JPH08120031A - Continuous production of ultrahigh-gloss abs resin - Google Patents

Abstract

PURPOSE: To obtain a high-gloss ABS resin without detriment to its impact resistance. CONSTITUTION: This process for continuously producing an ultrahigh-gloss ABS resin by solution or bulk polymerization comprises the steps of: producing an ABS resin by polymerization, separating and recovering unreacted monomers and/or the solvent from the resin component by heating the mixture containing the polymer, unreacted monomers and/or the solvent and introducing the mixture into a vacuum chamber during or after the heating, feeding the resin component into the extruder and passing it through the extruder to obtain a product. In the process, a zone (zone X) for adding water, a zone (zone Y) for evaporating the added water and a zone (zone Z) for kneading the resin after the evaporation of the water are provided between the exit of the recovery step and the exit of the extrusion step (particularly zones Y and Z are provided in the extruder) and water is added to the resin in zone X and then evaporated in zone Y to adjust the temperature of the resin to a temperature lower than that of the resin at the exit of the recovery step by 10-60%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ABS resin having high gloss while maintaining impact strength.

[0002]

2. Description of the Related Art Conventionally, ABS resins have been widely used as resins having excellent gloss. However, in recent years, in order to increase the commercial value of home electric appliances and electronic products,
There is a demand for ABS resins having a high gloss. Conventionally, when the molding temperature is lowered, the gloss of the product is generally lowered, but there is a demand for an ABS resin which lowers the processing temperature and retains a high gloss in order to improve the cycle during molding.

Generally, in ABS resins, the size of rubber particles in the resin is known as a key factor in determining gloss and other physical properties. For each application, gloss and impact properties, for example, The rubber particle size is designed while balancing the molding characteristics. However, the conventional methods have a limit in improving the gloss while maintaining the physical properties of the ABS resin, and a new method has been required. For example, rather than modifying the resin itself, it has been practiced to increase molding conditions, such as mold temperature, at the molding stage. In this case, molding conditions are limited, a molding injection cycle becomes long, and an important problem remains in productivity.

Further, JP-A-62-164707, page 38
From the 17th line on the upper right side to the 6th line on the lower left side, in the ABS resin by the emulsion polymerization method, the rubber particles are provided with a suitable graft layer on the surface of the rubber, and the thickness thereof is 100 to 200Å, thereby providing a high gloss ABS system. There is a description that a resin can be obtained. However, this method is not suitable for continuous bulk polymerization or solution polymerization because it controls the chemical composition in a complicated manner.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for increasing the surface gloss of ABS resin while maintaining impact strength and the like.

[0006]

In the present invention, the gloss of the surface of the molded product is improved by using a technical means which is completely different from the conventional one.

That is, in the present invention, in the ABS resin solution or continuous bulk polymerization method, surprisingly, the gloss of the surface of the molded product of the resin obtained by adding water in the extrusion step and further kneading The inventors have found that they can be improved and have reached the present invention.

That is, in the method for producing an ABS resin by the solution or continuous bulk polymerization method of the present invention, the extruder has a portion for adding water to the resin and a portion for evaporating the added water. The temperature of the resin in the extruder is lowered by evaporating the water, so that the resin is kneaded in the extruder. By such a method, a resin having an excellent surface gloss as compared with the ABS resin obtained by the conventional method is provided.

That is, according to the present invention, a raw material containing at least a styrene-based monomer, an acrylonitrile-based monomer, and a rubber-like polymer is supplied to a polymerization step, the monomer is polymerized, and rubber-like polymer particles ( (Rubber particles) through a polymerization step of polymerizing the monomer, and then heating a mixed solution containing a polymer, an unreacted monomer and / or a solvent, simultaneously with heating, or after heating, a decompression chamber Via a separation and recovery step in which the monomer and / or solvent is separated from the resin component by introducing into
In the continuous method for producing an ABS resin by the solution or bulk polymerization method, which is introduced into an extruder after the recovering step and passed through the extruder to obtain a product, water is collected between the recovering step outlet and the extrusion step outlet. Has a portion for adding (X portion), a portion for evaporating the added water (Y portion), and a portion for kneading the resin after evaporation (Z portion). Particularly, the Y portion and the Z portion are provided in the extruder (E). It is provided, and is characterized by adding water to the X part and then evaporating the water in the Y part so that the temperature of the resin is lowered by 10 to 60% of the temperature of the resin at the exit of the recovery process. Is a method for producing an ABS resin.

The portion to which water is added (X portion) has a structure in which a pipe for passing water to be added to the portion is connected, and water is forcibly introduced into the extruder by using, for example, a plunger pump. Therefore, the screw may have a kneading portion so that the resin and water can be sufficiently mixed. In addition, the portion (Y portion) where the added water is evaporated is connected to a pipe connected to a decompression device such as a vacuum pump, and is kept in a depressurized state so that the added water passes through the portion in the extruder and can be removed. It has a structure.

The portion to which water is added may be one place,
You may provide in three places. Further, one or more 3 to 5 portions can be provided to evaporate water. The amount of water added is
The amount of the extruded resin per unit time is 2 to 15 parts by weight, preferably 2.5 to 15 parts by weight, and more preferably 4 to 15 parts by weight with respect to 100 parts by weight of the extruded resin. If the amount of water added exceeds 15 parts by weight, the processing capacity of the extruder is lowered and the productivity is affected, which is not preferable.

In the method of the present invention, the resin in the process of being introduced into the extruder after the (I) separation and recovery step is 0 from the surface of the molded product (molded product 1) obtained when the resin is injection molded. When the rubber particles present at a depth of 0.5 to 1.5 μm are observed on an electron micrograph of a plane parallel to the surface of the molded article by an ultrathin section method, the ratio a / b of the major axis a and the minor axis b is 1 Particle A of less than or equal to 5
And at least two types of particles B having a ratio a / b of the major axis a to the minor axis b of 5 or more and the total area of the rubber particles observed by an electron micrograph by the ultrathin section method is 10
The area of particles A is at least 10% or more when 0%,
ABS in which the area (B ₁ ) of particles B is 0.001 to 2%
The area (B ₂ ) of the particles B, which is a system resin and is observed by the same analysis method as the above (I) in the product after passing through the (II) extruder, has the following relational expression 0.001 ≦ B ₂
/ B ₁ × 100 ≦ 50 is satisfied, which is a method for producing a high-gloss ABS resin.

Here, the particle B is 0.0 on the surface of the molded article 1.
It is preferable that the content is 01 to 2%. B ₁ particle 0.0
When it is less than 01, the effect of the present invention is not exhibited, and 2
If it exceeds%, it is difficult to obtain a resin having high gloss, which is not preferable.

The molded product 1 has a rubber particle average diameter of 0.05 to 1.5 μm, preferably 0.1, as measured by the following method.
˜1.0 μm, more preferably 0.15 to 0.7 μm. When the rubber particle size is 0.1 μm or less, the impact strength is lowered, and when it is 1.5 μm or more, high gloss cannot be obtained. The average particle diameter of the rubber particles is measured by taking an electron microscope photograph by the ultrathin section method and measuring the rubber particles 50 in the photograph.
From 0 to 700 minor and major diameters are respectively measured, the average value is taken as the particle diameter, and the volume average diameter is determined by the following formula. Volume average diameter = ΣnD ⁴ / ΣnD ³ (where n is the particle diameter D μm
Is the number of rubber particles. Further, as the extruder used in the present invention, it is preferable to use a twin-screw or single-screw extruder having a kneading section.

In the present invention, the average diameter of the rubber particles is determined in consideration of the balance with the performance of the resin other than the gloss. The method of the present invention dramatically improves the conventional balance between gloss and other physical properties.

In the present invention, the ABS resin can add and evaporate water in the extruder to sufficiently lower the temperature of the resin, so that the deterioration of the resin in the extruder is suppressed and the hue of the product becomes good. is there.

Conventionally, a method of adding water to an extruder in order to remove volatile components has been known. However, in the process for producing an ABS resin by a continuous polymerization method of a solution or a block, water is added to the resin in the extruder. There has been no known method for reducing the temperature of the resin and kneading the resin having the lowered temperature.

It is presumed that this is due to a mechanism that has never been known from the knowledge of ABS resins. That is, generally, the ABS resin is composed of a copolymer of styrene / acrylonitrile and rubber particles obtained by grafting and occluding a part of these copolymers. The surface of the rubber particles is covered with the graft portion so that the shape of the rubber particles is stabilized and the performance of gloss and impact is exhibited. However, upon further study, it was found that the method of the present invention can further improve gloss. Although the reason for the manifestation of the effect of the present invention is not clear, an extremely small portion of the rubber particles is not stable as described above, and therefore, only a small portion of the rubber particles are deteriorated during molding, It is speculated that the gloss of the surface still has room for improvement, and that the treatment with the extruder in the present invention completely stabilizes the rubber particles and brings about the effect.

As a preferred method in the present invention, particles A and particles B are observed in the resin molded product (molded product 1) entering the extruder after the recovery step, and the particle B is introduced at the exit of the extruder. However, it is presumed that the particles B can be an index for the degree of surface protection.

The extruder in the present invention is one of the equipment used for extrusion molding and compounding,
The material is continuously heated, melted, and kneaded between a part called a cylinder and a rotating screw, and is extruded from a die to be molded or pelletized.The kneading condition varies depending on the shape of the rotating screw and the like. .

The kneading in the present invention refers to the action of uniformly dispersing and mixing the respective elements in the fluid in the extruder, and a preferable screw shape as the portion (Z portion) to be kneaded is "extruder which is utilized in the field". Manual “Hiroaki Hamada, Industrial Research Society, page 113, figures 4.12, 114, figures 4.13, 115, figures 4.14, 116, figure 4.1.
5, 117, Fig. 4.16, the screw shape of the single-screw extruder is described, and 148, Fig. 5.1, the screw type of the twin-screw extruder is described. Examples include screws, co-rotating meshing twin screw, co-rotating partially meshing twin screw,
Page 151, FIG. 5.2 describes the screw elements of a twin-screw extruder, and these extruders can be used. From page 150, line 8 to page 151, line 7, there is a forward screw part and a reverse screw part for the element to be attached to the screw, and a mixing part called a kneading disk for kneading is provided in the middle. Also, an extruder having a twin screw having a kneading disk in 10 to 50% of the effective screw length is preferably used. These parts are distinguished from other parts, and the kneading part is intended to give a shearing force to the resin, while the other parts are intended to advance the resin.

The kneading disc in the present invention is a part constituting a screw of a twin-screw extruder, and is a mixing section for the purpose of kneading. For example, the above-mentioned "Extruder manual to be utilized in the field", page 150, line 14 to page 152, line 14, page 151, FIG. Ding disks are also preferably used.

The effective screw length in the present invention means the length of the screw excluding the gland portion at the base of the screw and the conical portion at the tip, and is usually the screw length L, the ratio L / D of the cylinder diameter D, or The number of times D is displayed.

The ABS resin used in the present invention is a rubber-like polymer, a styrene monomer, an acrylonitrile monomer, and
If necessary, it is a resin composed of a copolymer of other monomers. Here, as the styrene-based monomer, styrene, α-
Alkyl monovinylidene aromatic monomers (eg α-methylstyrene; α-ethylstyrene; α-methylvinyltoluene; α-methyldialkylstyrene; etc.), ring-substituted alkylstyrenes (eg om- and p-vinyltoluene) O-ethylstyrene; p-ethylstyrene;
2,4-dimethyl styrene; p-tertiary butyl styrene; etc.), ring-substituted halostyrenes (eg o-chlorostyrene; p-chlorostyrene; o-bromostyrene;
2,4-dichlorostyrene; etc.), ring-alkyl, ring-halo substituted styrene (for example, 2-chloro-4-methylstyrene; 2,6-dichlorostyrene; etc.) vinylnaphthalene, vinylanthracene, or a mixture thereof. To be

Alkyl substituents generally have 1 to 4 carbon atoms and include isopropyl and isobutyl groups. One or a mixture of these monovinylidene aromatic monomers is used. Examples of the acrylonitrile-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and mixtures thereof.

The rubbery polymer is not particularly limited as long as it shows a rubbery state at room temperature, but preferably polybutadienes such as conjugated 1,3-dienes (eg butadiene; isoprene; etc.) and styrene. Examples thereof include butadiene copolymer and EPDM (ethylene-propylene-diene copolymer).

The other monomer in the present invention is styrene,
The monomer is not particularly limited as long as it is a monomer copolymerizable with acrylonitrile, and examples thereof include acrylates such as methyl methacrylate and maleimides such as N-phenylmaleimide and cyclohexylmaleimide.

The ABS resin composition is styrene 5
0 to 95 parts by weight, acrylonitrile 5 to 50 parts by weight, butadiene polymer, or styrene-butadiene block copolymer 3 to 30 parts by weight are preferred.

The ABS resin used in the present invention is a resin containing the above ABS resin and ABS resin as components.
The resin containing the ABS resin as a component means a mixture of the ABS resin and other resins such as polycarbonate, polyphenylene ether, polypropylene, polystyrene, acrylonitrile-styrene copolymer resin, a mixture of the ABS resin and a flame retardant, and glass. There is no particular limitation as long as it is a resin containing ABS resin as a component, such as a mixture of filler and talc.

The ABS resin molded product used in the present invention is a molded product obtained by molding the ABS resin.
Utilizing the mechanical and chemical characteristics of the system resin, it is used as a mechanical component, or as a final product such as stationery supplies and toys. As the molding process, a conventional resin molding method known so far is used, and examples thereof include injection molding and extrusion molding. The injection molding method is preferred. As preferable injection molding conditions, the cylinder temperature of the molding machine is 170 ° C to 280 ° C, preferably 180 ° C.
To 260 ° C, more preferably 200 ° C to 250 ° C,
The mold temperature is 30 to 90 ° C. In the present invention, it is remarkable that the gloss is improved particularly when molding is performed at low temperature molding conditions, for example, when the cylinder temperature of the molding machine is 190 to 220 ° C.

In the present invention, the region which determines the morphology (morphology) of the rubber particles is set to have a depth of 0.5 to 1.5 μm from the surface, because the rubber particles present in this range of depth have a specific morphology that has never been found. It is based on the finding that the surface characteristics of the molded product can be controlled by The fact that 0.5 to 1.5 μm in the vicinity of the surface is based on the fact that the existence state of the rubber particles is substantially constant without being dependent on the depth between this depth. . That is, when the depth is less than 0.5 μm, there are many variations in the morphology of the rubber particles and 1.5 μm.
Beyond the range, the existing state changes depending on the depth, so that it is not suitable for specifying the morphology of rubber particles that correlates with the surface characteristics.

In the present invention, the morphology of the rubber particles is measured in parallel to the surface of the molded product. This parallel cross section is obtained by cutting the molded product into ultrathin sections parallel to the surface of the molded product using a microtome. At this time, the thickness of each sample cut out by a microtome is set to 0.05 μm and cut out in order from the surface, and the morphology is measured using the 11th to 30th samples.

The particle A in the present invention means, in an electron micrograph of such a sample, when the major axis of the rubber particles is a μm and the minor axis is b μm, the ratio a / b of a and b is 1.5.
The following is defined as particle A. B is a particle having a / b of 5 or more.

The major axis a referred to in the present invention represents the maximum length of the distance between two points on the circumference of the rubber particles observed in the electron micrograph by the ultrathin section method, and the minor axis b is the major axis a. Shows the length of the rubber particles perpendicular to the major axis a at the point a / 2. Under such a constraint condition, when calculating the areas of the particles A and B, the size of the visual field to be observed with the electron microscope is determined so that the total area can be 1000 μm ² or more. This number is not particularly limited, but the field of view of the electron microscope is the size of the field of view containing 1000 or more rubber particles.

A introduced into the extruder (E) in the present invention
The BS-based resin is characterized in that it contains particles B when the surface vicinity is observed with an electron microscope when it is formed into a molded product.
The production method is not limited as long as the particles B are present. For example, in the case of the bulk polymerization method, the particles (B) are produced by changing the recovery temperature in the recovery step. For example, the average resin temperature (T _AV ) at the recovery outlet in the separation / recovery step of separating the solvent and unreacted monomer from the resin component in the ABS resin manufacturing step by the bulk polymerization method is set in the range of 170 to 280 ° C. Particles B are generated by changing the temperature of the resin at the outlet and adjusting the product of the rate of change of the temperature at the outlet of recovery with respect to T _AV (T _de ) and the number of times of temperature change per hour (N _CT ). . The average value (T _AV ) of the recovery temperatures referred to in the present invention is calculated by the following formula.

[0036]

[Equation 1] The temperature variation rate (T _de : temperature variation rate per hour) in the present invention is calculated by the following formula. Temperature fluctuation rate (T _de ) = ((T _max −T _min ) / T _AV ) ×
100 (however, T _max is the maximum temperature of recovery temperature per hour, T _max
min is the minimum temperature. The number of temperature changes per hour is called the number of temperature changes per hour (N _CT ) (however, changes within a temperature change rate of 0.5% are ignored), and the temperature is differentiated with respect to time. The number of times the value fluctuates between positive and negative.

In the present invention, the average value T _AV of recovery temperature, the temperature variation rate T _de, and the number of times of temperature variation per hour are calculated by operating with the average value of the recovery temperature constant for 3 hours or more and operating from the measured values in that section.

The ratio of particles B can be controlled by adjusting the product (F) of T _de and N _CT . In the present invention, those having the value of F within the range of 0.5 to 20 can be used. In the present invention, the above-mentioned molded product 1 (in order to obtain the molded product 1, the resin is taken out in the form of a string from the sample valve provided at the outlet of the recovery step, cooled in a water tank to obtain a strand, and this is cut to form a pellet. The obtained pellets are introduced into an injection molding machine and molded under the same conditions as the molded product 2.) A parallel surface having a depth of 0.5 to 1.5 μm from the surface of the molded product is observed by an electron microscope using an ultrathin section method. When observed, the resin having the particles A and the particles B is fed into the extruder after exiting the separation and recovery step. The resin thus obtained is molded (molded product 2),
When the surface of the molded product was observed by an electron micrograph in the same manner as in the molded product 1, the ratio of the particles B in the molded product 1 was B ₁ , the ratios of the particles B observed in the molded product 2 were B ₂ , B ₂ / B ₁ x 10
_BD represented by 0 is 0.001 to 50, preferably 0.
The surface gloss of the molded product can be improved by reducing the particle B so as to be 1 to 45, more preferably 0.1 to 30.

For example, the area ratio of the particles B observed in the molded article 1 is generated by the fluctuation of the recovery temperature in the separation / recovery step of the ABS resin manufacturing step by the solution or bulk polymerization method.

In the present invention, the greater the degree of temperature fluctuation in the separation / recovery step and the greater the degree of shearing applied to the resin in the extrusion step, the smaller the proportion of the area of the particles B observed on the surface of the molded article and the glossiness. Is improved.

The resin molded product obtained by the method of the present invention can control surface properties without deteriorating other physical properties such as impact strength, and is therefore widely useful as a component in the industrial field such as electric equipment and computers. Further, it is particularly useful as a molded product such as a cosmetic container, toy, stationery and the like.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0043]

The present invention will be described in more detail with reference to the following examples. The performance evaluation was measured according to the following criteria. (1) Gloss measurement Measurement of gloss level in JIS K7105 (60 ° specular gloss)
According to the measuring method of No. 3, three 100 mm × 50 mm test pieces were measured, and the average value was obtained. (2) Measurement of Impact Strength The impact strength was measured by the Izod impact test method (JIS-K7110) using a molded product cut out as a test piece. (3) Measurement of heat resistant temperature The Vicat softening point was evaluated according to ASTM DI525 using a sample obtained by cutting a test piece from a molded product. (4) Measurement of rubber particle morphology The shape of rubber particles was measured by the ultrathin section method of TEM (transmission electron microscope). (5) Measurement of average particle diameter of rubber particles An electron micrograph is taken by the above ultra-thin section method, 500 to 700 minor and major diameters of each rubber particle in the photograph are measured, and the average value is taken as the particle diameter, The volume average diameter was calculated by the following formula. Volume average diameter = ΣnD ⁴ / ΣnD ³ (where n is the particle diameter D μm
Is the number of rubber particles. ) Example 1 75.8 parts by weight of styrene, 24.2 parts by weight of acrylonitrile, 20 parts by weight of ethylbenzene, a rubber-like polymer (styrene-butadiene block copolymer, solution viscosity 11 ct)
s 5% styrene solution 25 ° C.) 9 parts by weight, organic peroxide [1,1-bis (t-butylperoxy) 3,3,5
-Trimethylcyclohexane] 0.035 parts by weight and a mercaptan 0.15 parts by weight to prepare a raw material solution.
This raw material was polymerized in a three-stage stirring type polymerization tank array reactor. The raw material solution was continuously supplied from the first-stage tank. 1
The reaction temperature in the second tank is 100 ° C and 110 in the second tank.
C. and 120.degree. C. in the third tank. The polymerization liquid was introduced from the third tank to a separation and recovery process consisting of a preheater and a decompression chamber.
The average temperature (T _av ) of the resin at the outlet of the separation and recovery process is set to 25
0 ° C, temperature fluctuation rate (T _de ) 3%, number of fluctuations per hour (N) 2 times, part of the resin discharged from the recovery process is injected at a cylinder temperature of 200 ° C and a mold temperature of 50 ° C. Molded (molded product 1). The surface of the obtained molded product was observed with an electron microscope. In the extruder shown in Table 1, the resin discharged from the separation / recovery step was added with 4% of water with respect to 100 parts by weight of the resin extruded per hour at the extruder inlet under the condition of the screw rotation speed of 3 rps, After the treatment, injection molding was performed (molded product 2). The molding conditions are the same as in the case of the molded product 1 at a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C., and the same applies hereinafter. Table 2 shows the results. Resin temperature of Y part (T ₁ )
Was 205 ° C. The rate of decrease (D) from the temperature (T ₀ ) at the exit of the recovery process to the temperature at the entrance of the pine nut pull screw section
_{When e} ) is (T ₀ −T ₁ ) / T ₀ × 100, D _e is 1
8%, the particles B is set to _{B 2 / B 1 × 100 =} B D B D
Became 48. The gloss of the molded product 1 was 73% and that of the molded product 2 was 84%. The temperature fluctuation rate and the temperature fluctuation rate per hour were adjusted by the average temperature and flow rate of the heating medium in the jacket of the preheater. The pellets used in this experiment are 3
The time was mixed as one lot and used.

Example 2 A molded product 2 was obtained under the same conditions as in Example 1 except that the screw rotation speed in the extruder was 4.2 rps. Table 2 shows the results. B _D was 40, and the gloss of the molded product 2 was 87%.

Example 3 A molded product 2 was obtained under the same conditions as in Example 1 except that the amount of water added at the extruder inlet was 8%. Table 2 shows the results. D
_{The e} was 35.4%, the B _D was 33, and the gloss was 93%.

Example 4 The resin discharged from the recovery step was introduced into the extruder shown in Table 1, and water was extruded at the inlet of the extruder at an extrusion amount of the resin of 10 per hour.
6% was added to 0 part by weight, and a molded product 2 was obtained under the condition that the screw rotation speed of the extruder was 3.3 rps. Table 2 shows the results. D _e is 22.4%, B _D 30, and the gloss 9
It became 0%.

Example 5 A molded product 2 was obtained under the same conditions as in Example 4 except that the screw rotation speed of the extruder was 4.3 rps. Table 2 shows the results. B _D was 21 and gloss was 94%. Example 6 A molded product 2 was obtained under the same conditions as in Example 4 except that the addition amount of water at the inlet of the extruder was 10%. Table 2 shows the results.
B _D was 10 and gloss was 98%.

Comparative Example 1 Same as Example 1 except that water was not added in the extruder. The results are shown in Table 3. The B _D was 90, and the gloss of the molded product 2 was 73%, which was almost the same as that of the molded product 1.

Comparative Example 2 Same as Example 4 except that water was not added in the extruder. The results are shown in Table 3. B _D is 88, gloss is 74%
Met.

Comparative Example 3 The same procedure as in Example 4 was carried out except that the resin discharged from the recovery step was introduced into the extruder shown in Table 1 and the screw rotation speed of the extruder was set to 3.0 rps. The results are shown in Table 3. B _D is 85,
The gloss was 74%.

Comparative Example 4 The same procedure as in Example 4 was conducted except that the resin discharged from the recovery step was introduced into the extruder shown in Table 1 and the screw rotation speed of the extruder was set to 4.3 rps. The results are shown in Table 3. B _D is 81,
The gloss was 76%.

Comparative Example 5 80 parts by weight of a monomer mixture consisting of 72% styrene and 28% acrylonitrile was emulsion polymerized in the presence of 20 parts by weight of polybutadiene latex. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with chemical conversion soda, washed, filtered and dried to obtain an ABS resin. The obtained resin was melted with an extruder shown in Table 1 at a cylinder temperature of 250 ° C. and a screw rotation speed of 2.
Melt at 2 rps, introduce the molten resin into the extruder,
10% of water per 100 parts by weight of resin extrusion per hour at the extruder rotation speed of 3 rps
After adding and treating, injection molding was performed. The results are shown in Table 3 as a molded product 1 obtained by injection molding using the resin discharged from the extruder and as a molded product 2 obtained by injection molding using the resin discharged from the extruder. No particles B were observed on the surfaces of the molded products 1 and 2, and the gloss did not change.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

By the method of the present invention, it is possible to produce an ABS resin having high gloss while maintaining impact resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nao Morita 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Kagaku Co., Ltd. (72) Masato Takahisa 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Kagaku Incorporated (72) Inventor Tomofumi Shirato 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Chemical Co., Ltd.

Claims (7)

[Claims] 1. Rubber-like polymer particles (rubber particles) by supplying a raw material containing at least a styrene-based monomer, an acrylonitrile-based monomer, and a rubber-like polymer to a polymerization step to polymerize the monomer. Through a polymerization step of polymerizing the monomer including formation, and then heating a mixed solution containing a polymer, an unreacted monomer and / or a solvent, at the same time as heating, or after heating and introducing into a decompression chamber. ABS system by solution or bulk polymerization method in which a monomer and / or solvent is separated from the resin component through a separation and recovery step, introduced into an extruder after the recovery step, and passed through the extruder to obtain a product. In the continuous resin production method, between the recovery process outlet and the extrusion process outlet,
It has a part for adding water (X part), a part for evaporating the added water (Y part) and a part for kneading the resin after evaporation (Z part), and particularly the Y part and the Z part are extruders (E). The water temperature is adjusted to 1 of the resin temperature at the exit of the recovery process by adding water to the X part and then evaporating the water in the Y part.
A characterized in that the temperature is lowered by 0 to 60%
Manufacturing method of BS resin. 2. The method for producing an ABS resin according to claim 1, wherein the proportion of water added is 2 to 15 parts by weight per 100 parts by weight of resin extruded per unit time. 3. The method according to claim 1, wherein the resin in the process of being introduced into the extruder after (I) the separation and recovery step is a molded article (molded article 1) obtained when the resin is injection-molded. When the rubber particles existing at a depth of 0.5 to 1.5 μm from the surface are observed by an electron micrograph by the ultrathin section method on a plane parallel to the surface of the molded product, the ratio a of the major axis a to the minor axis b. Particle A having a / b of 1.5 or less,
And at least two types of particles B having a ratio a / b of the major axis a to the minor axis b of 5 or more and the total area of the rubber particles observed by an electron micrograph by the ultrathin section method is 10
The area of particles A is at least 10% or more when 0%,
ABS in which the area (B ₁ ) of particles B is 0.001 to 2%
The area (B ₂ ) of the particles B, which is a system resin and is observed in the same manner as in the above (I) in the product (II) after passing through the extruder, has the following relational expression 0.001 ≦ B ₂ / The method for producing an ABS resin according to claim 1, wherein B ₁ × 100 ≦ 50 is satisfied. 4. The molded article 1 according to claim 3 has an average rubber particle diameter of 0.05 to 1.5 μm measured by the following method.
The method for producing an ABS resin, which is m. Electron micrograph taken by ultra-thin section method, and rubber particles 500 to 7 in the photo were taken.
Each of the 00 short diameters and long diameters was measured, and the average value was used as the particle diameter, and the volume average diameter was calculated by the following formula. Volume average diameter = ΣnD ⁴ / ΣnD ³ (where n is the particle diameter D μm
Is the number of rubber particles. ) 5. A method for producing an ABS resin, which uses a twin-screw extruder having a kneading section as the extruder according to claim 1. 6. A method for producing an ABS resin, which uses a uniaxial extruder having a kneading section as the extruder according to claim 1. 7. The method for continuously producing an ABS resin according to claim 1, wherein the temperature of the resin after evaporation of water is 20 to 50% lower than the temperature of the resin at the inlet of the extruder. A method for producing an ABS resin.