WO2006098287A1

WO2006098287A1 - Method and apparatus for recovering (rubber-reinforced) styrene resin composition

Info

Publication number: WO2006098287A1
Application number: PCT/JP2006/304931
Authority: WO
Inventors: Kenichi Urabe
Original assignee: Techno Polymer Co., Ltd.
Priority date: 2005-03-15
Filing date: 2006-03-13
Publication date: 2006-09-21
Also published as: CN101175794A; KR101279244B1; CN101175794B; JP2006291187A; KR20070110940A; JP5064701B2

Abstract

A method by which various kinds of rubber-reinforced styrene resin compositions of good quality can be recovered in a small amount of energy in a satisfactory yield without posing a problem concerning environmental pollution. The method for recovering a (rubber-reinforced) styrene resin composition is characterized by conducting: a plastication step in which a styrene resin (A) is plasticated; a coagulation step in which a (rubber-reinforced) styrene resin latex (B) is mixed with a coagulant (C) to obtain a creamy substance (D); a mixing step in which the creamy substance (D) is fed to an extruder in which the styrene resin (A) which has undergone the plastication step is present, and they are mixed in the extruder to obtain a mixture (E); a draining step in which water is removed from the mixture (E) and discharged from the extruder; and a volatilization step in which volatile matters are removed from the mixture which has undergone the water removal and discharged from the extruder, the (rubber-reinforced) styrene resin composition being recovered from the extruder.

Description

Specification

(Rubber reinforced) Recovery method and apparatus for styrene resin composition

Technical field

The present invention relates to a method for recovering a (rubber reinforced) styrene resin composition from a (rubber reinforced) styrene resin latex. Specifically, various types of high-quality (rubber reinforced) styrene resin compositions with good yields can be recovered with small energy that does not cause fine powder scattering or a large amount of drainage, or cause environmental pollution problems. Regarding the method.

(Rubber-reinforced) Styrenic resin latex refers to rubber-reinforced styrene resin latex and / or styrene resin latex. Similarly, the (rubber reinforced) styrene resin composition represents a rubber reinforced styrene resin composition and / or a styrene resin composition.

Background art

[0002] Rubber-reinforced styrene-based resin compositions used in the manufacture of ABS resin pellets are conventionally manufactured by coagulating and slurrying rubber-reinforced styrene-based resin latex, washing and dehydrating, and drying. .

However, the conventional method has problems such as a large amount of drainage in the washing and dehydration process, a large amount of energy in the drying process, generation of exhaust gas, and generation of fine powder and scattering. There were problems such as poor productivity and high environmental pollution measures. For this reason, the following method has been proposed.

(1) Solidification → Washing 'Dehydration → Drawing dewatering extrusion' Pelletization.

This is a method in which a rubber-reinforced styrene resin latex is coagulated and slurried, washed and dehydrated, then supplied to an extruder, squeezed and dehydrated, and then extruded from the extruder as it is to pelletize.There is no drying process in this method. There are advantages such as saving energy for drying and less exhaust gas, but separate processes such as coagulation, dehydration, and washing are required, and a large amount of waste discharged in the dehydration and washing process is still required. Waste water treatment is necessary. In addition, there are restrictions on the resin that is suitable for squeezing and dewatering, so it cannot be applied to all types of products. There is also a problem.

(2) Extruder coagulation → dehydration · drying → pelletization (Figure 3).

This is a method in which a rubber-reinforced styrene resin latex is coagulated in an extruder 10X to form a slurry, dehydrated, dried and pelletized (see Patent Document 1).

In general, resins with high molecular weight and resins with high rubber components have high melt viscosity, so when processing these resins by this method, very high power is required for melt extrusion in the extruder 10X. The resin temperature may increase due to large heat generation. As a result, there were cases where the impact strength of the resin discharged from the extruder 10X was lowered or the color tone deteriorated.

In addition, since the solidified resin is washed and drained in a state where it is not sufficiently melted, the resin having a small particle size is discharged together with water through the mechanical filter 61, and the recovery is greatly enhanced. It may be necessary.

In addition, since the length (L / D) of the extruder 10X with respect to the cylinder diameter becomes long, there are problems in terms of operation operability and machine maintenance.

In addition, since the coagulation process and the molten resin extrusion process are performed in a single extruder, it may not be possible to select an optimum rotation speed suitable for both, in which case operation may be performed at a certain compromise rotation speed. I do not get. As a result, stable operation may be difficult, or an excessive rotational speed may cause problems that deteriorate the physical properties of the resin.

(3) Solidification → Cleaning · Dehydration → Plasticizing resin mixing · Drawing dewatering extrusion * Pelletization.

After the rubber-reinforced styrene resin latex is coagulated and slurried, washed and dehydrated and recovered as a wet powder, this wet powder is fed into an extruder that is plasticizing a styrene resin, and is then put into the extruder. This is a method of mixing with the plasticized styrenic resin, dehydrating and discharging moisture, devolatilizing and discharging the volatile matter, and pelletizing (see Patent Document 2).

Similar to (1) above, this method has advantages such as saving energy for drying and reducing exhaust gas, since there is no drying process. However, there is still a problem that a separate process such as coagulation and dehydration washing is necessary, and a large amount of wastewater treatment is necessary in the process. Patent Document 1: USP3993292

Patent Document 2: Japanese Patent No. 3597070

Disclosure of the invention

Problems to be solved by the invention

[0003] The present invention has a small yield that does not cause fine powder scattering and a large amount of drainage, and does not cause environmental pollution problems. The present invention also has a separate solidification, dehydration, and washing process. It is an object of the present invention to provide a method for recovering high-quality (rubber reinforced) styrene resin compositions of various varieties.

Means for solving the problem

[0004] The present invention is configured as the following [1] to [9].

[1] Configuration 1:

A plasticizing process for plasticizing the styrene resin (A),

(Rubber Reinforcement) Coagulation process to obtain cream-like substance (D) by mixing styrene resin latex (B) and coagulant (C),

A mixing step of supplying the cream-like substance (D) into an extruder in which the styrenic resin (A) after the plasticizing step is present and mixing in the extruder to obtain a mixture (E);

A drainage step of removing water from the extruder by removing water from the mixture (E), a devolatilization step of devolatilizing the mixture after removing the water and discharging volatile matter from the extruder,

To recover the (rubber reinforced) styrene-based resin composition from within the extruder.

Here, (rubber reinforced) styrene resin latex (B) represents rubber reinforced styrene resin latex (B) and / or styrene resin latex (B). Similarly, (rubber reinforced) styrene resin composition represents a rubber reinforced styrene resin composition and / or a styrene resin composition. The same shall apply hereinafter.

Creamy substance (D) is a paste-like (rubber reinforced) styrene resin that does not separate into a solid and a liquid even when left at room temperature for a long time (eg 1 day). (Rubber reinforced) Use styrene resin. (Rubber reinforced) Creamy substance by coagulating styrene resin latex (B) Since there is no water separated at that time as (D), it can be well mixed in the extruder with the styrenic resin (A) after the plasticizing step.

[2] Configuration 2:

In configuration 1,

Performing the plasticizing step in the extruder upstream of the supply position of the cream substance (D),

A method for recovering a (rubber reinforced) styrene-based resin composition.

This collection method can be realized by using the collection apparatus illustrated in FIG.

[3] Configuration 3:

In configuration 1,

The plasticizing styrenic resin (A) is supplied into the extruder on the upstream side of the supply position of the cream-like substance (D) by performing the plasticizing step in a plasticizer. (Rubber Reinforcement) A method for recovering a styrene resin composition.

This collection method can be realized by the collection apparatus illustrated in FIG.

[4] Configuration 4:

In any of configurations 1 to 3,

The coagulation temperature in the coagulation step is (Tm-70) ° C or more when the Vicat softening temperature of the resin of the (rubber reinforced) styrene resin latex (B) is Tm ° C.

A method for recovering a styrene-based resin composition (rubber reinforced).

When the coagulation temperature is less than (Tm-70) ° C, the mixture of the styrene resin latex (B) and the coagulant (C) has many non-creamy parts, resulting in the plasticization process. There will be many parts that cannot be mixed well with the later styrenic resin (A).

[5] Configuration 5:

In any of configurations 1 to 4,

The solid content concentration of the cream substance (D) obtained in the coagulation step and fed into the extruder is in the range of 15 to 40% by mass.

A method for recovering a (rubber reinforced) styrene-based resin composition.

When the solid content of the cream substance (D) is less than 15% by mass, In the mixture of latex (B) and coagulant (C), there may be a lot of separated water that is not creamy. As a result, it can be mixed well with the styrenic resin (A) after the plasticization process. There are many parts that can't be heard. When the solid content concentration of the cream substance (D) exceeds 40%, the viscosity becomes too high, and the mixture of the styrene resin latex (B) and the coagulant (C) is mixed with the styrene resin after the plasticization process. It becomes difficult to supply the resin (A).

[6] Configuration 6:

In any of configurations 1 to 4,

Wash water at 100 ° C. or more is supplied into the extruder downstream from the supply position of the cream substance (D), and the wash water and the mixture (E ) To discharge the moisture in the extruder,

A method for recovering a (rubber reinforced) styrene-based resin composition.

[7] Configuration 7:

In configuration 6,

A gas-liquid separation tank is provided at the subsequent stage of the mechanical filter, and drainage is performed while controlling the pressure of the gas phase in the gas-liquid separation tank.

A method for recovering a styrene-based resin composition (rubber reinforced).

[8] Configuration 8:

It has a main extruder, an auxiliary extruder for plasticizing styrene resin, and a solidification device.The main extruder has a first supply port for the auxiliary extruder at the most upstream position. A second supply port for the coagulation apparatus downstream of the first supply port, and further on the downstream side of the supply port for cleaning water, the drainage port for cleaning water, and Has a devolatilization outlet,

A discharge port of the auxiliary extruder is connected to the first supply port;

A discharge port of the coagulation apparatus is connected to the second supply port;

The styrenic resin plasticized in the auxiliary extruder is supplied to the first supply loci and the main extruder and creamed (rubber reinforced) styrene resin in the coagulation apparatus is supplied to the second supply loca. The mixture is fed and mixed, and the mixture is melted in the main extruder and washed with washing water supplied from the water supply port. Drain through the Kal filter, devolatilize the mixture after water drainage under negative pressure, and discharge the volatile components to the devolatilization loca.

A (rubber reinforced) styrene-based resin composition recovery device.

An example of this collection device is shown in FIG.

[9] Configuration 9:

In configuration 8,

A gas-liquid separation tank is provided downstream of the mechanical filter, and a drainage device is provided for draining water while controlling the pressure in the gas phase in the gas-liquid separation tank. (Rubber-reinforced) Styrenic resin composition Collecting device.

The invention's effect

In the collection method of Configuration 1, a plasticizing step for plasticizing the styrene resin (A), (rubber reinforcement) a styrene resin latex (B) and a coagulant (C) are mixed to obtain a cream substance (D) Mixing to obtain the mixture (E) by supplying the tar-like substance (D) into the extruder in which the styrenic resin (A) after the coagulation step and the plasticizing step is present and mixing in the extruder A drainage step of removing moisture from the mixture (E) and draining the internal force of the extruder, and a devolatilization step of devolatilizing the mixture after removing the moisture and discharging volatiles from the extruder. The (rubber reinforced) styrene-based resin composition is recovered from the inside of the extruder, so that even if a large-scale facility is not used, fine powder scattering and a large amount of wastewater are not generated, and environmental pollution problems do not occur. High quality (rubber reinforced) styrene of various varieties with low energy and good yield It can be recovered resin composition.

In the recovery method of Configuration 2, since the plasticizing step is performed in the extruder on the upstream side of the supply position of the cream substance (D) in Configuration 1, the styrenic resin (A) is plasticized. , Which requires a separate facility to convert.

In the collection method of Configuration 3, in the configuration 1, the plasticizing styrene resin (A) is performed upstream of the supply position of the cream-like substance (D) by performing the plasticizing step in a plasticizer. In order to supply into the extruder on the side, the plasticization of the styrene resin (A) and the mixing step of mixing and melting the plasticized styrene resin (A) and the slurry (D) are performed separately. Therefore, it is possible to operate by setting optimum conditions for each. This Therefore, it is possible to recover various types of high-quality (rubber strong) styrene resin compositions.

In the collection method of Configuration 4, in any of Configurations 1 to 3, the solidification temperature in the solidification step is set to the Vicat softening temperature of the (rubber reinforced) styrene resin latex (B) as T m ° C. In this case, since it is set to (Tm_70) ° C. or more, the plasticized styrene resin (A) and the talium-like substance (D) can be mixed well.

In the recovery method of Configuration 5, in any of Configurations 1 to 4, the solid content concentration of the cream substance (D) obtained in the coagulation step and supplied into the extruder is in the range of 15 to 40% by mass. Therefore, it is possible to mix the plasticized styrene resin (A) and the cream substance (D) well.

In the recovery method of Configuration 6, in any of Configurations 1 to 4, wash water of 100 ° C. or more is supplied into the extruder downstream from the supply position of the cream substance (D). In order to discharge the water in the washing water and the mixture (E) from the inside of the extruder using a shaft screw type mechanical filter, the plasticized styrenic resin (A) and the creamy material (D) It is possible to satisfactorily remove moisture containing almost no resin component from the mixed melt.

In the recovery method of Configuration 7, in Configuration 6, a gas-liquid separation tank is provided after the mechanical filter, and drainage is performed while controlling the pressure in the gas phase in the gas-liquid separation tank. When separating the resin and water, it is possible to keep the water under pressure and separate it as a liquid without evaporating.

The recovery device of configuration 8 can provide a specific example of a device that can implement the recovery method of configuration 3 (and configurations 4 to 6 that cite configuration 3).

The recovery device of configuration 9 can provide a specific example of a device that can implement the recovery method of configuration 7.

Brief Description of Drawings

FIG. 1 is an explanatory diagram of a collecting apparatus used for producing pellets of an example. Corresponds to configuration 3.

FIG. 2 is an explanatory view of a recovery device of Configuration 2 of the present invention.

FIG. 3 is an explanatory view of a (or conventional) recovery device used for manufacturing pellets of a comparative example. [FIG. 4] In the apparatus of FIG. 1, the auxiliary extruder 20, the coagulator 30 and the main extruder 10 are shown in a simplified manner, the front part of the auxiliary extruder 20, the front part of the coagulator 30, and the mechanical filter. Explanatory drawing which shows the back | latter stage part collectively.

Explanation of symbols

[0007] 10 Main extruder of the recovery apparatus of the present invention

10B Main extruder of the recovery apparatus of the present invention

10X Conventional Recovery Equipment Extruder

20 Auxiliary extruder

30 Coagulator

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] 1. Raw materials and conditions:

(I) Styrenic resin (A):

Examples of the styrenic resin (A) include polystyrene, styrene monomethyl methacrylate (MS resin), styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile trimethyl methacrylate (MAS resin), and styrene. Rigid resin polymers such as monoacrylonitrile N-phenylmaleimide, acrylonitrile-butadiene-styrene copolymer (ABS resin), ethylene-propylene-modified styrene-acrylonitrile resin (AES resin), methyl methacrylate-butadiene Resinous polymers such as one styrene resin (MBS resin), methyl metatalylate one talironitrile butadiene styrene resin (MABS resin), high impact polystyrene resin (HIPS resin), acrylic rubber-based modified styrene-acrylonitrile resin (AAS resin) Can be mentioned.

When AS resin is used as the styrenic resin (A) as a matrix to adjust the physical properties of the product, the temperature of the plasticized AS resin is in the range of 100 to 200 ° C, preferably 110 to 160 ° C. is there.

(Mouth) (Rubber reinforced) Styrenic resin latex (B):

Examples of the (rubber reinforced) styrene-based resin latex (B) include the following polymer latex obtained by emulsion polymerization. For example, rubbery polymers such as styrene butadiene rubber (SBR), polystyrene, styrene monomethyl methacrylate (MS resin), Acrylonitrile copolymer (AS resin), styrene acrylonitrile 1 methyl methacrylate (MAS resin), styrene acrylonitrile 1 N-phenylmaleimide and other hard resin polymers, acrylonitrile butadiene styrene copolymer (ABS) Resin), ethylene-propylene-modified styrene-acrylonitrile resin (AES resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), high impact Examples thereof include latex such as polystyrene resin (HIPS resin) and resinous polymers such as acrylic rubber-based modified styrene-acrylonitrile resin (AAS resin).

The (rubber reinforced) styrene resin composition recovery method of the present invention is a resin latex obtained by emulsion polymerization or a resin latex obtained by re-emulsification of the resin, and adjustment of physical properties, appearance, and other performances. It is useful when mixing with a resin compounded for improvement. Specifically, as styrene resin (A) / (rubber reinforced) styrene resin latex (B), AS resin / ABS resin latex, MAS resin latex / MABS resin latex, AS resin / ASA resin latex, AS resin / AES resin latex, AS resin / AS resin latex, etc.

(Rubber Reinforcement) When ABS resin latex is used as the styrene resin latex (B), the resin concentration is 25 to 45% by mass, and the amount of coagulant added is 100 to 10 parts by weight of ABS resin:! A range of parts is preferred. Thereby, the solid content concentration of the cream-like substance (D) obtained by mixing (rubber-reinforced) styrene resin latex (B) and coagulant (C) and coagulating is 15 to 40% by mass, preferably 20 -40 mass%, more preferably 25-35 mass%. If the solid content concentration of the cream substance (D) is less than 15%, there may be a lot of non-creamy separated water in the mixture of styrene resin latus status (B) and coagulant (C), As a result, there are many portions that cannot be mixed well with the styrenic resin (A) after the plasticizing step. When the solid content concentration of the cream substance (D) exceeds 40%, the viscosity becomes too high, and the mixture of the styrene resin latex (B) and the coagulant (C) is mixed with styrene after the plasticizing step. It becomes difficult to supply into the resin (A). When the solid content concentration of the cream substance (D) is 20 to 40% by mass, the mixing with the styrenic resin (A) after the plasticizing step is good, and the more preferable range is 25 to 35% by mass. Percentage is acceptable Mixing with the styrenic resin (A) after the plasticizing process is even better.

(C) Coagulant (C):

As the coagulant (C), those usually used for coagulation of polymer latex can be used. Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as acetic acid and formic acid, and metal salts of these acids. Examples of the metal salt include inorganic salts such as calcium chloride, vinyl chloride, aluminum sulfate and magnesium sulfate, and organic salts such as calcium acetate and aluminum acetate. The metal salt may be used as a solid or dissolved in water or the like, but is preferably used as a 3 to 25% by weight aqueous solution. The above coagulants can be used singly or in combination of two or more. The amount of coagulant (C) added is (rubber reinforced) solid content concentration of styrene resin latex (B), (rubber reinforced ) It is determined in consideration of the coagulation value of the styrene resin, but is usually 1 to 10 parts by weight, preferably 1 to 8 parts by weight with respect to 100 parts by weight of the (rubber reinforced) styrene resin. If the amount of the coagulant added is less than parts by weight, the (rubber reinforced) styrene resin latex (B) may not be sufficiently coagulated. In that case, as described above, there may be a large amount of separated water that is not creamy in the mixture of the styrene resin latex (B) and the coagulant (C), and as a result, the styrene resin (( There are many parts that cannot be mixed well with A). If the amount exceeds 10 parts by weight, the required amount of coagulant may be exceeded and waste may occur. In addition, as described above, the viscosity of the mixture of the styrene resin latex (B) and the coagulant (C) becomes too high, and the mixture of the styrene resin latex (B) and the coagulant (C) is plasticized. It may be difficult to supply into the styrene resin (A) after the process. Here, the above “coagulation value” refers to a mixture of a styrene resin latex (B) having a predetermined solid content concentration (rubber reinforcement) and a coagulant (C) having a different solid content concentration, and a certain time has elapsed. This is the lowest concentration at which precipitation occurs (concentration after mixing) when precipitation is confirmed.

(U) Solidification temperature:

(Rubber-reinforced) Styrenic resin latex (B) and coagulant (C) are mixed to obtain a cream-like substance (D). When the conversion temperature is Tm ° C, it is (Tm-70) ° C or higher. If the coagulation temperature is (Tm-70) and the temperature is lower, the coagulum does not solidify into a paste and remains in a low-viscosity liquid, so it may not be possible to mix it with the plasticized styrene resin (A). is there. The upper limit of the coagulation temperature is determined by the restriction that the (rubber reinforced) styrene resin latex can be heated and heated stably, and is about 90 ° C.

A cream-like product obtained by mixing and coagulating a styrene resin latex (B) and a coagulant (C) into an extruder in which the styrene resin (A) is present after the plasticization step. The temperature of the mixture after supplying the quality (D) is from 1¾ to (1¾ + 100) ° 0 when the Vicat softening temperature of the styrene resin (A) is T n ° C. (8) and (Tm—70 0) The force determined by the blending ratio of the cream-like substance (D) solidified above (° C) 70 ° C (D).

(E) Wash water:

In the mixing step of mixing the creamy substance (D) with the styrene resin (A) that is plasticized, the high-temperature high-pressure water of 100 ° C or higher, or 100 Supplying steam at ~ 200 ° C can be used as washing water for washing polymerization aids such as emulsifiers, coagulants, etc., and separating the water in the mixture (E) together with the washing water in the subsequent drainage process 'It may be drained. When water or steam at a high temperature and high pressure is supplied in this way, the coagulated substance in the cream-like substance (D) can be heated to have an effect of promoting plasticization. The supply amount (mass) of the high-temperature high-pressure water or steam is preferably 2 times or less that of the resin. Further, the temperature of the steam is ί, preferably 110 to 180 ° C, and more preferably 120 to 160 ° C. Since the heat energy is low at temperatures lower than 110 ° C, there is a problem that the effect of plasticizing the resin is insufficient.At temperatures higher than 180 ° C, the steam pressure increases, so high-pressure equipment is required. There is a problem that handling becomes difficult.

(F) Mixing ratio:

The mixing ratio of styrene resin (A) to (rubber reinforced) styrene resin latex (B) is (B) force S rubber reinforced styrene resin latex contains the rubber component in the resin composition after mixing. The amount is preferably 10 to 35% by mass. When (B) does not contain a rubber component, the proportion of component (B) after mixing is preferably 10 to 80% by mass. 2. Collection device:

The force for specifically explaining the recovery apparatus for carrying out the present invention with reference to FIGS. 1, 2 and 4 and referring to FIG. 3 The present invention is not limited to FIGS. . In the description, AS resin is exemplified as the styrene resin (A), and ABS resin latex is exemplified as the rubber-reinforced styrene resin latex (B). However, the present invention is not limited to this.

Fig. 1: Recovery device:

First, the collection device in FIG. 1 will be described. This recovery device is used in the following embodiments:! This recovery device comprises a main extruder 10, an auxiliary extruder 20 for plasticizing the styrene resin (A), a rubber-reinforced styrene resin latex (B) and a coagulant (C). And a coagulation device 30 for making a cream.

The main extruder 10 is a squeezing and twin screw system, with a screw diameter of 40 mm, a cylinder length Z cylinder diameter (L / D) of 40, a motor rating of 75 kw, and a maximum rotation speed of 700 rpm.

The auxiliary extruder 20 is a squeezing and twin screw system, with a screw diameter of 30 mm, cylinder length / cylinder diameter (L / D) of 18, motor rating of 37 kw, and maximum rotation speed of 900 rpm. Since the auxiliary extruder 20 has a small cylinder length / cylinder diameter (L / D) and a low indentation pressure to the main extruder, it can be operated at ultra high speed and high flow. A relatively small device is sufficient.

Coagulator 30 is a squeezing and twin screw extruder, screw diameter is 30mm, cylinder length / cylinder diameter (L / D) is 8, motor rating is 1.5kw, maximum rotation speed is 12 ( kpm.

The main extruder 10 is provided with a first supply port 101 for the auxiliary extruder 20 at a position on the most upstream side, and a second supply for the coagulator 30 on the downstream side of the first supply port 101. A supply port 102 is provided. Further, on the downstream side, a cleaning water supply port 103, a cleaning water drain port 104, and a plurality of devolatilization ports 105a and 105b for removing volatile components are provided in this order. The die plate at the tip of the main extruder 10 is a 5φ * 20 hole die plate (having 20 through holes with a diameter of 5 mm (5 φ)).

The discharge port of the auxiliary extruder 20 is connected to the first supply port 101, and the discharge port of the coagulation device 30 is connected to the second supply port 102. Further, a supply pipe for cleaning water (or steam) is connected to the water supply port 103, and a mechanical filter 41 is connected to the drain port 104. Also, vacuum suction devices (vents) 43 and 43 are connected to the devolatilization ports 105a and 105b. It is. The drain port 104 and the mechanical filter 41 may have a plurality of stages. In other words, a plurality of resins may be arranged in order in the resin traveling direction in the main extruder 10. Further, the devolatilization ports 105a and 105b and the vacuum suction devices 43 and 43 may be provided in three or more stages, which is two stages in the illustrated example.

The auxiliary extruder 20 is injected with an AS resin, which is a styrene resin (A), and an additive, and is melted (plasticized). The plasticized molten or semi-molten matrix is supplied from the supply port 101 into the main extruder 10.

As shown in FIG. 4, the ABS resin latex (= rubber reinforced styrene resin latex (B)) force supplied from outside the system to the coagulator 30 is emulsion-polymerized in the reactor 301 and temporarily stored in the tank 302. The pumps are sequentially supplied at the pressure of the pump 303. Further, the coagulant (C) is put into the coagulator 30 in order.

The ABS resin latex and the coagulant supplied into the coagulator 30 are made into a cream by being pushed by a screw in the cylinder and proceeded, and the main extruder is driven by the pressure of the pump 303. 10 is pushed into. That is, it is brought into contact with the plasticized AS resin (= styrene resin (A)) and mixed.

In this way, the AS resin (= styrene resin (A)) and the solidified ABS resin latex (= cream-like substance (D)) are mixed in the main extruder 10 to obtain a molten state. Is done. High-temperature and high-pressure washing water (or steam) is supplied to the molten mixture from the water supply port 103. This washing water is discharged by the mechanical filter 41 along with the water contained in the cream substance (D).

As shown in FIG. 4, a gas-liquid separation tank 411 is provided downstream of the mechanical filter 41. A control valve 412a is provided in the drain line of the gas-liquid separation tank 411, and the degree of opening and closing thereof, that is, the amount of drainage, is adjusted so that the liquid level in the gas-liquid separation tank 411 is maintained at a predetermined level. Controlled by controller 412. In addition, a control valve 415a is provided in the exhaust line of the gas-liquid separation tank 411, and the pressure of the gas phase part in the gas-liquid separation tank 411 is maintained at a predetermined pressure with respect to the opening / closing degree, that is, the exhaust amount. Thus, it is controlled by the pressure controller 415. Here, the predetermined pressure that should be maintained in the gas phase section means that the mechanical filter 41 separates and removes water from the main extruder 10. The pressure is maintained at a pressure equal to or higher than the vapor pressure of water at that temperature, which makes it possible to separate the liquid in a liquid state without evaporating it. In addition, from the water discharged through the control valve 412a, the resin slightly leaking is recovered by the auto filter 413, and returned to the inlet of the coagulation apparatus 30 by the pump through the fine powder recovery tank 414. The filtrate from which the resin has been removed by the autofilter 413 is drained.

In this way, the mixture from which the water contained in the washing water and the cream-like substance (D) has been removed is further vacuumed by the vacuum suction device 43. As a result, the volatile matter is discharged from the devolatilization ports 105 and 105b.

After the water was removed in this way and the devolatilized mixture was discharged from the die plate at the tip of the main extruder 10 in a strand shape, cooled in the cooling water tank 71, cut by the cutter 72 and pelletized, Fine deposits are removed by vibration fluid 73 and recovered by a cyclone.

[0012] Figure 2 Recovery Device:

Next, the collection device of FIG. 2 will be described. The recovery device in FIG. 2 is the same as the recovery device in FIG. 1. Therefore, the same components as those in FIG. 1 are denoted by the same reference numerals, and different configurations will be mainly described. It is to be noted that the mechanisms shown in FIG. 4 are attached to the coagulation apparatus 30 and the mechanical filter 41 as in the case of the recovery apparatus in FIG.

The recovery device in FIG. 2 does not have the auxiliary extruder 20 in FIG. That is, the system configuration is simplified. In the recovery device of Fig. 2, the matrix body (AS resin and additive) is plasticized in the uppermost stream area of the main extruder 10B, and the supply for the coagulation device 30 is supplied to the area where the plasticized matrix body exists. Mouth 102 is provided. Because of this configuration, in FIG. 2, the cylinder length of the main extruder 10B is longer than the cylinder length of the main extruder 10 of FIG.

[0013] FIG. 3 recovery device (comparative recovery device):

The recovery device of FIG. 3 is not a device that performs the recovery method of the present invention, but will be briefly described because it is used in a comparative example described later.

In the apparatus of FIG. 3, the main extruder 10X is provided with a plurality of supply ports (not shown) for cleaning steam and a plurality of discharge ports (not shown) for discharging cleaning water, and a plurality of mechanical filters 61 and A vacuum suction device 43 is arranged. The main extruder 10X is a non-combination twin-shaft system (the same type of non-combination system used in Patent Document 1), with a screw diameter of 40 mm, cylinder length / cylinder diameter (L / D) Is 72, the motor rating is 75kw, and the maximum speed is 900rpm.

The equipment shown in Fig. 3 feeds raw materials (ABS resin latex and coagulant) into the main extruder 10X and proceeds while plasticizing, supplying cleaning steam, cleaning and draining, and then devolatilizing. , A device for discharging. Since the raw materials are melted, washed and devolatilized in the same cylinder, it is not possible to select the optimum number of revolutions for each. For this reason, each process cannot be optimally controlled, and the quality of the discharged resin may not be sufficient. For example, when the temperature of the molten resin becomes too high, the deterioration of the resin (molecular cutting) progresses, the MFR increases, the impact strength decreases, and the color tone increases bL (yellowishness). was there. Since the amount of the rubber component cannot be adjusted by the matrix body, it may be complicated if it is necessary to adjust in a later process.

Example

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following. In the examples, parts and% are based on mass unless otherwise specified. Each evaluation in the examples is a value measured as follows.

[Evaluation methods]

(1) MFR: IS 220, based on IS 0133. C, measured with a load of 98N.

(2) Charpy impact strength: The obtained resin pellets were molded by an injection molding machine (NN30 B manufactured by Niigata Iron Works) and measured based on IS0179.

(3) Color tone: Using the above injection molding machine, a 3.2 X 40 X 80 mm test piece was molded and evaluated using a color difference meter (Gardner, TCS-Π (light source C, reflection method d_8)) did.

[Raw materials]

(1) Styrenic resin (A):

Sanrex SAN-C (melt flow rate: 25 g / 10 min (220 ° C., 98 N), AN content: 26%) manufactured by Techno Polymer Co., Ltd. was used.

(2) (Rubber reinforced) Styrenic resin latex (B):

B-1: Butadiene rubber latex 50 parts (solid content conversion), Styrene 36.5 parts, Atarylonite ABS resin latex was prepared according to a known method using 13.5 parts of ril. The resulting ABS resin latex has a solid content of 33%, the rubber component in the resin is 50%, the matrix part (aceton soluble part) has an AN% of 27%, the intrinsic viscosity is 0.41 dl / g, graft The rate was 55%.

B-2: A butadiene rubber latex 40 parts (in terms of solid content), 43.8 parts of styrene, and 16.2 parts of attalononitrile were used to produce an ABS resin latex according to a known method. The obtained ABS resin latex had a solid content of 34.5%, a rubber component in the resin of 40%, and an AN% of the matrix part (aceton soluble part) was 27. / ₀ , the intrinsic viscosity was 0.45 dl / g, and the graft ratio was 62%.

[Examples:! To 3, Comparative Examples 1 and 2]

The pellets of Examples 1 to 3 were manufactured using the apparatus shown in FIG. Table 1 shows the components of Examples 1 to 3 and details of the manufacturing process (such as operating conditions).

The pellets of Comparative Examples 1 and 2 were produced using the apparatus shown in FIG. Table 2 shows details of the comparative examples:! ~ 2 and details of the manufacturing process (operating conditions, etc.).

Furthermore, AS pellets were blended in each pellet of Comparative Examples 1 and 2 and kneaded and pelletized with a single screw extruder, and the Comparative Example Pellet for physical property evaluation was made to have the same rubber content as in Examples 1 to 3. 11 , 12, 21. here,

Comparative Example Pellet 11 is a pellet in which the pellet of Comparative Example 1 has the same rubber content as Example 1,

Comparative Example Pellet 12 is a pellet in which the pellet of Comparative Example 1 has the same rubber content as Example 2,

Comparative Example Pellet 21 is a pellet in which the pellet of Comparative Example 2 has the same rubber content as Example 3.

The quality of each of the pellets of Examples 1, 2, and 3 and Comparative Examples 11, 12, and 21 was evaluated. Table 3 shows the evaluation results.

[Assessment result]

1) As is clear from Tables 1 and 2 in Comparative Examples 1 and 2, the amount of water-entrained resin recovered is higher than that in Examples:!

2) As seen in Tables 1 and 2 for Comparative Examples 11, 12, and 21, as a result of the higher tip resin temperature in Comparative Examples 1 and 2, the MFR increases as shown in Table 3. , Charpy impact strength The color tone decreases, the yellowness increases, and the whiteness decreases.

In addition, when the example product was manufactured using the apparatus of FIG. 2 and the comparative product was manufactured in the same manner as described above, the same results as above were obtained.

[table 1]

[Table 2]

Comparative Example 1 Comparative Example 2 Types B-1 B-2 Solid Concentration [Quality

33 34.5%]

(B) (Rubber reinforced) Styrenic resin rubber component in resin

50 40 tex [mass <½]

Vicat softening temperature

101 106

[. c]

Feed amount [L hr]

300 (99) 360 (124. 2) (Solid content [kg hr])

Magnesium sulfate

(C) Coagulant feed amount [L hr] 25 30

Aqueous solution (8% by mass)

120-130. C high

High temperature water for cleaning 1 Feed amount [L hr] 50 50

'Dish [BjCh Water

120 ~ 130 ° C high

High temperature water for cleaning 2 Feed amount [L hr] 30 30

½lIBj £ t water

Barrel heater temperature [° c] 150 to 200 150 to 200 Recovered water from both filters [L hr] 285 327 Main extruder

Amount of resin with moisture accompanying [kg no hr] 15 20

Tip resin temperature [¾] 290 283

[Table 3]

Industrial applicability

The present invention produces high-quality (rubber-rich) styrene resin compositions of various varieties with low energy without causing environmental pollution problems that do not cause fine powder scattering and large amounts of wastewater, and can produce high yields. Can be used for any purpose.

Claims

The scope of the claims

[1] A plasticizing process for plasticizing the styrene resin (A),

To recover the (rubber reinforced) styrene resin composition from the inside of the extruder.

[2] In claim 1,

A method for recovering a styrene-based resin composition (rubber reinforced).

[3] In claim 1,

The plasticizing apparatus performs the plasticizing step and supplies the plasticized styrene resin (A) into the extruder on the upstream side of the supply position of the cream-like substance (D). (Rubber reinforced) A method for recovering a styrene resin composition.

[4] In any one of claims 1 to 3,

A method for recovering a (rubber reinforced) styrene-based resin composition.

[5] In any one of claims 1 to 4,

A method for recovering a styrene-based resin composition (rubber reinforced).

[6] In any one of claims 1 to 4, Wash water at 100 ° C. or more is supplied into the extruder downstream from the supply position of the cream substance (D), and the wash water and the mixture (E ) To discharge the moisture in the extruder,

A method for recovering a (rubber reinforced) styrene-based resin composition.

[7] In claim 6,

A method for recovering a (rubber reinforced) styrene-based resin composition.

[8] A main extruder, an auxiliary extruder for plasticizing a styrene resin, and a solidification device, wherein the main extruder is a first supply port for the auxiliary extruder at a position on the most upstream side. A second supply port for the coagulation apparatus on the downstream side of the first supply port, and further on the downstream side, in turn, a wash water supply port, a wash water drain port, and a volatile component. Has a devolatilization port for removal,

The styrenic resin plasticized in the auxiliary extruder is supplied to the first supply loci to the main extruder and creamed (rubber reinforced) styrene resin in the coagulator. The mixture is melted in the main extruder, washed with washing water supplied from the water supply port, and the washed water is drained from the drain port through a mechanical filter. The mixture after drainage is devolatilized under negative pressure, and the volatile components are discharged to the devolatilization locus.

(Rubber-reinforced) styrene-based resin composition recovery device.

An example of this collection device is shown in FIG.

[9] In claim 8,