JPH01121311A - Production of rubber-modified thermoplastic resin - Google Patents

Abstract

PURPOSE:To efficiently obtain the title resin having excellent dispersibility of rubber particles using a simple apparatus, by blending and extruding coagulated material of a vinyl based monomer graft-rubber polymer latex and thermoplastic resin in the presence of a specific organic chemical in a mixer and extruder. CONSTITUTION:A graft rubber polymer latex prepared by emulsion graft polymerizing a vinyl based monomer with a rubber latex is fed from a feed port 2 into a mixer 7 and a water-soluble chemical in an amount of <=10wt.% based on the polymer is fed from a feed port 1 into the mixer 7. Both are mixed with stirring blades 6 to provide a coagulated material of the latex from a discharge port 3. The resultant coagulated material is then fed from a feed port II of an extruder 10 and a thermoplastic resin is subsequently fed from a feed port VII. Other thermoplastic resins, as desired, are fed from a feed port I, etc., and an organic chemical, capable of dissolving a thermoplastic resin in an amount of 10-600wt.% based on the total amount of the graft polymer and thermoplastic resin and having <=5wt.% solubility in water at the temperature of the water drain port V is fed from a feed port III. Kneading is then carried out to separate the resultant kneaded material into an organic phase and aqueous phase, which is subsequently discharged from the water drain hole V and heated to deaerate and remove the organic chemical from a vent hole VIII. Thereby the aimed resin is obtained from a discharge hole XI.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a rubber-modified thermoplastic resin by mixing grafted rubber particles obtained by graft polymerizing a vinyl/l' monomer with a thermoplastic resin. For more information on how to manufacture
By mixing the coagulated product of graft rubber polymer latex and thermoplastic resin in the presence of a specific organic agent using a simple mixer and extruder, rubber modification heat with excellent dispersibility of graft rubber particles can be obtained. This invention relates to a method for efficiently producing plastic resin using a simple device and using a small amount of heat.

[Conventional technology]

Most of the rubber-modified thermoplastic resins represented by kBBm resin are resins obtained by mixing and kneading a polymer obtained by graft polymerizing a vinyl monomer to rubber latex and a thermoplastic resin. be. The manufacturing process generally includes an emulsion graft polymerization process, a coagulation process, a dehydration drying process, a blending process, and a melt extrusion process.

In the emulsion graft polymerization process, acrylic monomer, vinyl cyanide monomer, aromatic vinyl monomer, etc. are added to diene rubber latex, vinyl rubber latex, natural rubber latex, silicone rubber latex, etc. This is a process of producing graft polymer latex by emulsion graft polymerization. The coagulation step is a step in which a coagulant such as a polyvalent salt or an acid is added to the graft polymer latex to break the emulsified state, and the polymer is coagulated into powder.

The dehydration and drying process is a process in which the aqueous phase is separated from a mixture of powdered polymer and water by means such as centrifugal dehydration, and then the powder is dried by means such as fluidized drying to obtain dry powder. It is. The blending process is a process of blending the dry powder with other thermoplastic resins and additives such as stabilizers, lubricants, and plasticizers.The melt extrusion process involves melting the blended raw materials using a device such as a screw extruder. This is the process of kneading, extruding into strands, and shaping into pellets.

The first problem in terms of production and quality of the rubber-modified thermoplastic resin produced through each of the above steps is that the amount of heat used is large. This is due to the use of a large amount of hot air in the drying process. The second problem is that when the graft rubber particles are completely fixed during the coagulation process, it takes a lot of power to disperse the fixed graft rubber particles into the thermoplastic resin during the melting and kneading operations after blending. It is necessary to. In the worst case, it becomes industrially impossible to uniformly disperse graphite rubber particles into the thermoplastic resin.

Several proposals have been made known to improve the traditional manufacturing methods of rubber-modified thermoplastics, which include such problems that lead to reduced industrial competitiveness, some of which It is being carried out on a regular basis. One of them is to reduce the amount of heat used in the drying process, and uses a screw extruder with a dehydration function, which is generally referred to as a dehydration extrusion type. This method consists of a first method in which the grafted rubber wet powder after coagulation and dehydration is blended with other thermoplastic resins and additives, or the grafted rubber wet powder is fed alone to a dehydrating extruder; There is a second method in which rubber latex and a coagulant are supplied to the dehydration extruder together with other thermoplastic resins and additives as the case may be.

Since this method does not involve a drying process that uses a large amount of hot air, it is highly effective from the perspective of reducing the amount of heat used, but it is not at the same level as conventional techniques from the perspective of uniformly dispersing the rubber particles in the thermoplastic resin. be. That is, in the first method, since the graft rubber particles are processed in a completely fixed state, the method is equivalent to the conventional technique from the viewpoint of particle dispersion. In the second method, the latex and coagulant are first mixed in the processing equipment, and then heated to 100°C.
Dehydration is carried out at or below a temperature range at which point the grafted rubber particles are usually stuck together. Thereafter, as the temperature rises, the thermoplastic resin and the thermoplastic resin melt together and undergo a crosstalk operation, so the first method differs only in the state of the raw material supplied, and from the perspective of particle dispersion, it is different from the conventional technology. It's not out of bounds.

Another method is to mix the grafted rubber polymer latex, coagulant, and monomer into a two-phase mixture consisting of an organic phase and an aqueous phase, and then separate the aqueous phase and remove the monomers contained in the organic phase. A method of polymerizing monomers and a method of polymerizing monomers in the two-phase mixture without separating the aqueous phase, then separating the aqueous phase and drying the polymer have been proposed. These methods do not have a process in which the grafted rubber particles completely stick to each other, so they are very unique in terms of particle dispersion compared to the above-mentioned method using a dehydrating extruder.

However, the former method requires the polymerization of a highly viscous mixture consisting of a cake-like graft polymer and a monomer without causing a runaway reaction, and is not necessarily superior because it involves difficulties in terms of equipment and operation. It is hard to say that it is a good method. Moreover, in rubber-modified thermoplastic resins, because the content of the rubber component has a great effect on the basic physical properties of the resin, polymerization is not carried out at a low polymerization rate with large fluctuations, as is done in ordinary bulk polymerization methods. It is not possible to use a method of devolatilizing the remaining monomer after the completion of the polymerization process, and the reaction must proceed until a high polymerization rate is reached at which fluctuations in the polymerization rate become small due to operational reasons. In comparison, it has a high viscosity and high temperature, making it extremely difficult to handle. In addition, the latter method is a method of polymerizing monomers by suspension polymerization, and while the viscosity of the system is low and it is easy to remove the heat, it has the problem of requiring dehydration and drying steps. left behind.

[Problems to be Solved by the Invention] As described above, many proposals have been made regarding the production method of rubber-modified thermoplastic resin. At present, a high-quality and competitive manufacturing method for the resin has not yet been completed, which simultaneously solves the problems of dispersion and reduction of the amount of heat used.

In view of the current situation, the present inventors have proposed a method for producing a rubber-modified thermoplastic resin that enables a similar dispersion of grafted rubber particles in a thermoplastic resin and is energy-saving. Gansho 60-110
No. 989, Japanese Patent Application No. 1983-295952, Special Application No. 1987-
293955, Japanese Patent Application No. 60-295569, Japanese Patent Application No. 60-295370, Japanese Patent Application No. 61-166571, and Japanese Patent Application No. 61-175508, etc., in an attempt to solve the problems of conventional methods. As a result of further investigation, the inventors of the present invention discovered a method for producing rubber-modified thermoplastic resin with a simple device and high productivity, which does not lack the advantages of the above proposal, and completed the present invention. I came to the conclusion.

[Means for solving problems]

That is, the method for producing a rubber-modified thermoplastic resin of the present invention is as follows:
A graft rubber polymer (III) obtained by emulsion graft polymerization of a vinyl monomer to rubber latex, a thermoplastic resin (
3) and, if desired, the rubber-modified thermoplastic resin consisting of the thermoplastic resin (2), first, the latex (A) of the grafted rubber polymer (1) and the grafted rubber polymer (1) are Latex (A) weighing less than 10% by weight
A water-soluble drug (Cl) capable of coagulating is mixed in a mixer to obtain a coagulum of latex (A), and then the following (IF), (
III), (V), (VIII) and (XI) have a supply port, a drain port, a vent hole and a discharge port, (II): The coagulated product of the latex (A) obtained from the mixer is Supply port, (■): Located on the discharge side from the supply port (It), the following organic chemicals (supply port for organic chemicals (a.
) and has the ability to dissolve the thermoplastic resin (2), and has a solubility in water of the following wastewater o (V) O/< 1//L / temperature (organic agent (V) of 5 weight or less in IIO: 4 of the screw diameter (to) from the supply port (II)
a drain port located on the discharge side by a distance (r, 1) greater than or equal to 20 times and discharging the aqueous phase separated from the mixture of substances added up to the supply port (IV); (VIII): organic drug ( 1 to 4 vent ports for vaporizing and removing the remaining aqueous phase that is not discharged from the IO and drain port (V); (IV): outlet for discharging the molten rubber-modified thermoplastic resin; ) and/or (N) thermoplastic resin (3), (VII): a vent port (VII) closest to the supply port (■);
II), the thermoplastic resin (3
) supply port, (IX): supply port for thermoplastic resin (3) located on the discharge side from Pentro (■), and when using thermoplastic resin (2), the following (
1″), (IVχ (IV) has one supply port for the thermoplastic resin (2), and (I) ζ has a thermoplastic resin (2) supply port located on the driving side from the supply port (I). ) supply port, (IV): supply port for the thermoplastic resin (2) located on the discharge side from the supply port (II), (VI): if it has a supply port (VII), the supply port (B) 1) Located on the drive side by a distance (L2) that is 2 times or more and 10 times or less of the cylinder diameter (D), and the supply port (VI
I), there is a supply port for the thermoplastic resin (2) located on the drive side by a distance (L2) from the vent port (VIII) closest to the supply port (A); IX), if desired, use an extruder having the following pentro (X), (X):
Located on the discharge side by a distance (X) from the supply port (IX), one or more vent ports or more than two vent ports are provided for removing volatile components contained in the rubber-modified thermoplastic resin that is the product, from the mixing machine. The feed port (II) of the extruder is connected to the mixture containing the coagulated product of the supplied latex (A) through the feed port Cm)'
By feeding the organic agent (times) and kneading it in the interval of distance (L1), the latex (薊) is grafted onto the rubber polymer (
The mixture containing the grafted rubber polymer (1) was heated, and the aqueous phase was discharged from the extruder through the drain port (v). ) from the organic agent (through the paper and outlet (V)), and remove the moisture that was not discharged from the organic agent (from the outlet (V)), and if desired) from the thermoplastic resin (2
) to supply port (1) or supply port (IV) or supply port (
The thermoplastic resin (3) is supplied from the supply port (VII) and mixed with the mixture containing the graft rubber polymer (1) and the organic agent (B) at a distance (TJ2), and the thermoplastic resin (3) is supplied from the supply port (VII) and
is mixed with the mixture containing the Guftgo pentapolymer (1) from the supply port (IX) over a distance (L3), and if desired, volatile components are degassed with Pentro (X).

The rubber latex used in the present invention is not limited to any polymer latex as long as it has rubber elasticity within the operating temperature range of the target rubber-modified thermoplastic resin. For example, polybutadiene, polyisoprene, etc. Latex of diene rubber such as , 81R; Latex of olefin rubber such as ethylene-propylene rubber, ethylene-vinyl acetate rubber; Acrylic rubber such as polyethyl methacrylate, polyethyl acrylate V-), polybutyl methacrylate, polyethyl acrylate, etc. latex; latex of silicone rubber such as boridimethysiloxane; and the like. These rubber latexes may be used alone or in combination with two types of dams.

It is extremely difficult to disperse the rubber particles contained in such rubber latex into a thermoplastic resin using conventional methods, and even if it is possible, the compatibility between the rubber and the thermoplastic resin may be affected. K was not able to exhibit satisfactory physical properties due to poor quality and other reasons. Graft polymerization is therefore carried out as a means of improving compatibility, enabling uniform dispersion of rubber particles, and exhibiting excellent physical properties. The monomer used in this graft polymerization is a vinyl monomer because the polymerization method is emulsion physical polymerization, and it is the most suitable vinyl monomer from the viewpoint of compatibility with the thermoplastic resin to be blended, adhesiveness, etc. Generally, things are selected. This situation does not change in the present invention. Therefore, the vinyl monomers to be graft-polymerized to the rubber used in the present invention include conventionally used vinyl cyanide monomers such as acrylonitrium and methacrylonitrile, styrene, and afamethylene!
Aromatic vinyl monomers such as styrene, methacrylates such as methyμ methacrylate and pheniμ methacrylate,
Methiμ chloroacrylate, 2-chloroethyl! These are halogenated bi=μ monomers such as methacrylate and other physically polymerizable monomers.

As the thermoplastic resin (2) used in the present invention, any resin soluble in the organic agent (B) described below can be used. Acrylonitrile-styrene copolymer, acrylonitrile-α
- Methyμ styrene copolymer, acrylonitriμ-α-methyμ styrene-N-phenymaleimide copolymer, folystyrene, polymethyμ methacrylate, polyvinyl chloride
, polycarbonate, polyμphone, polyethylene terephthalate, etc. are typical examples.

On the other hand, the thermoplastic resin (3) does not need to be soluble in the organic agent (B) K like the thermoplastic resin (2), but specifically, it can be used with the resins exemplified in the thermoplastic resin (2) above. Similar things can be mentioned. Thermoplastic resin (2) and thermoplastic resin (
5) may be the same or different.

The organic drug (B) that can be used in the present invention is an organic drug having a solubility in water of 5% by weight or less, preferably 2% by weight or less, and is an organic agent that can dissolve the thermoplastic resin (2).This organic agent accounts for 10 to 600% by weight based on the total amount of the graft rubber polymer (1) and the thermoplastic resin (2).
, preferably in the range of 20 to 200 weight.

In this case, the solubility of the organic drug (B) in water is determined by the temperature (II
If the weight is 5 - or more, the aqueous phase discharged from the drain port (V) will become cloudy. In other words, the organic drug (stainless steel) and its soluble polymer components are mixed into the aqueous phase;
Many facilities are required to treat the discharged aqueous phase.

Further, it is not preferable because the efficiency of using the added organic agent (Tsuru) decreases and the yield of the product polymer also decreases.

On the other hand, if the amount of the organic agent (B) used is less than 10% by weight based on the total amount of the graft rubber polymer (1) and thermoplastic resin a) contained in the latex (A), the effects of the present invention can be obtained. was not expressed, and on the contrary, organic drug (B) was added at 600% by weight.
If the amount is exceeded, a large amount of heat will be required to separate the organic drug), which is undesirable from an industrial standpoint.

Specific examples of the organic drug (B) that can be used in the present invention include:
Aromatic hydrocarbons such as petroleum ether, benzene, toene, xylene, ethylbenzene, diethylbenzene, p-cymene, tetrazine, #L flower methylene, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride, trichrene, chlorobenzene, and shrimp chlorohydrin, ketones such as methiμm rope tetrapiketone, acetophenone, and esters such as acetic acid-n-propyμ and acetic acid-n-butyμ μ, hexane,
Examples include, but are not limited to, aliphatic hydrocarbons such as heptane, copolymerizable organic agents such as 1-nitropropane, and polymerizable organic agents such as styrene, methyμ methacrylate, and α-methystyrene. Rather, as long as they satisfy the above conditions, they can be used alone or in combination of two or more.

The water-soluble agent (6) having coagulation ability that can be used in the present invention may be any water-soluble substance that has the ability to coagulate the latex (A) used, and the quality of the resin to be produced From the viewpoint of not causing deterioration, the amount used is 10 weight or less, preferably 5 weight or less, more preferably 3 weight or less based on the graft rubber polymer (1)K. In addition, water-soluble drugs are generally used at least (L2 weight). Specific examples of water-soluble drugs (C) include:
Examples include polyvalent salts such as aluminum sulfate, aluminum chloride, aluminum nitrate, magnesium sulfate, μsium chloride, and nitric acid, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and propionic acid. .

The thermoplastic resin (2) is mixed and kneaded with the graft rubber polymer (1) in the presence of a specific amount of organic agent (B) over a distance (IJ2) or longer in the extruder. , the graft rubber polymer particles in the graft rubber polymer (1) are uniformly dispersed in the thermoplastic resin (2) to prevent the graft rubber polymer particles from re-agglomerating and resulting in poor dispersion in subsequent treatments. It has the function of K, which exhibits this more "uniform dispersion function" or "reagglomeration prevention function", has a thermoplastic resin (2) in an amount similar to that of the "free polymer" described below.
Unless the graft rubber polymer (1) containing a large amount of ) is mixed and kneaded, a certain amount or more of the organic agent is present, and in order to obtain a uniform and dispersed state, the kneading is carried out in an area that is at least twice the barrel diameter. is important.

The feeding position of the thermoplastic resin (2) is preferably determined by taking into account the affinity of the graft rubber polymer (1) and the thermoplastic resin (21 with the organic agent (B) and the efficiency of use of the device.
That is, the graft rubber polymer (1) and the organic drug (B)
If the affinity is too high, the organic drug (1) will be strongly adsorbed to the graft rubber polymer (1), and even if the thermoplastic resin (2) is supplied from the supply port CM), the organic drug If the dissolution and mixing effect of the thermoplastic resin (2) is insufficient, the thermoplastic resin (2) and the graft rubber polymer (1) are not sufficiently mixed, and the graft rubber particles of the graft rubber polymer (1) If the thermoplastic resin (2) is not uniformly dispersed in the thermoplastic resin (2), the thermoplastic resin (2) is supplied from the supply port (RI) or the supply port (IV), and the latex (A) and the thermoplastic resin ( It is desirable to perform kneading in a state where 2) coexists.Which of the feed ports (RI and feed port CF/) to feed from may be determined depending on the raw materials and equipment used.

Generally, the thermoplastic resin (2) is supplied to the screw that is not filled with anything at the supply port (1), so the thermoplastic resin (2) is smoothly introduced into the extruder and stabilized. The vehicle can be operated in a controlled manner.

Furthermore, even if the thermoplastic resin (2) is supplied from the supply port (IV), if the graft rubber particles of the graft rubber polymer (1) are uniformly dispersed in the thermoplastic resin (2), It is better to supply thermoplastic resin (2) than (IV),
Aqueous phase and thermoplastic resin (2) discharged from drain port (v)
This is preferable because the volumetric efficiency of the device is improved without the coexistence of

The amount of thermoplastic resin (2) added is determined by the amount of graft rubber polymer (
Although it varies depending on the type of 1) and the desired physical properties of the final rubber-modified thermoplastic resin product, it is usually appropriate to use less than the thermoplastic resin contained in the rubber-modified thermoplastic resin product.

When the entire amount of thermoplastic resin required to make a rubber-modified thermoplastic resin product is added as thermoplastic resin (2), a large amount is added to uniformly disperse the grafted rubber polymer particles in thermoplastic resin (2). Cipentro (which requires organic drugs)
VW) and the amount of organic agent to be removed at the vent port increases, resulting in the disadvantage that the thermal energy required for removal increases. Furthermore, graft rubber polymer (1)
Since the amount of polymer to be mixed and kneaded increases in order to uniformly disperse the grafted rubber particles, the disadvantage is that the mixing energy μ increases and the productivity of the mixing device decreases.

In order to avoid such disadvantages, in the present invention, the thermoplastic resin necessary for producing the rubber-modified thermoplastic resin product (1) is combined with the thermoplastic resin (2) soluble in the organic agent (B) and the thermoplastic resin (2) that is soluble in the organic agent (B). Mix the plastic resin (3) separately.

On the other hand, if a large amount of vinyl monomer is used when obtaining graft rubber polymer (1) by emulsion graft polymerization of vinyl monomer to rubber latex, the vinyl monomer will graft polymerize to rubber. The graft polymer contains a large amount of a polymer that is polymerized alone without being combined (hereinafter referred to as "free polymer"), and the "free polymer" is a substitute for the above-mentioned thermoplastic resin (2). In some cases, it exhibits a "reaggregation prevention function". Therefore, in such a case, the supply port (1)
Or, at the supply port (IV), the entire amount of thermoplastic resin (3) necessary to obtain one rubber-modified thermoplastic resin product without supplying any thermoplastic resin (2) at the supply port (IV) ), supply port (to) and /l or supply port (I
X) may be supplied.

The thermoplastic resin (3) is supplied at the supply port (VII) and /l or supply port (EK). Among these, the thermoplastic resin (3) added at the supply port (■) has the function of reducing coloring of the mixture in the next degassing step. In other words, in ventro (■), the mixture is usually heated and the organic agent (■) in the mixture is removed while reducing pressure if desired.
B) Evaporate the dead particles and remaining moisture to remove them. When the organic agent (crow) is removed from the mixture, the organic agent (
The dissolution or plasticizing effect caused by B) disappears, and the mixture here is composed of graft rubber polymer (III), thermoplastic resin (
2) and thermoplastic resin (3). In order to process the mixtures smoothly in the extruder, it is necessary to keep the temperature of these mixtures above the flow initiation temperature. In addition, organic drugs (
The evaporation of B) and residual moisture takes place in a relatively short period of time, and heating from external heat supply and shear heat generation is also sufficient.
Considering that most of the latent heat of vaporization of the organic agent (B) and residual water must be covered by the sensible heat generated by the temperature reduction of the mixture, the mixture is heated to a temperature considerably higher than its flow initiation temperature. The need arises.

However, when exposed to such high temperatures, the rubber components contained in the graft rubber polymer (1), particularly diene rubbers such as polybutadiene, deteriorate due to heat and turn yellow. This yellowing phenomenon becomes particularly noticeable when the amount of the rubber component in the mixture increases, and is particularly noticeable in the above mixture where the amount of the diene rubber component exceeds 40% by weight. In other words, even if the product has the same amount of rubber component, the above mixture with a large amount of rubber component is degassed and then the supply port (I
The colored state of the product to which the thermoplastic resin (3) was added in X) is determined by mixing the thermoplastic resin (5) at the supply port (■) and degassing it while reducing the amount of rubber components contained in the mixture. The coloring condition is worse than that of the treated product. therefore,
In order to reduce the coloring of rubber-modified thermoplastic resin products, at least a portion of the thermoplastic resin (3) is supplied to the supply port (■).
It is preferable to add it at

On the other hand, when a large amount of organic agent remains in a rubber-modified thermoplastic resin product, its plasticizing effect lowers the heat distortion temperature and hardness, and furthermore, air bubbles of organic agent vapor get mixed into the molded product during molding. Since the toxicity of organic chemicals is a problem in food applications, etc., it is desirable that the residual amount of organic chemicals in rubber-modified thermoplastic resin products be as small as possible.Normally, 1 weight or less, more preferably 15 weight or less. It is necessary to For this "residual organic drug concentration reduction function", it is desirable to add the thermoplastic resin (3) at the supply port (IX).

The reason is believed to be the evaporation rate characteristics of the organic drug from the mixture of polymer and organic drug.

That is, in a region where the concentration of the organic drug in the mixture is high, by raising the temperature of the mixture to the boiling point of the organic drug or higher, the organic drug in the mixture can be removed by degassing relatively quickly. However, when the concentration of the organic drug in the mixture is low, approximately 5 to 1% by weight or less (although this value varies depending on the combination of polymer and organic drug), the rate of evaporation of the organic drug decreases significantly. However, it becomes difficult to degas and remove the organic drug from the mixture. Therefore, after degassing the thermoplastic resin (3) without mixing it to reduce the organic drug concentration in the mixture to 5 to 1 weight or less, the thermoplastic resin (3) is added at the supply port (IX). Therefore, it is advantageous to dilute the organic agent in the mixture.

Therefore, the entire amount of thermoplastic resin (3) is transferred to the supply port (■).
The above-mentioned "coloring reduction function" and "residue" may be mixed at either one of the supply port (IX) and the supply port (IX).

It is desirable to distribute and mix the thermoplastic resin (5) between the supply port (■) and the supply port (IX) so as to harmonize the function of reducing the concentration of existing organic drug.

In the present invention, the raw material latex (A), the organic drug (B)
), a water-soluble agent, a thermoplastic resin (2) (which may not contain thermoplastic resin (2)), and a thermoplastic resin (3) using a mixer and a screwdriver in order to process the above-mentioned procedure. Use a type of extruder.

As the mixer, a fin mixer, a static mixer, etc. can be used. FIG. 1 is a cross-sectional view of an example of a mixer for obtaining a coagulum used in the embodiments of the present application. The mixer has a structure that can be heated by a jacket 8 and a hot water inlet/outlet 4.5, and a lid 9 is attached to the mixer main body 7 by a bolt (not shown). The latex (A) is supplied from the supply port 2 by a metering pump, and the water-soluble drug (0) is supplied from the supply port 1 by a metering bonder, and is stirred by a rotating stirring blade 6 by a drive device not shown in the figure. and latex (
It becomes a coagulated product of A). The coagulated product of the latex (A) is
It is discharged from the discharge port 3.

On the other hand, screw type extruders include single screw extruders,
Although a twin-screw counter-rotating extruder, a twin-screw co-rotating extruder, etc. can be used, a twin-screw co-rotating extruder is most preferred. It is necessary to provide a supply port, a drain port, a vent port, and a discharge port in the pallet μ of the extruder in a predetermined order and at predetermined intervals.

Figure 2 shows all the supply ports that may be used in the present invention (
I), (II), (II), CPU), (VI), (
VII) and (IX), drain (V), ventro (V
III) and (X) and a cross-sectional view in the axial direction of the extruder having a discharge port CM>. The extruder shown in Fig. 2 has a barrel m0, a pare μ outer surface 11, and a barrel inner hole 12, and a screw (not shown in the figure) having approximately the same diameter (D) as the barrel inner hole is installed in the barrel inner hole 12. The screw is rotated and operated by a drive device (not shown).

FIG. 3 is a diagram schematically showing an axial cross-sectional view of the barrel of the extruder used in the examples of the present application, including the supply port (II),
(III), drain port (V), supply port (IV), ventro (■), supply port (DO and ventro (X), and discharge port CM>).

When producing rubber-modified thermoplastic resin using the extruder shown in Fig. 3, latex (A) and water-soluble drug (
A coagulated product of latex (A), which is a mixture of No. 0), is supplied into the extruder from the supply port (II).

The organic drug (B) is fed under pressure by a metering pump to the supply port (I
II) into the extruder. Drain port (V) is the fourth
As shown in Figures to Figure 5, on the side of 1 barre/L/10,
A part 13 having an opening 14 with a height H1 width W in a hole made to penetrate the barrel inner hole 12 and the outer surface 11 of the barrel μ.
, and connect part 1 with a port not shown in the diagram.
5 is attached to the barrel m0<.

The supply port (IV) and the supply port (IX) have a cross section perpendicular to the axial direction of the extruder as shown in FIG. /10
A hole 15 provided above is used. Ventro (V
III) and ventro (X) have a structure in which, as shown in FIGS. 7 to 8, a sealing lid 16 with a ventilation hole 17 is attached to the hole 15 in FIG.

FIG. 9 schematically shows an axial cross-sectional view of the extruder plate μ used in another example.
), supply port (II), supply port (III), drain port (V
), a supply port (■), two ventros (VIII) and (X), a supply port CK), and a discharge port (XI). The structure of each supply port, drain port, and vent port is shown in Figures 4 to 8.
The structure is as shown in the figure and FIG. Further, it is desirable that the screw installed in the pallet μ has a shape that provides a transport function and a kneading function in accordance with the position of each opening. FIG. 10 is a front view of an example of a screw element that exhibits a transport function used in the embodiment of the present application, and FIG. 11 is a side view thereof, in which 18 is the top of the flight of the screw, and 19 is the screw element. groove, 20
is the hole through which the screw shaft passes. In addition, Fig. 12 is a front view of an example of a so-called 21-dying desk that exhibits the crosstalk function used in the embodiment of the present application, and Fig. 13 is a side view of the desk. The hole, 21, is the top of the kneading disc. Figures 12-13
Usually, several kneading disks as shown in the figure are used in combination by changing the phase of their top portions 21. Furthermore, the 17th
A front view and a side view of other examples of the screw element are shown in FIGS.

Next, a process for producing a rubber-modified thermoplastic resin from raw materials according to the present invention using the above-mentioned apparatus will be explained. In order to simplify the explanation, the thermoplastic resin (2) is supplied from the supply port CM), and the thermoplastic resin (2) is supplied from the supply port (VII) and the supply port (X
) will be explained taking as an example the case where the thermoplastic resin (3) is supplied from the thermoplastic resin (3).

Latex (A) fed to the mixer shown in Figure 1
and the water-soluble drug (0) are mixed in a mixer to form a coagulated latex (A). The coagulated product of latex (A) is supplied into the extruder from the supply port (II) of the extruder, which has a structure as shown in FIG. 14. Reference numeral 22 in FIG. 14 is an opening that serves as a supply port for the latex (A) precipitate. Supply port (
III) is a supply port for the organic drug (B), and its shape may be similar to the dissolution supply port (II). Supply port (III)
must be located on the discharge side from the supply port (II).

When an organic agent is added at the supply port (III) and mixed with the coagulated product of the latex (A) of the graft polymer (1), the resulting mixture contains the graft rubber polymer (III), the organic agent (B) and a fine amount. The organic phase is separated into an organic phase composed of a small amount of a polymerization aid soluble in the organic drug, and an aqueous phase composed of a coagulant, water, and a small amount of a water-soluble polymerization aid.

The separation phenomenon progresses through the following process.

That is, first, prior to separation, the latex (A) coagulates form granules with a diameter of 15 to several square meters, and as the mixing continues, the granules adhere to each other and thicken while draining water.
Eventually, the mixture becomes a highly viscous cake-like substance that wraps around the extruder screw. In order to complete such a separation phenomenon, it is usually necessary to mix the latex (Al coagulate) and the organic agent (Bl) over a distance L1 that is four times or more, preferably six times or more, the inner diameter of Paléμ.

Further, since the separation phenomenon is completed by mixing in a section approximately 20 times the screw diameter (Ill), it is desirable that the distance 111 is 20 times or less from the viewpoint of miniaturizing the apparatus.

The two-phase mixture separated into an organic phase and an aqueous phase is transported to the screw of the extruder and reaches the drain port (V) K. Drain port (v
) is for discharging the aqueous phase in the two-phase mixture to the outside of the extruder and separating it from the organic phase. Figures 4 and 5 show the simplest structure of the drain port. An opening with a height of 1 to 10 days is formed on the side of the extruder barrel in the axial direction of the extruder.
The length is approximately 1 to 3 times the screw diameter (D). Even if an opening having such a simple shape is used, the organic phase, which has been completely separated into two phases, is well wrapped around the screw, so that almost no leakage of the organic phase from the opening occurs.

Figures 15 to 16 show other examples of the structure of the drain port (V). Figure 15 is a front view, and Figure 16 is a front view of the drain port (V).
It is a sectional view taken along the line X in the figure. In the example shown in FIGS. 15 and 16, since the comb-tooth-shaped slit portion 23 is provided, even if the separation phenomenon described above is incomplete and particulate matter is contained in a part of the organic phase, this can be filtered out. However, only the aqueous phase can be discharged from the extruder. If a drain port (V) as shown in Figs. 15 to 16 is used, the section in which the separation phenomenon takes place can be made shorter within the above range, that is, within the range of 4 to 20 times the screw diameter (D). Can be done.

Most of the aqueous phase of the two-phase mixture is separated at the drain port (v), but some of it is dispersed as small water droplets in the highly viscous organic phase or is entrained by the screw and sent to the discharge side of the extruder. I will be sent. Such water is degassed and removed in the vent louver (■) described below, but water has a large latent heat of vaporization, and removing a large amount of moisture by vaporizing it in the vent louver (■) requires a large amount of energy μ. ζ is undesirable. Therefore, a compression dehydration section was installed after the outlet (V) to compress and dehydrate the aqueous phase dispersed in the highly viscous organic phase, fill the barrel with the highly viscous organic phase, and entrain the aqueous phase with a screw. It is preferable to prevent In order to compress the organic phase, there are known techniques such as compressing the screw by gradually reducing the groove depth, decreasing the pitch of the screw flights, and inserting a barrier into the screw or barrel to obstruct the flow of high viscosity materials. can be used. The compressed and dehydrated aqueous phase flows to the rear end of the extruder, and the drain port (V
) is discharged from the extruder. The organic phase from which the aqueous phase has been separated is transported by a screw and reaches the supply port (IV) K. The supply port (W) is the supply port for the thermoplastic resin (2), which penetrates into the pallet 1v10 from above the barrel, and the thermoplastic resin (2) is normally transported into the extruder by falling under gravity. It is sent to the discharge end side by a functional screw. The thermoplastic resin (2) is transferred to the supply port (1) for the above-mentioned reason.
In the case of supplying from the main supply port (IV) or the main supply port (IV), the main supply port (IV) may not be provided.

When the thermoplastic resin (2) is supplied from the main supply port (VI), the thermoplastic resin (2) is mixed with the grafted rubber polymer (1) in order to exhibit the "reaggregation prevention function" as described above.
In the presence of the predetermined amount of the organic agent (a), it is necessary to knead in section L2 at a distance of at least twice the screw diameter (]), preferably at least four times the screw diameter. It is sufficient to conduct the test in a section approximately 10 times the distance of (D), and from the viewpoint of downsizing the device, L2 is preferably 10 times or less the screw diameter (D).Thermoplastic resin (
3) from the supply port (VII), the supply port (
The distance between VI) and the supply port (■) must be a distance 'L2 that is between twice and 10 times the screw diameter (to), and if there is no supply port (■), it is necessary to separate the distance between the supply port (VI) and the supply port (■). Mouth (VI
) is the closest ventro (■) to the screw diameter (
A distance L2 that is twice or more and 10 times or less of D) is required.

The thermoplastic resin (2) is fed through the supply port (I) or the supply port (IV).
), the graft rubber polymer (1) and the thermoplastic resin (force mixing) are performed in the interval TJ1 necessary for the above-mentioned two-phase separation to express the "reaggregation prevention function".

As mentioned above, the thermoplastic resin (2) is mixed to "prevent reaggregation" of the grafted rubber particles of the grafted rubber polymer (1).
The affected mixture of graft rubber polymer (III), thermoplastic resin (2) and organic agent (B) is transported to the supply port (■) by the screw.

The supply port (■) is for supplying part or all of the thermoplastic resin (3), and its structure and method of supplying the thermoplastic resin (3) may be the same as the supply port (VI). .

The thermoplastic resin (3) supplied through the main supply port (■) has the above-mentioned "coloring reduction" function. Therefore, the main supply port (
The thermoplastic resin (3) supplied in step (2) is mixed with a mixture of graft rubber polymer (III), thermoplastic resin (2) and organic agent (B), and then the thermoplastic resin (3) supplied in
) is preferable. In order to ensure this mixing, the main supply port (■) needs to be separated from the vent port (VIII) by a distance II3 that is at least one time, preferably at least twice the screw diameter (D). In addition, it is usually sufficient to mix in a section about 10 times the length of the screw diameter (D), and in order to downsize the device, L5 is preferably 10 times or less the screw diameter (orifice). III), thermoplastic polymer (2) and organic drug (B
) and the thermoplastic resin (3) supplied through the main supply port (■) are mixed by the screw while being mixed by the ventro (
■) will be transported to.

Ventro (■) is a mixture (organic phase mainly composed of grafted rubber polymer, thermoplastic resin and organic agent)
In particular, the organic agent (B) and the remaining moisture are vaporized and degassed from the mixture by heating. In particular, if a large amount of organic agent remains in the rubber-modified thermoplastic resin that is the product, the plasticizing effect will lower the heat deformation temperature, hardness, etc., and furthermore, bubbles of organic agent vapor may be mixed into the molded product during molding. Since the toxicity of organic drugs is a problem in food applications, etc., it is desirable that the residual amount of organic drugs in rubber-modified thermoplastic resin products be as small as possible. Usually, it needs to be less than 1% by weight, more preferably less than 15% by weight.

In order to satisfy this condition, ventro (■) is required at one or more locations, preferably two or more locations.

For example, as shown in Figures 7 and 8, the structure of Venthro (■) is that a mixture of graft rubber polymer (III), thermoplastic polymer (2), and organic agent (B) is used as Benthro (■).
It is preferable to have a structure in which it is difficult to vent up from the ventilation hole 17 of (2), and other known techniques can also be applied. Furthermore, the ventilation hole in the vent part can be made into an axially elongated hole to enhance the deaeration effect.

The polymer mixture, which has been degassed and removed from the organic agent in the ventro (■), is sent to the feed port (IX) by a screw.

At the first supply port (X), the remainder of the thermoplastic resin (3) added at the supply port (■) is supplied. The structure of the main supply port (IX) and the method of supplying the thermoplastic resin (3) are shown in the supply port (IV).
) is fine. The thermoplastic resin (3) supplied through the main supply port (IX) has the "residual organic drug concentration reducing function" as described above. When the thermoplastic resin (3) is supplied and mixed at the main supply port (DO), the mixture in the extruder becomes a rubber-modified thermoplastic resin composition as a product.
I) is discharged and subjected to post-processing steps such as pelletizing.

In addition, if necessary, volatile components contained in the rubber-growing thermoplastic resin that has been degassed with Pentro (X) to become the product composition (for example, volatile components contained in the rubber-growing thermoplastic resin that can be removed with Ventro (■) or supply It is also possible to remove residual volatile components such as residual sludge contained in the thermoplastic resin (3) supplied at the port (1).

The reason why the graft rubber particles can be uniformly dispersed in the thermoplastic resin by the method of the present invention is that the graft rubber particles are always in a dispersed state or in a soft agglomerated state without going through the conventional process of completely fixing them. This is thought to be due to the process of reaching the final product. Furthermore, in the method of the present invention, there is no need to use a dryer, which conventionally causes a large amount of heat loss.
Furthermore, if a mixer with a simple structure is used for the coagulation treatment of the latex (A) of the rubber-modified rubber polymer (1), the extruder can be downsized and productivity can be improved. A significant cost contribution is made to the resin industry.

[Examples of the Invention] The method of the present invention will be specifically explained below using Examples and Reference Examples. Note that all parts in Examples and Reference Examples are based on weight.

Polymerization of raw material polymer> Polymerization of Goft rubber polymer (i): Polybutadiene latex having an average particle size of 136 μm is subjected to Goft polymerization of acrylonitrile and styrene according to the recipe shown in Table 1 to obtain Goft rubber polymer (i).
of latex was obtained.

Table 1 Polybutadiene latex 1144 parts (
Polybutadiene solid content equivalent: 40 parts) Acrylonitrile A
/ 15 parts styrene
45 1 Sodium funate
α51 sodium hydroxide
α01 tt Rongarit
[1L21 Ferrous sulfate
α0021)! ! D Mu-disodium salt
IILl Tart-Buty Hydroperoxide 131 Fully μm Captan
0.31 deionized water
1251 Polymerization temperature 70℃
Polymerization time: 240 minutes Polymerization of graft rubber polymer (ii): Using the same chemicals as graft rubber polymer (i), graft polymerization was carried out according to the recipe in Table 2 to obtain a latex of graft rubber polymer (11). .

Table 2 Polybutadiene latex 22a6 parts (polygetadiene solid content equivalent: 80 parts) Acrylonitrile/I
/ 51 styrene
15 1Sodium urinate
α41 Sodium hydroxide [
LO1# Rongarit α
15 Ferrous sulfate α001
11!8DTmu-disodium salt α05y
tart-butyl peroxide (
Ll 1 fluffy μme captan Q
, 11 Deionized water 50 1 Heavy metal content 70°C polymerization time
280 minutes Gufufuto rubber polymer (i
Polymerization of i): Using the same chemical as the graft rubber polymer (1),
Graft polymerization was carried out according to the recipe shown in the table to obtain a latex of graft rubber polymer (ii).

Table 3 Polybutadiene latex 817 parts (polybutadiene solid content equivalent: 30 parts) Acrylonitrile/'
"17.5# styrene
525N Sodium Turiphosphate
(161 Sodium hydroxide
αo11 Rongalit
α3I ferrous sulfate [L 0
021EDTmu-disodium salt α121
Jest;-butiμ hydroperoxide
α351 Tourilme Captan (
L35# Deionized water 1431 Heavy metal content 70℃ polymerization time
240 minutes Gufufuto rubber polymer (1
Polymerization of v): EIBR rubber latex having a flat particle size of α14 μm was mixed with methiμ methacrylate and methiμ acrylate as a fourth polymer.
Graft polymerization was carried out according to the recipe shown in the table to obtain a latex of graft rubber polymer (iv).

Table 4 ffB! Rubber Wotechs IQO Department (8B
R Rubber solid content equivalent 5f1 part) Methyl methacrylate N 45p Acryμ
Methyl acid/I/ 5〃Potassium rosinate -1# Rongalit α21 ferrous sulfate 0. ．． 0011DT Mu-2 Sodium Salt Ill 1 Qumen Hydroperoxide α41 Octime μ
Captan (12N deionized water
150 I polymerization temperature
65℃ polymerization time
Polymerization of acripnitriμm styrene copolymer for 240 minutes:
Thermoplastic resins (2) and (3) according to the formulations in Table 5
An acrylonitrium styrene copolymer was prepared to be used as a styrene copolymer.

Table 5 Acrylonitrile / I / 25 parts Styrene 75 1 Azobisisobutyronitri A / f13z Furi〃meμ Captan (L5 #Bo9 k'
21V1fil/l/(degree of polymerization 900)
0.071 Sodium sulfate 0.
5 1 water
250 1 Heavy metal level 75
℃ polymerization nrj 240 minutes After completion of the polymerization, the suspension of the obtained acrylonitrile-styrene copolymer was centrifugally dehydrated and dried at 80° C. to obtain a powder of the polymer.

Polymerization of polymethyl methacrylate: Thermoplastic resins (2) and (3) according to the formulation in Table 6
Polymethacrylic acid methacrylic acid was prepared.

Table 6 Metacritic! Acid Methi/L/100
part azobisisobutyronitrium 1131 lauri μ memu captan (L5 #Polyvinyl 7A/: l-1v (degree of polymerization 900) C
LO7p Sodium Sulfate α25
1 water
200 1 Polymerization temperature 80
C. Polymerization time: 180 minutes After completion of the polymerization, the resulting suspension of methyμ polymethacrylic acid was centrifugally dehydrated and dried at 80°C to obtain a powder of the polymer.

Examples 1 to 6 A latex of the graft rubber polymer of the type and amount shown in Table 8 and an aqueous sulfuric acid solution having a concentration of 15% by weight were fed into a mixer as shown in FIG. 1, and mixed in the mixer to form the latex. The coagulated product was obtained, and the waste water shown in Figs. 4 and 5 was put into a co-rotating twin screw extruder with a diameter of 30mm and an effective screw part length of 1075cm as shown in Fig. 3 and Table 7. Mouth (II=3
■, W-10-), and the vent ports shown in Figures 7 to 8 should be installed using organic chemicals of the type and amount shown in Table 8.
And acrylonitri! - supplying a styrene copolymer as a thermoplastic resin (2) and a thermoplastic resin (3),
An attempt was made to manufacture rubber-modified thermoplastic resin pellets (in addition,
The thermoplastic resin (3) K was prepared by dispersing and mixing 15% by weight of a molding aid (Aramide HT, trade name, manufactured by Lion Armor Co., Ltd.) with respect to the total polymer.

First, the mixer jacket temperature was set to 60°C, the stirring blade rotation speed was set to 200 rpm, and the extruder temperature was set as shown in Table 7.
The screw rotation speed was 200 rpm. The latex of the graft rubber polymer, which is supplied in a fixed quantity from the supply port 2 of the mixer by a Pfunger pump, is mixed with a 15% by weight aqueous sulfuric acid solution, which is supplied in a fixed quantity from the supply port 1 by a 1-land gear pump, and completely mixed. It coagulated and became a cream-like substance, which was discharged from the discharge port 3 and supplied into the extruder from the supply port (II) in FIG. The creamy substance is supplied through the supply port (I
II) is mixed with the organic agent shown in Table 8, Column 5 (to-ene or ethylbenzene) supplied quantitatively by a Putsenger type bonder in section I11, separated into a rice cake-like organic phase and an aqueous phase, and then drained into the drain port. A clear aqueous phase was discharged from (V). The mochi-like organic phase wraps around the screw and passes through the outlet (
V) was not discharged. The organic phase is in sections L1 and L2
The combination of the Nucle Element shown in FIGS. 10 to 11 and the kneading disk shown in FIGS. It was discharged from the drain port (V).

The amount of acrylonitrium styrene copolymer powder shown in column 7 of Table 8 was supplied as a thermoplastic resin (2) to the dehydrated organic phase through the supply port (VI) using a veterinary feeder. ! , 2 with a kneading disk having the shape shown in FIGS. 12 to 13. After heating, the pressure was reduced to the pressure shown in column 10 of Table 8 using a ventilator (■), and the organic phase was heated. The organic agent and remaining aqueous phase were removed by degassing to obtain a mixture of graft rubber polymer and thermoplastic resin (2). The resin mixture K, supply port (D.

Then, acrylonitrium styrene copolymer powder was fed as the thermoplastic resin (3) using a pet feeder, mixed in section L3, and then added to Table 8, Table 10, in a K ventro (X).
The pressure is reduced to the pressure shown in the column, the volatile components in the acrylo-tolyl-styrene copolymer added at the supply port (IX) are degassed, and the discharge port (XI) is removed. A 7 m product of rubber-modified thermoplastic resin was discharged in the form of a strand. This was water-cooled and made into pellets. The obtained pellet was smooth, and no uneven portions called fish eyes were observed. This was injection molded to create various test pieces, and various physical property values were measured, and the results shown in Table 9 were obtained. These values indicate that the rubber-modified thermoplastic resin produced in this example is excellent.

Table 7 Example 8 Figures 15 to 16 (W=(15■, H=
A rubber-modified thermoplastic resin was produced under the conditions shown in Table 8 using the same mixer and extruder as in Example 1, except that the same mixer and extruder as in Example 1 were used, except that the same mixer and extruder were used.

At the drain port (V), the separation of the organic phase and aqueous phase was incomplete, and part of the organic phase became particulate matter and was dispersed in the aqueous phase, but it was filtered through the slits shown in Figures 15 and 16. The aqueous phase that was removed and drained contained almost no organic phase.

Comparative Example The latex of the grafted rubber polymer produced in Example 1 was coagulated with sulfuric acid by a conventional method, and the resulting wet polymer powder was washed, dehydrated, and dried to obtain a dried grafted rubber polymer powder. This graft rubber polymer, an acrylonitrile-styrene copolymer prepared according to the recipe shown in Table 5, and the same amount of additives as used in Example 1 were mixed and processed into a pellet using a screw extruder. The composition of the pellet obtained at this time was the same as that of the pellet obtained in Example 1, but there were many lumps on the surface and the pellet had no commercial value. Furthermore, the obtained pellets were injection molded and the same tests as in Example 1 were conducted to obtain the evaluation results shown in Table 10.

Table 10 Examples 9 to 10 Using the same mixer and extruder as in Example 1, the jacket temperature of the mixer was 70°C, the stirring blade rotation speed was 200 rpm, and the extruder was heated at the temperature shown in Table 11. Rotation speed to 20
Orpm, a latex of graft rubber polymer (iv) as shown in Table 12, an aqueous solution of magnesium sulfate at a concentration of 3% by weight, chloroform, and polymethacrylic acid methane thermoplastic resins (2) and (3). A rubber-modified thermoplastic resin pellet was produced in the same manner as in Example 1.

The obtained pellet was smooth, and no uneven portions called fish eyes were observed. When various test pieces were prepared by injection molding and various physical property values were measured, the results shown in Table 11 were obtained. These values indicate that the rubber-modified thermoplastic resin produced in this example is excellent.

Table 11 Example 11 Using the same mixer and extruder as in Example 1, the jacket temperature of the mixer was 60°C, the stirring blade rotation speed was 200 rpm, and the extruder was set at the temperature shown in Table 13 with a screw rotation speed of 250 r.
pm, latex 5 of Gofuft rubber polymer (11)
7.5 parts, 50 parts of (L3% by weight aqueous sulfuric acid solution) were each supplied from mixers 2 and 1, and 20 parts of Diku p/I/methane was supplied from the supply port (III) of the extruder. 12.5 parts of acrylonitrium styrene copolymer was supplied as the thermoplastic resin (2) from the supply port (IV), and
X) to polycarbonate resin C barrecks 7022.
1 product name, manufactured by Mitsubishi Chemical Industries, Ltd.) 75 parts,
A rubber-modified thermoplastic resin pellet was produced in the same manner as in Example 1. This pellet contains 110 tons of butadiene.
*Oshi and pu are not included. Table 14 shows the test results of test pieces obtained by injection molding the pellets.

Table 13 Table 14 (Test method is the same as Example 1) 5I! Examples 12 to 14 To the same mixer as in Example 1, a latex of the graft rubber polymer of the type and amount shown in Table 15 and an aqueous sulfuric acid solution with a concentration of 15% by weight were fed, and mixed in the mixer to coagulate the latex. A co-rotating twin-screw extruder K with a diameter of 30 cm and an effective screw part length of 1110 m as shown in Fig. 9 and Table 16 was used. ! Drain ports (I) shown in Figures 1 to 5
I-5■, W, 10■) and centotate shown in FIGS. 6 to 8 were installed, and organic chemicals of the types and amounts shown in Table 15 were added, and acrylonitrile! - A rubber-modified thermoplastic resin pellet was produced in the same manner as in Example 1 by supplying the styrene copolymer as the thermoplastic resin (2) and the thermoplastic resin (3) (note that the thermoplastic resin (3) K is a molding aid (Aramide H) containing 15% by weight of CL based on the total polymer.
! (trade name, manufactured by Buion Armor Co., Ltd.) were dispersed and mixed in advance. ).

The obtained pellet was smooth, and the presence of non-uniform portions called "fits V" was not observed. This was injection molded to create various test pieces, and various physical property values were measured, and the results shown in Table 17 were obtained. These values are book 97! This shows that the rubber-modified thermoplastic resin produced in the example is excellent.

Table 16 [Effects of the Invention] Comparing the effects of the method of the present invention with the conventional method, the first advantage in terms of process is that there is no need to powderize the polymer. More specifically, (1) dehydration after coagulating latex and obtaining wet powder;
Steps such as drying, air transportation of powder, and storage can be omitted, simplifying the process.

(2) Heat loss in the dryer can be avoided.

etc., the cost reduction effect is significant. Furthermore, (3) no dust is generated and the work environment is not contaminated.

There are also other effects.

In addition, when compared with the conventional method in terms of quality, (4)
In the present invention, since the graft rubber polymer is dispersed in the thermoplastic resin in the presence of an organic agent, the graft rubber polymer particles do not stick to each other, and homogeneous dispersion of the graft rubber polymer is possible. It becomes possible to produce high-quality rubber-modified thermoplastic resin.

(5) In particular, it is possible to produce a rubber-modified thermoplastic resin with less appearance defects such as fish eyes.

There is an effect.

Furthermore, in the present invention, when the timing of addition of the thermoplastic resin and the effects of use are analyzed in detail, (6) the amount of organic chemicals used can be reduced.

(7) It is possible to improve the volume usage efficiency of the device.

This effect also occurs.

Furthermore, in the present invention, we investigated in detail the process in which polymer latex is separated into an organic phase and an aqueous phase, and then a thermoplastic resin is mixed to produce a rubber-modified thermoplastic resin. The mixer replaced the conventional steps of coagulation, dehydration, drying, blending, and melt extrusion, greatly simplifying the process, and by providing one mixer, we succeeded in further increasing the productivity of the process. .

Thus, the present invention provides a technique for producing high quality rubber-modified thermoplastic resins at low cost.

[Brief explanation of the drawing]

Figure 1 is a sectional view of the mixer used in the examples, and Figure 2 is an extruder equipped with all the supply ports, drain ports, vent ports, and discharge ports that may be provided in the extruder used in the present invention. FIG. 3 is an axial cross-sectional view of the extruder barrel used in the example of the present invention, and FIG. 4 is a front view of the drain port (V) used in the example. Figure 5 is the X in Figure 4.
-X' sectional view, Figure 6 is a sectional view perpendicular to the barrel axis of the supply port used in the example, Figure 7 is a plan view of the nine vent port used in the example, and Figure 8 is the X of Figure 7. -X' sectional view, 9th
The figure is an axial cross-sectional view of the barrel used in other examples, the first
Fig. 0 is a front view of an example of the screw element used in the example, Fig. 11 is a side view thereof, Fig. 12 is a front view of an example of the kneading disk, Fig. 15 is a side view thereof, and Fig. 14 is the implementation. A sectional view perpendicular to the barrel axis of the supply port ω) used in the example, FIG. 15 is a front view of another example of the drain port (V), FIG. 16 is a sectional view taken along line Xf in FIG. The figure is a front view of another example of the screw element, and FIG. 18 is a side view thereof. In Figures 1 to 18, 1 is a water-soluble drug (mouth supply port, 2 is
are the supply port for latex (A), 3 the discharge port for coagulate, and 4
is the hot water inlet, 5 is the hot water outlet, 6 is the stirring blade, 7 is the mixer body, 8 is the jacket, 9 is the lid, 10 is the barrel, 11 is the barrel outer surface, 12 is the barrel inner hole, 13 is the parts, 14 is the opening 15 is a hole, 16 is a lid, 17 is a ventilation hole, 18 is a flight top of a screw, 19 is a groove of a screw, 20 is a hole through which a screw shaft passes, 21 is a top of a kneading disk, 22 is an opening, 25 is the slit part, (L) is the supply port for thermoplastic resin (2), (II) is the supply port for latex coagulate, (■) is the supply port for organic agent), (IV
) is the supply port for thermoplastic resin (2), (V) is the drain port, (
W) is the supply port for thermoplastic resin (2), (■) is the supply port for thermoplastic resin (5), (■) is the vent port, (X) is the supply port for thermoplastic resin (3), and ω is the supply port for thermoplastic resin (3). The vent port and (IV) indicate the discharge port, respectively. Collected 1 concave 4 illustrations, 5 illustrations, Otsu Ward, 7 illustrations of Hata, 14 illustrations, 70 illustrations, 11 volumes of Hata, 9 books, 12 illustrations, 73 illustrations of Taisho, 15 illustrations &/ 4 Rino 7, Shiko
4s18 Figure/q

Claims (1)

[Scope of Claims] 1. A graft rubber polymer (1) obtained by emulsion graft polymerization of a vinyl monomer onto a rubber latex, a thermoplastic resin (
3) and, if desired, a thermoplastic resin (2), when producing a rubber-modified thermoplastic resin consisting of the latex (A) of the graft rubber polymer (1) and the graft rubber polymer (1) by 10% by weight. % or less of latex (A)
A water-soluble drug (C) that can coagulate is mixed in a mixer to obtain a coagulated product of latex (A), and then the following (II), (III), (V), (VIII) and (
X I) has a supply port, a drain port, a vent port, and a discharge port, (II): a supply port for supplying the coagulated product of the latex (A) obtained from the mixer, (III): a supply port A supply port for the following organic agent (B) located on the discharge side from (II), organic agent (B): grafted rubber polymer and thermoplastic resin (
It has the ability to dissolve 10 to 600% by weight of the thermoplastic resin (2) based on the total amount of the thermoplastic resin (2), and its solubility in water is at the barrel temperature (E) of the drain port (V) described below. Organic agent containing 5% by weight or less, (V): 4 of the screw diameter (D) from the supply port (III)
Located on the discharge side by a distance (L1) that is greater than or equal to 20 times,
A drain port for discharging the aqueous phase separated from the mixture of substances added up to the supply port (IV); (VIII): vaporizing the organic agent (B) and the remaining aqueous phase that has not been discharged from the drain port (V); 1 or more places to be removed 4
(X I): A discharge port for the molten rubber-modified thermoplastic resin, and a supply port for the thermoplastic resin (3) shown in (VII) and/or (IX) below, (VII) : A supply port for the thermoplastic resin (3) located on the drive side from the vent port (VIII) closest to the supply port (VII) by a distance (L3) of 1 to 10 times the screw diameter (D), ( IX): Supply port for thermoplastic resin (3) located on the discharge side from the vent port (VIII). When using thermoplastic resin (2), the following (
One of the supply ports (I), (IV), and (VI) has a thermoplastic resin (2) supply port, and (I): The thermoplastic resin (2) is located on the drive side from the supply port (II). 2) supply port, (IV): supply port for thermoplastic resin (2) located on the discharge side from supply port (II), (VI): supply port (VII), if it has a supply port (VII),
I) is located on the drive side by a distance (L2) from 2 times to 10 times the screw diameter (D), and if it does not have a supply port (VII), the vent port closest to the supply port (VI) ( VIII) from the distance (L
2) is located on the drive side, and if the extruder also has a supply port (IX), use an extruder having the following vent port (X) if desired: (X): A vent port located at a distance (L3) from the supply port (IX) on the discharge side, and having one or more and two or less vent ports for removing volatile components contained in the rubber-modified thermoplastic resin product, By supplying the organic agent (B) from the supply port (III) to the mixture containing the coagulated latex (A) supplied to the supply port (II) of the extruder, and kneading it in the interval of distance (L1), The latex (A) is separated into an organic phase containing the graft rubber polymer (1) and an aqueous phase, and the aqueous phase is discharged from the extruder through the drain port (V). The mixture containing the organic agent (B) is removed from the vent port (VIII) and the moisture that has not been discharged from the discharge port (V) is degassed, and if desired, the thermoplastic resin (
2) is supplied from the supply port (I) or the supply port (IV) or the supply port (VI) and mixed with the mixture containing the graft rubber polymer (1) and the organic agent (B) over a distance (L2), In addition, the thermoplastic resin (3) is mixed with the mixture containing the graft rubber polymer (1) from the supply port (VII) and/or the supply port (IX) over a distance (L3), and if desired, the thermoplastic resin (3) is mixed with the mixture containing the graft rubber polymer (1) from the supply port (VII) and/or the supply port (IX), and if desired, the thermoplastic resin (3) is ) A method for producing a rubber-modified thermoplastic resin, characterized by degassing volatile components. 2. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is not supplied. 3. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is supplied from the supply port (I). 4. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is supplied from the supply port (IV). 5. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is supplied from a supply port (VI). 6. The method for producing a rubber-modified thermoplastic resin according to any one of claims 1 to 5, characterized in that the thermoplastic resin (3) is supplied entirely from the supply port (VII). 7. The method for producing a rubber-modified thermoplastic resin according to any one of claims 1 to 5, characterized in that the thermoplastic resin (3) is supplied from the entire supply port (IX). 8. A part of the thermoplastic resin (3) is supplied from the supply port (VII), and the remaining part is supplied from the supply port (IX), according to any one of claims 1 to 5. A method for producing a rubber-modified thermoplastic resin. 9. Claims 1 to 8, characterized in that a part of the organic agent (B) is degassed and removed through the vent port (VIII), and the remainder is degassed and removed through the vent port (X). A method for producing the rubber-modified thermoplastic resin described above. 10. A compression part is provided between the drain port (V) and the supply port or vent port adjacent to the discharge side, and the graft rubber polymer (1) is
and the organic phase containing the organic agent (B) is compressed and dehydrated, and the compressed and dehydrated water is discharged from the discharge port (V). Method of manufacturing thermoplastic resin.