous dispersion of this invention. It is the figure which expanded the connecting pipe which comprises the manufacturing apparatus of the aqueous dispersion of FIG. 1, and its vicinity.

(Method for producing aqueous dispersion)
One embodiment of the method for producing an aqueous dispersion of the present invention will be described.
1 and 2 show a manufacturing apparatus used in the manufacturing method of this embodiment. The manufacturing apparatus 1 includes a twin screw extruder 10 in which two screws 12a and 12b are disposed in a heatable barrel 11, and a cooling extruder 20 provided on the barrel tip 11b side of the twin screw extruder 10. A connection flow path 30 for connecting the twin screw extruder 10 and the cooling extruder 20 in an airtight state, a first supply means 40 for supplying an ethylene polymer to the end 11a side of the barrel 11, and a barrel 11 And a second supply means 50 for supplying water to the intermediate portion of the.

The twin-screw extruder 10 constituting the production apparatus 1 is used to invert water after adding water to the ethylene polymer (A). The term “phase inversion” as used herein means conversion from a state in which water is dispersed in the ethylene polymer (A) to a state in which the ethylene polymer (A) is dispersed in water. Moreover, in this specification, what was obtained by carrying out phase inversion with the twin-screw extruder 10 is called a phase inversion body.
The rotation directions of the two screws 12a and 12b of the twin-screw extruder 10 may be the same direction or different directions.

  The cooling extruder 20 is a cooling means used for cooling the phase inversion body obtained by the twin-screw extruder 10. The configuration of the cooling extruder 20 is not particularly limited as long as the temperature can be adjusted, and may be a single screw extruder or a twin screw extruder. Moreover, there is no restriction | limiting in particular also in a screw structure.

Most of the connection flow path 30 is constituted by a connecting pipe 30a. The part other than the connecting pipe 30a is a part for attaching the connecting pipe 30a to the twin screw extruder 10 or the cooling extruder 20.
The connecting pipe 30a is for transferring the phase inversion body obtained by the twin screw extruder 10 to the cooling extruder 20, and is a straight pipe in this embodiment.
As shown in FIG. 2, the connecting pipe 30a has a diameter D (mm) of the screw 12a of the twin screw extruder 10, a hole diameter d (mm) of the connecting pipe 30a, and a length L (mm) of the connecting flow path 30. Preferably satisfies the relationship of the following formula (1).
Formula (1) 2 ≦ {(D ³ · L) / d ⁴ } ≦ 300
When the hole diameter of the connecting pipe 30a is small or the length of the connection flow path 30 is long and {(D ³ · L) / d ⁴ } exceeds 300, the resin pressure at the tip of the twin screw extruder 10 increases. As a result, the phase inversion body and water vapor may leak. Once the water vapor begins to leak, an aqueous dispersion cannot be obtained, and production must be stopped, making continuous operation impossible.
On the other hand, when the hole diameter of the connecting pipe 30a is large and {(D ³ · L) / d ⁴ } is less than 2, it is difficult to obtain an aqueous dispersion having a small average particle diameter and a small amount of non-emulsified material. Become.

  It is preferable that the connecting pipe 30a is provided with an external heater, a temperature controller, and, if necessary, a heat insulating material, a cooling mechanism of air cooling or water cooling, so that the temperature of the outer wall of the pipe can be controlled. If the temperature of the outer wall of the tube can be controlled, an aqueous dispersion (AW) having a smaller average particle size, a smaller amount of non-emulsified material, and a narrower particle size distribution can be stably produced.

As the 1st supply means 40, the fixed_quantity | feed_rate feeder generally used with an extruder can be used, for example. If a quantitative feeder is used, an aqueous dispersion (AW) having a desired average particle diameter can be more easily produced, and the amount of non-emulsified material in the aqueous dispersion (AW) can be reduced.
As the second supply means 50, for example, a container 51 filled with water, a pump 52 for feeding water in the container 51 to the twin screw extruder 10, and a supply pipe 53 connecting the pump 52 and the twin screw extruder 10 are connected. And a liquid supply means. As the pump 52, for example, a diaphragm pump, a plunger pump, or the like can be used.

The manufacturing method of the aqueous dispersion (AW) using the manufacturing apparatus 1 mentioned above is demonstrated.
In the manufacturing method of the aqueous dispersion (AW) of this embodiment, first, while rotating the two screws 12a and 12b of the twin screw extruder 10 heated in the barrel 11, the first supply means 40 The ethylene polymer (A), the acid-modified polyolefin (B), and the emulsifier (C) are continuously supplied to the end 11a side of the barrel 11 and melt kneaded.
The supply amount of the ethylene polymer (A) is preferably selected as appropriate according to the scale of the twin-screw extruder 10 (specifically, the diameters of the screws 12a and 12b).

  It is preferable that the supply amount of the emulsifier (C) is 1 to 20 parts by mass with respect to 100 parts by mass of the ethylene polymer (A). If the supply amount of the emulsifier (C) is 1 part by mass or more with respect to 100 parts by mass of the ethylene polymer (A), the ethylene polymer (A) can be easily dispersed in water, and 20 mass If it is at most parts, foaming of the aqueous dispersion (AW) can be prevented.

The temperature inside the barrel 11 of the twin screw extruder 10 is preferably adjusted to 130 to 250 ° C. If the temperature in the barrel 11 of the twin-screw extruder 10 is 130 ° C. or higher and 250 ° C. or lower, an aqueous dispersion (AW) can be stably produced.
The temperature of the barrel tip 11b of the twin-screw extruder 10 is preferably adjusted to 130 to 250 ° C.

Next, water is continuously supplied to the middle part of the barrel 11 by the second supply means 50, and further melt-kneaded and phase-inverted to prepare a phase inversion body.
It is preferable that the supply amount of water is 1 to 8 parts by mass with respect to 100 parts by mass of the ethylene-based polymer (A). If the amount of water supplied is 1 part by mass or more with respect to 100 parts by mass of the ethylene polymer (A), an aqueous dispersion can be easily produced, and if it is 8 parts by mass or less, the ethylene polymer (A ) Can be easily made into fine particles.
It is preferable to supply water at a constant rate because an aqueous dispersion (AW) having a desired average particle diameter can be easily produced and the amount of non-emulsified material can be reduced. For that purpose, it is preferable to use a highly accurate pump 52 of the second supply means 50.

Thereafter, the phase inversion body obtained by the twin-screw extruder 10 is transferred to the cooling extruder 20 via the connecting pipe 30a.
At that time, the temperature difference (T ₁ −T ₂ ) between the temperature T ₁ of the barrel tip 11 b of the twin-screw extruder 10 and the temperature T ₂ of the connecting pipe 30 a is set to 30 to 100 ° C., preferably 50 to 90 ° C. 70 to 90 ° C. is more preferable. Here, the temperature T ₁ at the barrel tip 11 b of the twin-screw extruder 10 is the temperature of the barrel at the extreme tip of the twin-screw extruder 10. The temperature T ₂ of the connecting pipe 30a, a temperature of the center portion of the connecting pipe 30a which is connected to the twin-screw extruder 10.
Moreover, the temperatures T ₁ and T ₂ are substantially the same as the temperature of the phase inversion body moving inside the measurement point.
Therefore, (T ₁ −T ₂ ) can be regarded as a temperature difference between the temperature of the phase change body moving the barrel tip 11b of the twin-screw extruder 10 and the temperature of the phase change body moving the connecting pipe 30a.
When (T ₁ -T ₂ ) is less than the lower limit, the particle size ratio of 0.5 μm or more increases, the average particle size increases, the particle size distribution increases, and the filterability decreases. On the other hand, when (T ₁ -T ₂ ) exceeds the upper limit, the amount of non-emulsified product increases.
In order to set (T ₁ -T ₂ ) to the above temperature, at least one of the temperature of the barrel tip 11b of the twin screw extruder 10 and the temperature of the connecting pipe 30a may be adjusted.

Next, the phase inversion body transferred to the cooling extruder 20 is cooled by the cooling extruder 20 to obtain an aqueous dispersion (AW). At that time, in order to prevent flashing of water contained in the phase inversion body (a phenomenon in which water vapor evaporates and repels in the phase inversion body), cooling to below the boiling point of water (100 ° C at an absolute pressure of 0.1 MPa). Is preferable, and cooling to 95 to 70 ° C. is more preferable.
After cooling, an aqueous dispersion (AW) is discharged from the tip of the cooling extruder 20. The aqueous dispersion (AW) discharged from the cooling extruder 20 may be diluted in a tank equipped with a stirrer. At that time, the dilution tank may be heated.

Examples of the ethylene polymer (A) used in this production method include ethylene polymers, ethylene and propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl. Copolymers of -1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene or 1-dodecene, these monomers and non-conjugated dienes, conjugated dienes, unsaturated carboxylic acids, unsaturated carboxylic anhydrides And the like.
Specifically, polyethylene, ethylene-propylene copolymer, ethylene-propylene-conjugated diene copolymer, ethylene-butene copolymer, ethylene-butene-propylene copolymer, and ethylene-octene copolymer are preferable. Further, modified polymers obtained by introducing acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and maleic anhydride into these copolymers are also preferred, and those having a mass average molecular weight of 5000 or more are preferred.
Further, the ethylene polymer (A) preferably has a mass average molecular weight of 5000 or more. The upper limit of the mass average molecular weight of the ethylene polymer (A) is not particularly limited, but is preferably 1000000 or less.

Examples of the ethylene polymer (A) include random copolymers of styrene and butadiene or isoprene, block copolymers, hydrogenated products thereof, various copolymers of vinyl esters such as vinyl acetate, A decomposition product or the like can also be used. Among various vinyl ester copolymers and hydrolysates thereof, it is preferable to use ethylene-vinyl acetate and partially saponified products or highly saponified products thereof.
An ethylene polymer (A) may be used individually by 1 type, and may use 2 or more types together.

  For example, an additive such as an antioxidant, a stabilizer, a lubricant, a plasticizer, or an inorganic filler may be added to the ethylene polymer (A).

The acid-modified polyolefin (B) is an α-olefin copolymer having an acid group, and its mass average molecular weight is preferably less than 5,000. The lower limit of the mass average molecular weight is not particularly limited, but is preferably 1000 or more. Examples of the α-olefin include ethylene, and examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic acid monoamide.
Acid-modified polyolefin (B) may be used individually by 1 type, and may use 2 or more types together.
The supply amount of the acid-modified polyolefin (B) is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the ethylene polymer (A). When the supply amount of the acid-modified polyolefin (B) is 5 parts by mass or more with respect to 100 parts by mass of the ethylene polymer (A), the ethylene polymer (A) can be easily dispersed in water. However, when it exceeds 30 mass parts, when it uses as a thermoplastic resin composition, it exists in the tendency for a physical-property balance to fall.

Examples of the emulsifier (C) used in the production method include various anionic surfactants and nonionic surfactants.
Examples of the anionic surfactant include primary higher fatty acid salts, secondary higher fatty acid salts, primary higher alcohol sulfates, secondary higher alcohol sulfates, primary higher alkyl sulfonates, Secondary higher alkyl sulfonate, higher alkyl disulfonate, sulfonated higher fatty acid salt, higher fatty acid sulfate ester salt, higher fatty acid ester sulfonate salt, higher alcohol ether sulfate ester, higher alcohol ether sulfonate salt, Examples include alkylolated sulfates of higher fatty acid amides, alkylbenzene sulfonates, alkylphenol sulfonates, alkylnaphthalene sulfonates, and alkylbenzoylimidazole sulfonates. An anionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.
Higher fatty acids constituting the emulsifier (C) include capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid and other saturated fatty acids, Linderic acid, Tuzic acid, Petroceric acid , Unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and arachidonic acid, or mixtures thereof.
Examples of elements for forming salts with higher fatty acids include alkali metals such as sodium and potassium.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, Examples thereof include fatty acid sucrose esters, alkylolamides, and polyoxyalkylene block copolymers. A nonionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

  The emulsifier (C) may be a powdery or granular solid, or may be a liquid.

As an aqueous medium used in this production method, for example, water or an aqueous solution of a basic substance (D) is used.
Examples of the basic substance (D) include alkali metals, alkaline earth metals, ammonia, amines and alkali metal oxides, hydroxides, weak acid salts, hydrides, and alkaline earth metal oxides, hydroxides, Examples include weak acid salts and aqueous solutions of hydrides. A basic substance (D) may be used individually by 1 type, and may use 2 or more types together.
As a specific example of the basic substance (D), an aqueous solution of potassium hydroxide is preferable.
In order to obtain an aqueous dispersion having a narrower particle size distribution, the basic substance (D) is added to the acid derived from the ethylene polymer (A), the acid-modified polyolefin (B) and the emulsifier (C). The amount is preferably 0.8 to 1.5 times, more preferably 1.0 to 1.3 times. If the addition amount of the basic substance (D) is less than 0.8 times, the average particle size may be large and the amount of the non-emulsified product may increase. If the addition amount exceeds 1.5 times, the particle size distribution is wide. May be.
1-8 mass parts is preferable with respect to 100 mass parts of ethylene-type polymer (A), and, as for the addition amount of the water used for a phase inversion, 2-5 mass parts is more preferable. If it is less than 1 part by mass and exceeds 8 parts by mass, it may become unstable during production and the amount of unemulsified product may increase.

  The aqueous dispersion (AW) may be subjected to a crosslinking treatment. As a method for the crosslinking treatment, 0.1 to 5 parts by mass of an organic peroxide such as t-butyl-cumyl peroxide and divinylbenzene with respect to 100 parts by mass of the solid content of the uncrosslinked aqueous dispersion (AW). Examples include a method in which 0.1 to 5 parts by mass of a polyfunctional compound such as the above is added and reacted at 60 to 140 ° C. for about 0.5 to 5 hours.

The aqueous dispersion (AW) obtained by the above production method can be used as a raw material for the graft polymer.
The aqueous dispersion (AW) exhibits adhesion, corrosion resistance, gas barrier properties, chipping resistance, heel mark resistance, and the like depending on the type of the ethylene polymer (A). Depending on the effect to be exhibited, it can be used as a moisture proofing agent, water repellent, film forming agent, coating agent on the product surface, or combined with other materials as a fiber treatment agent, heat sealant, binder, primer, etc. Or

In the above production method, since (T ₁ -T ₂ ) is within the above range, an aqueous dispersion having a small average particle size, a small amount of non-emulsified material, a narrow particle size distribution, and excellent filterability is easily produced. it can. Therefore, when the aqueous dispersion (AW) is used as the raw material for the AES resin, the surface smoothness, surface gloss, impact resistance and weather resistance of the AES resin can be improved.

(Method for producing graft polymer)
Next, an embodiment of the method for producing a graft polymer of the present invention will be described.
In one embodiment of the method for producing a graft polymer of the present invention, at least an aromatic vinyl monomer and a polymerization initiator are added to the aqueous dispersion (AW) obtained by the above-described method for producing an aqueous dispersion. This is a polymerization method. Thereby, graft polymer latex is obtained.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, and the like.
Further, in addition to the aromatic vinyl monomer, a vinyl cyanide monomer may be added, or other vinyl monomer that can be polymerized with the aromatic vinyl monomer and the vinyl cyanide monomer. Body may be added.
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.
Examples of other vinyl monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, methyl methacrylate, ethyl methacrylate, propylene methacrylate, and butyl methacrylate. Methacrylic acid alkyl ester and the like. Among these, butyl acrylate or methyl methacrylate is preferable.
Other vinyl monomers include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N N-substituted maleimide monomers such as -cyclohexylmaleimide can also be used.
Among them, it is preferable to add a vinyl cyanide monomer together with the aromatic vinyl monomer. In that case, since the physical property balance of the obtained thermoplastic resin composition is excellent, the aromatic vinyl monomer is used. It is preferable to set it as 60-80 mass%, and it is more preferable to set it as 60-76 mass%. Further, the vinyl cyanide monomer is preferably 40 to 20% by mass, and more preferably 40 to 24% by mass.

  As the polymerization initiator, an organic peroxide or an inorganic peroxide is used. Furthermore, the polymerization initiator is preferably a redox initiator in which an oil-soluble organic peroxide and a ferrous sulfate-chelating agent-reducing agent are combined. Examples of the oil-soluble organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, and the like. Among redox initiators, those composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate and dextrose are preferred.

  Specifically, in graft polymerization, a monomer mixture is prepared by mixing a redox initiator with an aromatic vinyl monomer and, if necessary, a vinyl cyanide monomer and another vinyl monomer. It is preferable to prepare and continuously add the monomer mixture to the aqueous dispersion (AW) over 1 hour. If the addition time of the monomer mixture is 1 hour or longer, the latex stability increases and the polymerization yield increases. The upper limit of the addition time of the monomer mixture is not particularly limited, but is preferably 10 hours or less.

Although there is no restriction | limiting in particular in the temperature in the case of graft polymerization, Usually, it shall be the range of 20-100 degreeC.
In the graft polymerization, the solid content of the aqueous dispersion (AW) is 40 to 80% by mass, the total monomer is 60 to 20% by mass (however, the total of the solid content of the aqueous dispersion (AW) and all the monomers is 100% by mass) is preferably added for polymerization. When the solid content of the aqueous dispersion (AW) is within the above range, impact resistance is enhanced.
After completion of the polymerization, an antioxidant may be added to the obtained graft polymer latex as necessary.
As a method for recovering the graft polymer (AG) from the graft polymer latex, for example, a precipitant is added to the graft polymer latex, and after heating and stirring, the precipitant is separated, washed with water, dehydrated, A drying precipitation method can be employed. As the precipitation agent in the precipitation method, for example, an aqueous solution of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, or the like can be used alone or in combination.

(Thermoplastic resin composition)
Next, an embodiment of a method for producing the thermoplastic resin composition of the present invention will be described.
One embodiment of the method for producing the thermoplastic resin composition of the present invention is a method in which a styrene polymer is mixed with the graft polymer produced by the method for producing a graft polymer described above.
Specifically, a graft polymer (AG), a styrene polymer (F) and, if necessary, an antioxidant, a lubricant, a processing aid, a pigment, and a filler are mixed, for example, an extruder, a banbury. A thermoplastic resin composition (AP) can be produced by melt-kneading using a mixer, a kneading roll or the like, and pelletizing.

<Styrene polymer (F)>
The styrene polymer (F) is a polymer having at least an aromatic vinyl monomer unit, and the styrene polymer (F) is composed of an aromatic vinyl monomer unit and a vinyl cyanide monomer. A copolymer having units is preferred.
In addition, the styrene polymer (F) may be copolymerized with other vinyl monomer units copolymerizable with the aromatic vinyl monomer units and the vinyl cyanide monomer units. .
Examples of the aromatic vinyl monomer, vinyl cyanide monomer, and other vinyl monomers are the same as those used during graft polymerization. It need not be the same as that used for the graft polymer.
Although there is no restriction | limiting in particular in a composition of a styrene-type polymer (F), What contains 60-76 mass% of aromatic vinyl-type monomer units and 40-24 mass% of vinyl cyanide-type monomer units is preferable. When it has another vinyl-type monomer unit, it is preferable that another vinyl-type monomer unit is 20 mass% or less. The other vinyl monomer units may be 0% by mass.

For the production of the styrenic polymer (F), a polymerization method such as suspension polymerization is employed for emulsion polymerization. When the styrene polymer (F) is produced by emulsion polymerization, each monomer, an emulsifier, a polymerization initiator, and a chain transfer agent are charged into the reactor and polymerized by heating to obtain the styrene polymer. A styrene polymer (F) is recovered from the latex by a precipitation method.
Here, as an emulsifier, general emulsifiers for emulsion polymerization such as potassium rosinate and sodium alkylbenzenesulfonate can be used. Moreover, organic and inorganic peroxide initiators can be used as the polymerization initiator, and mercaptans, α-methylstyrene dimers, terpenes, and the like can be used as the chain transfer agent. As the precipitation method, a method similar to that for recovering the graft polymer (AG) from the graft polymer latex can be employed.
When producing by suspension polymerization, each monomer, suspending agent, suspending aid, polymerization initiator, and chain transfer agent are charged into the reactor, polymerized by heating, and the resulting styrenic polymer. The slurry is dehydrated to recover the styrene polymer (F).
Here, as the suspending agent, tricalcium phosphite, polyvinyl alcohol or the like can be used, and as the suspending aid, sodium alkylbenzene sulfonate or the like can be used. Further, organic peroxides can be used as the polymerization initiator, and mercaptans, α-methylstyrene dimer, terpenes, and the like can be used as the chain transfer agent.

  The thermoplastic resin composition (AP) has a particularly good balance between surface appearance and mechanical strength. Therefore, the above-mentioned graft is added to 100 parts by mass of the graft polymer (AG) and the styrene polymer (F). The polymer (AG) content is preferably 5 to 70 parts by mass and the styrene polymer (F) content is preferably 95 to 30 parts by mass, and the graft polymer (F) content is 10 to 50 parts. It is more preferable that content of a mass part and a styrene-type polymer (F) is 90-50 mass parts. If the content of the graft polymer (AG) is less than the lower limit, the impact resistance may be lowered. Further, when the content of the graft polymer (AG) exceeds the upper limit, the surface appearance (flow mark) may be impaired.

<Other polymer (G)>
In addition to the graft polymer (AG) and the styrene polymer (F), the thermoplastic resin composition (AP) may contain another polymer (G). Examples of the other polymer (G) include polymethyl methacrylate resin, nylon 6 resin, nylon 66 resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate resin, polystyrene resin and high impact polystyrene resin ( HIPS resin). These other polymers (G) may be used alone or in a blend of two or more.

(Other embodiments)
The present invention is not limited to the exemplary embodiments described above. For example, in the present invention, the cooling means uses an extruder, but various machines such as a jacketed static mixer can also be used.

(Description of materials used in Examples)
<Ethylene polymer (A)>
(A-1): EPDM (Mitsui Chemicals, Tuffmer TP3180, MFR at 190 ° C. is 5.0 g / 10 min)
(A-2): EPDM (manufactured by Dow Chemical Co., Ltd., Nodel IP4520P, Mooney viscosity at 100 ° C. (ML1 + 4) 32)
(A-3): Linear low-density polyethylene (manufactured by Prime Polymer Co., Ltd., Evolution SP2540, MFR at 190 ° C. is 3.8 g / 10 min)
(A-4): Low density polyethylene (Tosoh Co., Ltd., Petrocene 353, MFR at 190 ° C. is 145 g / 10 min)
<Acid-modified polyolefin (B)>
(B): acid-modified polyethylene (manufactured by Mitsui Chemicals, high wax 2203A, mass average molecular weight; 2700, acid value; 30 mg / g)
<Emulsifier (C)>
(C): Semi-cured beef tallow fatty acid potassium (manufactured by Kao Corporation, KS soap)
<Basic substance (D)>
Potassium hydroxide

[Example 1]
In this example, first, the temperature T ₁ of the twin screw extruder (Ikegai PCM-30, screw diameter 30 mm, L / D = 40) barrel tip 11b (see FIG. 1) is set to 200 ° C. While the two screws of the twin screw extruder are rotated in the same direction, the ethylene polymer (A-1), the acid-modified polyolefin (B), and the emulsifier (C) are mixed in the twin screw extruder. Continuously fed to the end of the barrel. In this case, the supply amount of the acid-modified polyolefin (B) is 12 parts by mass with respect to 100 parts by mass of the ethylene polymer (A-1), and the supply amount of the emulsifier (C) is ethylene polymer (A-1). ) It was 2.4 parts by mass with respect to 100 parts by mass, and the total of the ethylene polymer (A-1), the acid-modified polyolefin (B) and the emulsifier (C) was 4 kg / hour. Moreover, it is 1. with respect to the quantity required in order to neutralize the acid derived from ethylene polymer (A-1), acid-modified polyolefin (B), and an emulsifier (C) from the aqueous solution supply port provided in the intermediate part. Three times the amount of basic substance (D) 0.4 parts by mass and 2.6 parts by mass of water were supplied. In the presence of the emulsifier (C), the ethylene polymer (A-1) and water were mixed and phase-inverted to prepare a phase-inverted body.
Thereafter, the phase change body obtained by the twin screw extruder was adjusted to a temperature of 130 ° C. (T ₂ = 130 ° C.), and the connecting tube 30a (the hole diameter d was 30 mm, the length was 400 mm, the flow path length L was 480 mm, {(D ³ · L) / d ⁴ } was transferred to a single screw extruder as cooling means via 16), cooled to 95 ° C. and taken out. The taken out aqueous dispersion was transferred to a dispersion tank equipped with a stirrer, and diluted with dilution water to a solid content concentration of around 40% by mass to obtain an aqueous dispersion (AW-1). The average particle size of this aqueous dispersion, the particle size ratio of 0.5 μm or more, the mass ratio of the non-emulsified product, and the filterability were measured by the following methods. The results are shown in Table 1.

<Average particle size>
The volume-based average particle diameter was measured using Nanotrack (Nanotrack 150) (measuring solvent: pure water) manufactured by Nikkiso Co., Ltd.
<0. Particle size ratio of 5 μm or more>
The particle size frequency (%) of 0.5 μm or more was determined from the particle size measured using Nanotrack (Nanotrack 150) (measuring solvent: pure water) manufactured by Nikkiso Co., Ltd.
<Mass ratio of non-emulsified>
The aqueous dispersion was filtered through a 100 mesh stainless steel wire mesh, and the residue on the mesh was washed with water and dried, and then the mass of the filtered solid residue was measured. The mass ratio of the non-emulsified product in the aqueous dispersion was determined by the following formula (2).
Formula (2) Mass ratio (% by mass) of non-emulsified material = [mass of residual solid content of filtration (g) / mass of total solid content (g)] × 100 (mass%)
<Filterability>
1000 g of the aqueous dispersion after being filtered with a 100 mesh wire mesh was filtered with a suction type filtration device sandwiching 300 mesh of nylon, and the amount of treatment passed was measured. The greater the throughput, the better the filterability.

[Example 2]
An aqueous dispersion (AW-2) was obtained in the same manner as in Example 1 except that the temperature of the connecting pipe 30a was 160 ° C. This aqueous dispersion (AW-2) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 3]
An aqueous dispersion (AW-3) was obtained in the same manner as in Example 1 except that the temperature of the connecting pipe 30a was changed to 110 ° C. This aqueous dispersion (AW-3) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 4]
An aqueous dispersion (AW-4) was obtained in the same manner as in Example 1 except that the temperature of the biaxial extruder barrel tip 11b was 180 ° C. and the temperature of the connecting tube 30a was 140 ° C. This aqueous dispersion (AW-4) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 5]
An aqueous dispersion (AW-5) was obtained in the same manner as in Example 1 except that the temperature of the biaxial extruder barrel tip 11b was 160 ° C. and the temperature of the connecting tube 30a was 120 ° C. This aqueous dispersion (AW-5) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 6]
An aqueous dispersion (AW-6) was obtained in the same manner as in Example 1 except that the temperature of the twin-screw extruder barrel tip 11b was 140 ° C and the temperature of the connecting tube 30a was 100 ° C. This aqueous dispersion (AW-6) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 7]
An aqueous dispersion (AW-7) was obtained in the same manner as in Example 1 except that the addition amount of the basic substance was changed to 0.2 part of 0.7 times the amount. This aqueous dispersion (AW-7) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Example 8]
An aqueous dispersion (AW-8) was obtained in the same manner as in Example 1 except that the amount of the basic substance added was 0.5 times the 1.6 times amount. This aqueous dispersion (AW-8) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Example 9]
An aqueous dispersion (AW-9) was obtained in the same manner as in Example 1 except that the amount of water added was 0.8 part. This aqueous dispersion (AW-9) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Example 10]
An aqueous dispersion (AW-10) was obtained in the same manner as in Example 1 except that the amount of water added was 8.2 parts. This aqueous dispersion (AW-10) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Example 11]
A twin screw extruder (Ikegai PCM-30 type, screw diameter 30 mm, L / D = 40) barrel tip 11 b (see FIG. 1) temperature T ₁ was set to 200 ° C. While rotating two screws in the same direction, ethylene polymer (A-2), acid-modified polyolefin (B), and emulsifier (C) are continuously connected to the end of the barrel of the twin screw extruder. Supplied. The ethylene-based polymer (A-2) is a bale-like rubber, which was used by adjusting in advance to 8 mm square using a pulverizer (DAS-14 type manufactured by Daiko Seiki Co., Ltd.). The supply amount of the acid-modified polyolefin (B) is 15 parts by mass with respect to 100 parts by mass of the ethylene polymer (A-2), and the supply amount of the emulsifier (C) is 100 masses of the ethylene polymer (A-2). The total amount of the ethylene polymer (A-2), the acid-modified polyolefin (B), and the emulsifier (C) was 4 kg / hour. Moreover, it is 1. with respect to the quantity required to neutralize to the acid derived from ethylene polymer (A-2), acid-modified polyolefin (B), and an emulsifier (C) from the aqueous solution supply port provided in the intermediate part. 0.4 parts by mass and 2.6 parts by mass of water of 3 times the basic substance (D) were supplied. In the presence of the emulsifier (C), the ethylene polymer (A-2) and the aqueous medium were mixed and phase-inverted to prepare a phase-inverted body.
Thereafter, the phase change body obtained by the twin screw extruder was adjusted to a temperature of 130 ° C. (T ₂ = 130 ° C.), and the connecting tube 30a (the hole diameter d was 30 mm, the length was 400 mm, the flow path length L was 480 mm, {(D ³ · L) / d ⁴ } was transferred to a single screw extruder as cooling means via 16), cooled to 95 ° C. and taken out. The taken-out aqueous dispersion was transferred to a dispersion tank equipped with a stirrer, and diluted with dilution water to a solid content concentration of around 40% by mass to obtain an aqueous dispersion (AW-11). This aqueous dispersion (AW-11) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Example 12]
Twin screw extruder (Ikegai PCM-30 type, screw diameter 30 mm, L / D = 40) The temperature T ₁ of the barrel tip 11b is set to 200 ° C., and the two screws of the twin screw extruder are While rotating in the same direction, ethylene polymer (A-3), acid-modified polyolefin (B), and emulsifier (C) were continuously supplied to the end of the barrel of the twin-screw extruder. In this case, the supply amount of the acid-modified polyolefin (B) is 15 parts by mass with respect to 100 parts by mass of the ethylene polymer (A-3), and the supply amount of the emulsifier (C) is ethylene polymer (A-3). And 3.0 parts by mass with respect to 100 parts by mass, and the total of the ethylene polymer (A-3), the acid-modified polyolefin (B) and the emulsifier (C) was 4 kg / hour. Moreover, it is 1. with respect to the quantity required to neutralize to the acid derived from ethylene polymer (A-3), acid-modified polyolefin (B), and an emulsifier (C) from the aqueous solution supply port provided in the intermediate part. 0.4 parts by mass and 2.6 parts by mass of water of 3 times the basic substance (D) were supplied. In the presence of the emulsifier (C), the ethylene polymer (A-3) and the aqueous medium were mixed and phase-inverted to prepare a phase-inverted body.
Thereafter, the phase change body obtained by the twin screw extruder was adjusted to a temperature of 130 ° C. (T ₂ = 130 ° C.), and the connecting tube 30a (hole diameter d was 30 mm, length was 400 mm, flow path length L was 480 mm, {(D ³ · L) / d ⁴ } was transferred to a single screw extruder as cooling means via 16), cooled to 95 ° C. and taken out. The taken out aqueous dispersion was transferred to a dispersion tank equipped with a stirrer, and diluted with dilution water to a solid content concentration of around 40% by mass to obtain an aqueous dispersion (AW-12). This aqueous dispersion (AW-12) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Example 13]
Twin screw extruder (Ikegai PCM-30 type, screw diameter 30 mm, L / D = 40) The temperature T ₁ of the barrel tip 11b is set to 200 ° C., and the two screws of the twin screw extruder are While rotating in the same direction, ethylene polymer (A-4), acid-modified polyolefin (B), and emulsifier (C) were continuously supplied to the end of the barrel of the twin screw extruder. In this case, the supply amount of the acid-modified polyolefin (B) is 15 parts by mass with respect to 100 parts by mass of the ethylene polymer (A-4), and the supply amount of the emulsifier (C) is ethylene polymer (A-4). And 3.0 parts by mass with respect to 100 parts by mass, and the total of the ethylene polymer (A-4), the acid-modified polyolefin (B) and the emulsifier (C) was 4 kg / hour. Moreover, it is 1. with respect to the quantity required in order to neutralize the acid derived from ethylene polymer (A-4), acid-modified polyolefin (B), and emulsifier (C) from the aqueous solution supply port provided in the intermediate part. 0.4 parts by mass and 2.6 parts by mass of water of 3 times the basic substance (D) were supplied. In the presence of the emulsifier (C), the ethylene polymer (A-4) and the aqueous medium were mixed and phase-inverted to prepare a phase-inverted body.
Thereafter, the phase change body obtained by the twin screw extruder was adjusted to a temperature of 130 ° C. (T ₂ = 130 ° C.), and the connecting tube 30a (the hole diameter d was 30 mm, the length was 400 mm, the flow path length L was 480 mm, {(D ³ · L) / d ⁴ } was transferred to a single screw extruder as cooling means via 16), cooled to 95 ° C. and taken out. The taken out aqueous dispersion was transferred to a dispersion tank equipped with a stirrer, and diluted with dilution water to a solid content concentration of around 40% by mass to obtain an aqueous dispersion (AW-13). This aqueous dispersion (AW-13) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Comparative Example 1]
The temperature _{T 2} of the connecting tube 30a except for using 180 ° C. in the same manner as in Example 1 to obtain an aqueous dispersion (AW-14). This aqueous dispersion (AW-14) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 2]
The temperature _{T 2} of the connecting tube 30a except for using 90 ° C. in the same manner as in Example 1 to obtain an aqueous dispersion (AW-15). This aqueous dispersion (AW-15) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 3]
The temperature _{T 2} of the connecting tube 30a except for using 180 ° C. in the same manner as in Example 11 to obtain an aqueous dispersion (AW-16). This aqueous dispersion (AW-16) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 4]
The temperature _{T 2} of the connecting tube 30a except for using 90 ° C. in the same manner as in Example 11 to obtain an aqueous dispersion (AW-17). This aqueous dispersion (AW-17) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 5]
The temperature _{T 2} of the connecting tube 30a except for using 180 ° C. in the same manner as in Example 12 to obtain an aqueous dispersion (AW-18). This aqueous dispersion (AW-18) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 6]
The temperature _{T 2} of the connecting tube 30a except for using 90 ° C. in the same manner as in Example 12 to obtain an aqueous dispersion (AW-19). This aqueous dispersion (AW-19) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 7]
The temperature _{T 2} of the connecting tube 30a except for using 180 ° C. in the same manner as in Example 13 to obtain an aqueous dispersion (AW-20). This aqueous dispersion (AW-20) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 8]
The temperature _{T 2} of the connecting tube 30a except for using 90 ° C. in the same manner as in Example 13 to obtain an aqueous dispersion (AW-21). This aqueous dispersion (AW-21) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Evaluation results)
In the aqueous dispersions (AW) of Examples 1 to 13 in which (T ₁ -T ₂ ) is within the scope of the invention according to claim 1, the mass ratio of the non-emulsified material was small. Moreover, there were few particle diameter ratios of 0.5 micrometer or more, and filterability was excellent. In particular, the amount of the base of the component (A) + (B) + (C) with respect to the acid is in the range of 0.8 to 1.5 times, and the amount of water added is in the range of 1.0 to 8.0 parts by mass. In Examples 1 to 6 and Examples 11 to 13, the particle diameter ratio of 0.5 μm or more was smaller, and the filterability was more excellent.
In the aqueous dispersions of Comparative Examples 1 to 8 where (T ₁ -T ₂ ) is outside the scope of the invention according to claim 1 of the present application, the particle size ratio of 0.5 μm or more was large, and the filterability was low.

[Example 14]
<Preparation of graft polymer (AG-1)>
To 100 parts by mass of the aqueous dispersion (AW-1) obtained in Example 1, 1 part by mass of t-butyl-cumyl peroxide and 1 part by mass of divinylbenzene were added and reacted at 135 ° C. for 5 hours. A crosslinked aqueous dispersion (AW-1 ′) was obtained.
In a stainless polymerization tank equipped with a stirrer, 240 parts by mass of ion exchange water, 65 parts by mass of cross-linked aqueous dispersion (AW-1 ′) as solids, 0.006 parts by mass of ferrous sulfate, 0.3 parts by mass of sodium pyrophosphate And 0.35 parts by mass of dextrose was charged, and the temperature was 80 ° C. Next, 6.6 parts by mass of acrylonitrile, 23.4 parts by mass of styrene and 0.6 parts by mass of cumene hydroperoxide were continuously added for 180 minutes, and the polymerization temperature was kept constant at 80 ° C. to carry out emulsion polymerization. After polymerization, an antioxidant is added to the aqueous dispersion containing the obtained graft polymer (AG-1), and further, sulfuric acid is added to precipitate a solid, followed by washing, dehydration, and drying steps. The graft polymer (AG-1) was obtained.
<Preparation of styrene polymer (F)>
In a stainless steel polymerization reactor equipped with a stirrer substituted with nitrogen, 120 parts by mass of ion exchange water, 0.1 part by mass of polyvinyl alcohol, 0.3 part by mass of azobisisobutyronitrile, 34 parts by mass of acrylonitrile, 66 parts by mass of styrene, 0.3 parts by mass of t-dodecyl mercaptan was charged. The temperature of the reactor was set to 50 ° C. and polymerization was performed for 5 hours, and then the temperature was raised to 120 ° C. and reacted for 4 hours. Next, the contents inside the reactor were extracted, washed and dried to obtain a powdery styrene polymer (F).
<Preparation of thermoplastic resin composition (AP)>
30 parts by mass of the graft polymer (AG-1) and 70 parts by mass of a styrene polymer (F) were mixed, and a twin screw extruder with a vacuum diameter of 30 mm (PCM-30 type, manufactured by Ikegai Co., Ltd.) was used. A thermoplastic resin composition (AP-1) was prepared by melting and kneading under vacuum conditions of 240 ° C. and 93.325 kPa.
A test piece for Charpy impact test measurement and a flat plate of 100 mm × 100 mm × 3 mm were molded from the obtained pellets using an injection molding machine. Using this molded plate, Charpy impact value, glossiness and surface smoothness were evaluated as follows. The results are shown in Table 4.

<Charpy impact strength>
About the said test piece, it measured on 23 degreeC conditions according to ISO179 specification.
<Glossiness>
The glossiness of the surface of the flat plate was determined from the reflectance at an incident angle of 60 ° and a reflection angle of 60 ° using a digital goniophotometer UGV-5D (manufactured by Suga Test Instruments).
<Surface smoothness>
The number of irregularities per 1 mm ² on the surface of the flat plate was visually counted using an optical microscope (manufactured by Nikon Corporation).

[Example 15]
A thermoplastic resin composition (AP-2) is obtained in the same manner as in Example 14 except that the graft polymer (AG-1) is changed to 40 parts by mass and the styrene polymer (F) is changed to 60 parts by mass. It was. This thermoplastic resin composition (AP-2) was evaluated in the same manner as in Example 14. The evaluation results are shown in Table 4.

[Example 16]
<Preparation of graft polymer (AG-2)>
A graft polymer (AG-2) was obtained in the same manner as in Example 14, except that the aqueous dispersion (AW) was changed to (AW-11) obtained in Example 11.
<Adjustment of thermoplastic resin composition (AP-3)>
A thermoplastic resin composition (AP-3) was obtained in the same manner as in Example 14 except that the graft polymer was changed to (AG-2). This thermoplastic resin composition (AP-3) was evaluated in the same manner as in Example 14. The evaluation results are shown in Table 4.

[Example 17]
A thermoplastic resin composition (AP-4) is obtained in the same manner as in Example 16 except that the graft polymer (AG-2) is changed to 40 parts by mass and the styrene polymer (F) is changed to 60 parts by mass. It was. This thermoplastic resin composition (AP-4) was evaluated in the same manner as in Example 14. The evaluation results are shown in Table 4.

[Comparative Example 9]
<Preparation of graft polymer (AG-3)>
A graft polymer (AG-3) was obtained in the same manner as in Example 14 except that the aqueous dispersion (AW) was changed to (AW-14) obtained in Comparative Example 1.
<Adjustment of thermoplastic resin composition (AP-5)>
A thermoplastic resin composition (AP-5) was obtained in the same manner as in Example 14 except that the graft polymer was changed to (AG-3). This thermoplastic resin composition (AP-5) was evaluated in the same manner as in Example 14. The evaluation results are shown in Table 4.

[Comparative Example 10]
A thermoplastic resin composition (AP-6) is obtained in the same manner as in Comparative Example 9, except that the graft polymer (AG-3) is changed to 40 parts by mass and the styrene polymer (F) is changed to 60 parts by mass. It was. This thermoplastic resin composition (AP-6) was evaluated in the same manner as in Example 14. The evaluation results are shown in Table 4.

[Comparative Example 11]
<Preparation of graft polymer (AG-4)>
A graft polymer (AG-4) was obtained in the same manner as in Example 14 except that the aqueous dispersion (AW) was changed to (AW-16) obtained in Comparative Example 3.
<Preparation of thermoplastic resin composition (AP-7)>
A thermoplastic resin composition (AP-7) was obtained in the same manner as in Example 14 except that the graft polymer was changed to (AG-4). This thermoplastic resin composition (AP-7) was evaluated in the same manner as in Example 14. The evaluation results are shown in Table 4.

[Comparative Example 12]
A thermoplastic resin composition (AP-8) is obtained in the same manner as in Comparative Example 11 except that the graft polymer (AG-4) is changed to 40 parts by mass and the styrene polymer (F) is changed to 60 parts by mass. It was. This thermoplastic resin composition (AP-8) was evaluated in the same manner as in Example 14. The evaluation results are shown in Table 4.

(Evaluation results)
In the thermoplastic resin compositions of Examples 14 to 17 using the aqueous dispersion (AW) of Example 1 or Example 11 as the graft polymer (AG), both the glossiness and surface smoothness of the molded product are excellent. It was.
In the thermoplastic resin compositions of Comparative Examples 9 to 12 using the aqueous dispersion (AW) of Comparative Example 1 or Comparative Example 3 as the graft polymer (AG), both the glossiness and surface smoothness of the molded article were low. .
In Examples 14-17 and Comparative Examples 9-12, there was no difference in Charpy impact strength.

  The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention. The present invention is not limited by the above description, but only by the scope of the appended claims.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 10 Twin screw extruder 11 Barrel 11a Terminal 11b Tip 12a, 12b Screw 20 Cooling extruder (cooling means)
30 Flow path 30a Connecting pipe 40 First supply means 50 Second supply means 51 Container 52 Pump 53 Supply pipe

Claims (3)

A phase change body is prepared by dispersing an ethylene polymer in an aqueous medium by a twin screw extruder in which two screws are provided in a barrel.
A method for producing an aqueous dispersion, wherein the phase inversion body is cooled using a cooling means,
The twin-screw extruder and the cooling means are connected by a connecting pipe, and the difference (T ₁ -T ₂ ) between the temperature T ₁ at the tip of the twin-screw extruder barrel and the temperature T ₂ of the connecting pipe is in the range of 30 to 100 ° C. A method for producing an aqueous dispersion, wherein An aqueous dispersion is produced by the method for producing an aqueous dispersion according to claim 1,
A method for producing a graft polymer, wherein at least an aromatic vinyl monomer and a polymerization initiator are added to the aqueous dispersion to perform graft polymerization. A graft polymer is produced by the method for producing a graft polymer according to claim 2,
A method for producing a thermoplastic resin composition, wherein the graft polymer is mixed with a styrene polymer having at least an aromatic vinyl monomer unit.

Images