JP2749529B2 - Continuous production method of impact-resistant styrenic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously producing an impact-resistant styrenic resin, and more particularly, to an impact-resistant styrenic resin whose gloss can be easily controlled and which has an excellent balance between impact strength and tensile strength. For a continuous production method.

[0002]

2. Description of the Related Art Impact-resistant polystyrene (hereinafter referred to as HIPS)
The term “resin” refers to a resin obtained by adding a rubber component to raw styrene and polymerizing the same in order to improve the impact resistance of polystyrene. When producing this HIPS resin, a usual batch polymerization method, for example, a bulk-suspension polymerization method can be adopted, but recently, a continuous bulk polymerization method is often used.

Further, an impact-resistant styrenic resin called ABS resin (acrylonitrile-butadiene-styrene) contains acrylonitrile, and its production method is considerably different from that of impact-resistant polystyrene.
Usually, it is produced by an emulsion graft polymerization method in which a latex containing a rubber component is mixed with styrene and acrylonitrile and polymerized. However, when such an emulsion graft polymerization method is performed, the following defects occur.

(1) The manufacturing process involves emulsification, coagulation, drying and other steps, and is very complicated and disadvantageous in terms of cost. (2) Additives such as an emulsifier and a flocculant must be added, which is disadvantageous in terms of cost, and these additives remain in the obtained polymer, which impairs quality. (3) It is practically difficult to produce a low gloss resin. (4) Since a large amount of wastewater is generated, the treatment cost increases,
Easy to cause environmental pollution. Another disadvantage is that the water consumption is high.

In order to solve the above-mentioned drawbacks, British Patent No. 1121885, German Patent No. 2152945, and US Pat. No. 4,198,383 propose a method of producing an ABS resin by a continuous bulk polymerization method or a solution polymerization method. . These methods have advantages such as simplification of the manufacturing process and post-treatment steps, and reduction of waste generation and environmental pollution.However, a styrene resin having excellent physical properties cannot be obtained, and the surface of the product cannot be obtained. It is difficult to obtain a resin with high impact strength to improve gloss, and to obtain a product with low surface gloss, the impact strength is low and the balance between impact strength and tensile strength is impaired. A resin having good impact strength and tensile strength cannot be obtained while adjusting the gloss according to the application. Therefore, these improved methods are not yet satisfactory.

[0006]

SUMMARY OF THE INVENTION The present invention eliminates the above-mentioned drawbacks of the emulsion graft polymerization method and enables the control of the surface gloss and the continuous use of an impact-resistant styrenic resin excellent in both tensile strength and impact strength. It is intended to provide a manufacturing method.

[0007]

SUMMARY OF THE INVENTION The present invention is a method for achieving the above-mentioned object, wherein a specific raw material solution (I) and a specific raw material solution (II) are continuously charged into a reactor to carry out a polymerization reaction. And a method for continuously producing an impact-resistant styrenic resin.

That is, according to the present invention, the raw material solution is continuously charged into a reactor and polymerized. After the conversion of all monomers contained in the raw material solution reaches 40 to 90% by weight, the polymer In the continuous method for producing an impact-resistant styrenic resin in which the solution is introduced into a degassing device to remove unreacted monomers and volatile components, the raw material solution may be an aromatic vinyl-based monomer, vinyl cyanide. Solution (I) containing an ethylene-based monomer and / or a solvent as an optional component containing an ethylene-based monomer and a diene-based rubber, and an aromatic vinyl-based monomer; A vinylated monomer, a rubbery graft copolymer (A) and an acrylic copolymer (B),
In addition, a raw material solution (II) containing an ethylene-based monomer and / or a solvent copolymerizable therewith as an optional component, and a rubbery graft copolymer is added to 100% by weight of the raw material solution (II). The combined (A) is 0.02 to 20% by weight, the acrylic copolymer (B) is 0.02 to 20% by weight, and the raw material solution is based on the total amount of rubber in the raw material solution (I) and the raw material solution (II). The present invention provides a method for continuously producing an impact-resistant styrene resin, wherein the rubber content in (II) satisfies the relationship of 1 to 35% by weight. The production method of the present invention will be described in detail below, following the procedure of the reaction.

[0009] The continuous production method of the present invention can be usually achieved by a reactor used for continuous bulk polymerization or solution polymerization. Examples of the reactor include a plug flow reactor (PFR), a complete mixing reactor (CSTR), and a stationary mixing reactor. In the production method, a raw material solution (I) and a raw material solution (II) are continuously charged into a reactor to carry out a polymerization reaction, and a conversion of all monomers contained in the raw material solution reaches a predetermined value. Thereafter, the polymerized polymer solution is continuously taken out of the reactor, introduced into a volatilizer to remove unreacted monomers and volatile components, and then granulated to obtain the styrene resin of the present invention. Get.

The raw material solution (I) used in the present invention comprises 90 to 40% by weight of an aromatic vinyl monomer, 5 to 50% by weight of a vinyl cyanide monomer, and an ethylene-based monomer copolymerizable therewith. 0-30% by weight of monomer, 0-60% by weight of solvent, diene rubber
Contains 0.5-20% by weight. Here, as the aromatic vinyl monomer, for example, styrene, α-methylstyrene, α-chlorostyrene, p-tert-butylstyrene, p-
-Methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromostyrene and 2,5-dibromostyrene, and the like, It is preferable to use styrene or a combination of styrene and α-methylstyrene.

Examples of the vinyl cyanide monomer include acrylonitrile, α-methacrylonitrile, isobutenylylonitrile, nitrile fumarate, and dinitrile maleate, with acrylonitrile being more preferred.

The copolymerizable ethylene monomer added to the raw material solution (I) is preferably a (meth) acrylate monomer or a maleimide monomer. here,
Examples of (meth) acrylate monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate,
Dodecyl (meth) acrylate, 2- (meth) acrylate
Hydroxyethyl, glycidyl (meth) acrylate,
Examples thereof include dimethylaminoethyl (meth) acrylate, with methyl methacrylate being particularly preferred.

The maleimide monomers include, for example, maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexyl Maleimide, N-phenylmaleimide, N-2,3-dimethylphenylmaleimide, N-2,4-dimethylphenylmaleimide, N-2,3
-Diethylphenylmaleimide, N-2,4-diethylphenylmaleimide, N-2,3-dibutylphenylmaleimide, N-2,4-dibutylphenylmaleimide, N-2,
6-dimethylphenylmaleimide, N-2,3-dichlorophenylmaleimide, N-2,4-dichlorophenylmaleimide, N-2,3-dibromophenylmaleimide, N-
2,4,6-tribromophenylmaleimide and the like.

Further, other copolymerizable ethylene monomers include, for example, (meth) acrylic acid monomer, maleic anhydride, methylene succinic anhydride, methylmaleic anhydride, fumaric acid And the like, unsaturated carboxylic acid compounds and their ester monomers, ethylene, propylene,
-Butene, 1-pentene, 4-methyl-1-pentene,
Examples thereof include ethylene chloride, vinylidene chloride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, butadiene, propenylamine, isobutylenylamine, vinyl acetate, ethyl vinyl ether, and methyl vinyl ketone.

Solvents that can be used in the raw material solution (I) include benzene, ethylbenzene, p-xylene, o-xylene, m-xylene, pentane, octane, cyclohexane, methyl ethyl ketone, acetone, and methyl isobutyl ketone. The use amount of the solvent is preferably 60% by weight or less, but if it exceeds 60% by weight, the molecular weight tends to be too low, and the production efficiency decreases.

The diene rubber in the raw material solution (I) refers to a polymer obtained by polymerizing a diene monomer component and having a glass transition temperature of -20 ° C. or lower. Examples of the diene rubber include butadiene rubber, isoprene rubber, chlorobutadiene rubber, ethylene-propylene-ethylidene norbornene rubber, and the like, with butadiene rubber being preferred. Butadiene rubbers are Hi-Cis and Low-Cis
Preference is given to the two polybutadiene rubbers of s). The high cis rubber has a typical weight ratio of the cis and vinyl groups of 94 to 99% and 5% or less, respectively, and the other components have a trans structure and a Mooney viscosity in the range of 20 to 120. The molecular weight range is preferably from 100,000 to 800,000.
The low-cis rubber has typical weight ratios of cis and vinyl groups of 20 to 40% and 6 to 20%, respectively, and the other components are in a trans structure and have a Mooney viscosity of 20%.
And the molecular weight is preferably in the range of 100,000 to 800,000. Other butadiene rubbers include acrylonitrile-butadiene rubber, styrene-butadiene rubber, and mixtures of the above rubbers. The styrene-butadiene rubber applied to the present invention is, for example, S
Examples include a B block copolymer, an SBS block copolymer, a random copolymer, or a star block copolymer.
The weight ratio of styrene of the styrene-butadiene rubber is preferably in the range of 20% by weight or less, and the molecular weight thereof is 50,000 to 600,000.
Is preferred.

The raw material solution (I) containing the rubber component includes:
If the content of the rubber component is 20% by weight or less, and if it exceeds 20% by weight, it becomes difficult to handle the dissolution, which causes inconvenience in the transport work.

The raw material solution (II) used in the present invention comprises 90 to 40% by weight of an aromatic vinyl monomer, 5 to 50% by weight of a vinyl cyanide monomer, and a copolymerizable ethylene monomer. 0 to 30% by weight of a monomer, 0 to 60% by weight of a solvent, 0.02 to 20% by weight of a rubbery graft copolymer (A), and 0.02 to 20% by weight of an acrylic copolymer (B). Among them, the aromatic vinyl monomer, the vinyl cyanide monomer, the copolymerizable ethylene monomer and the solvent used are the same as the monomers described in the raw material solution (I). can do.

The rubbery graft copolymer (A) can be obtained by performing a graft copolymerization using a rubber latex. A preferred method of producing a rubber latex is to polymerize a diene monomer with 0 to 50% by weight of another copolymerizable monomer such as styrene, acrylonitrile, (meth) acrylate, or the like, by an emulsion polymerization method. Let it be 0.05
After forming a rubber latex having a small particle size of 0.05 to 0.2 μm from the monomer by emulsion polymerization, a freezing method, a homogenizer treatment method and additive aggregation A method of producing a rubber latex having a large particle size of 0.22 to 0.6 μm by coagulating and enlarging the rubber latex having a small particle size by a method or the like. Examples of the additives used in the additive aggregation method include acidic substances such as acetic anhydride, hydrogen chloride and sulfuric acid, salts such as sodium chloride and potassium chloride, and (meth) acrylic acid-based additives.
Carboxyl group-containing polymer coagulants such as (meth) acrylate copolymers (for example, methacrylic acid-butyl acrylate copolymer, methacrylic acid-ethyl acrylate copolymer) are exemplified.

The rubbery graft copolymer (A) comprises the rubber latex 40 to 90% by weight (as solid content), an aromatic vinyl monomer 90 to 40% by weight, a vinyl cyanide monomer 5 to 50% by weight, other copolymerizable ethylene monomer 0 to 30% by weight of a monomer mixture of 60 to 10% by weight, mixed with a suitable emulsifier and initiator, if necessary,
Graft polymerization is carried out using a chain transfer agent to produce a rubbery graft copolymer latex, which is then subjected to coagulation, dehydration, drying, etc., to obtain the desired rubbery graft copolymer (A). The types of the emulsifier, initiator and chain transfer agent are not particularly limited. In addition, the monomers used for the grafting may be added all at once, but may be added stepwise or continuously in small amounts, or each monomer may be graft-polymerized stepwise. May be.

The rubbery graft copolymer (A) in the present invention can be produced by any of the above-mentioned methods. However, in order to shorten the polymerization time of the rubber latex and to improve the production efficiency, the above-mentioned enlargement is required. Rubber latex obtained by chemical conversion is desirable. Further, in order to achieve uniform particle size and to reduce coagulation unstable to latex, an enlarged rubber latex obtained by adding a polymer coagulant containing a carboxyl group is more preferable.

Further, the acrylic copolymer (B) in the present invention comprises at least one acrylic copolymer selected from the group consisting of (meth) acrylate monomers and vinyl cyanide monomers. It is composed of 10 to 100% by weight of a monomer, 0 to 80% by weight of an aromatic vinyl monomer, and 0 to 30% by weight of another copolymerizable ethylene monomer.

Here, the meanings of the (meth) acrylate monomer, vinyl cyanide monomer and aromatic vinyl monomer are the same as those described in the description of the raw material solution (I). Further, as a polymerization method of the acrylic polymer (B), a method such as solution, bulk, emulsification or suspension can be adopted.

In the production method of the present invention, the acrylic copolymer (B) accounts for 0.02 to 20% by weight of the raw material solution (II), preferably 0.08 to 10% by weight. When the content is lower than 0.02% by weight, the rubbery graft copolymer (A) contained in the raw material solution (II) is agglomerated and difficult to disperse in the solution. Began to contain coarse particles in the styrene resin, physical properties,
Not good from both sides of appearance. Acrylic copolymer (B)
If it exceeds 20% by weight, the viscosity of the raw material solution (II) is too high, making the operation difficult and disadvantageous from the economical point of view.

When the amount of the rubbery graft copolymer (A) added to the raw material solution (II) is lower than 0.02% by weight, the impact-resistant styrene having excellent balance of impact strength, tensile strength and gloss is used. No resin can be obtained. Conversely,
If it exceeds 20% by weight, the viscosity of the raw material solution (II) is too high, the dissolution and dispersibility is low, and there is a disadvantage that the operation becomes difficult.

On the other hand, the content of rubber in the raw material solution (II) should be 1 to 35% by weight of the total amount of rubber contained in the raw material solution (I) and the raw material solution (II). If this proportion is less than 1% by weight, the resin cannot obtain physical properties excellent in balance between impact resistance and tensile strength. On the other hand, if this proportion exceeds 35% by weight, no remarkable improvement in physical properties is exhibited, and the viscosity of the raw material solution (II) is too high, making it difficult to handle. The method of calculating the content of rubber in the raw material solution (II) with respect to the total amount of rubber contained in the raw material solution (I) and the raw material solution (II) is based on the method described in Examples described later.

The raw material solution (I) of the present invention and the raw material solution (I)
The impact-resistant styrene resin produced according to I) preferably has a rubber content of 2 to 30% by weight based on the total amount of the resin. When the rubber content is less than 2% by weight, the impact strength of the resin is poor, and when it exceeds 30% by weight, the workability is poor. The method for calculating the amount of rubber is based on the method described in Examples below.

The raw material solution (I) and the raw material solution (II) used in the present invention can be obtained by converting the above rubber or rubbery graft copolymer (A) into a monomer and / or a solvent by a known dissolving apparatus. By dissolving in water, the pumping work can be performed smoothly. As the dissolving device, for example, a ribbon-type screw stirring blade, a propeller-type stirring blade, or another dissolving device equipped with a stirring blade that generates high shearing force can be used. The rubbery graft copolymer (A) and the acrylic copolymer (B) used in the raw material solution (II) are melt-mixed with an extruder or the like in advance to form pellets, coarse particles, or powder. There is also a method of mixing and dissolving with other components to obtain (II) to obtain a raw material solution (II).

The rubber solution supply system used in the present invention comprises 98 to 60% by weight of the raw material solution (I) and 2 to 40% by weight.
There are two of the raw material solutions (II). Each of the two feed systems may be continuously charged into the first reactor, and then, if necessary, introduced into the second reactor and further to the subsequent reactor. In order to control the polymerization reaction in each of the above reactors, a chain transfer agent and an initiator can be added.

The reaction mixture is continuously taken out of the first reactor and introduced into a subsequent reactor such as the second reactor in accordance with the procedure to further carry out a polymerization reaction, and the addition rate is up to 40 to 90% by weight. When the reaction reaches the above, the polymerized reaction mixture is introduced into a degassing device, and the unreacted monomer and solvent are removed to obtain a resin as a target product. The type of the second or subsequent reactor is not particularly limited, but the first reactor is preferably a complete mixing reactor (CSTR) because rubber particles can be sufficiently dispersed.

The unreacted monomer and solvent removed by the degassing device may be used for preparing the raw material solution (I) and the raw material solution (II), and may be directly fed into each reactor. Can also.

Various additives such as antioxidants, lubricants, ultraviolet absorbers, ultraviolet stabilizers, antistatic agents, etc. may be added to the impact-resistant styrenic resin obtained by the present invention, if necessary.
A flame retardant, a colorant, and the like can be added, and the timing of the addition may be appropriately selected, such as at each polymerization stage of the resin or after the polymerization.

The impact-resistant styrenic resin obtained by the present invention can be used by mixing with various polymers, if necessary. As these polymers, acrylonitrile and styrene are added to butadiene rubber latex,
An acrylonitrile-butadiene-styrene copolymer produced by polymerization, a butadiene rubber is dissolved in a mixture of acrylonitrile and styrene, and a bulk polymerization method, a solution polymerization method,
Or acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-alpha-methylstyrene copolymer, acrylonitrile-styrene-methyl methacrylate copolymer produced by bulk-suspension polymerization method Coal, acrylonitrile-styrene-phenylmaleimide copolymer, styrene-maleic anhydride copolymer, styrene-phenylmaleimide-based copolymer, methyl methacrylate-based polymer, polycarbonate and other polymers. Alternatively, two or more kinds may be added and mixed. in this case,
The amount of these polymers used is usually 80% or less based on the sum of these polymers and the impact-resistant styrenic resin of the present invention.

The impact-resistant styrenic resin of the present invention can be used as a molded product by various molding methods such as injection molding, extrusion molding, extrusion molding, followed by thermoforming or blow molding.

[0035]

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

(Production Example 1) Production of rubbery graft copolymer (A1): Component weight part 1,3-butadiene 150.00 potassium persulfate solution (1%) 15.00 potassium oleate 2.0 distilled water 190.00 ethylene dimethacrylate Glycol 0.13 After reacting the above formulation at a temperature of 65 ° C. for 12 hours, a synthetic rubber latex having a conversion of 94%, a solid content of about 40% and a weight average particle size of about 0.1 μm is obtained.

On the other hand, a carboxyl group-containing polymer flocculant is produced from the following components. Ingredients Parts by weight Butyl acrylate 90.00 Methacrylic acid 10.00 Potassium persulfate solution (1%) 0.50 Sodium dodecyl sulfate (10%) 0.50 n-dotesylmercaptan 1.00 Distilled water 200.00 The above mixture is reacted at a temperature of 75 ° C for 5 hours. After the reaction, a latex of a carboxyl group-containing polymer flocculant having a conversion of about 95% and a pH of 6.0 is obtained.

Next, 3 parts by weight (as solids) of a polymer coagulant containing a carboxyl group were added to 100 parts by weight of the synthetic rubber latex (as solids) obtained in Production Example 1,
The obtained enlarged rubber latex is a rubber latex having a pH of 8.5 and a rubber particle diameter of 0.31 μm. Finally, the above-mentioned enlarged rubber latex is graft-polymerized according to the following formulation to prepare a rubber-like graft copolymer. Ingredients Parts by weight Enlarged rubber latex (solid content) 100 Styrene 75.0 Acrylonitrile 25.0 Tertiary dodecyl mercaptan 2.0 Cumene hydroperoxide 3.0 Iron (II) sulfate solution (0.2%) 3.0 Rongalite solution (10%) 0.9 Ethylenediaminetetraacetic acid solution ( 0.25%) 3.0 The rubber-like graft latex obtained by the above
After coagulation with CaCl ₂ , dehydration and further drying to a water content of 2% by weight or less, a rubbery graft copolymer (A1) having a rubber content of 50% by weight is obtained.

(Production Example 2) Production of styrene-acrylonitrile-methyl methacrylate copolymer (B1): A raw material mixture of 50% by weight of styrene, 18% by weight of acrylonitrile and 32% by weight of methyl methacrylate was subjected to a rate of 12 kg / hr. Of ethylene bis stearamide, 3.0 kg / hr, and tertiary decyl mercaptan, benzoyl peroxide, and a recovery solution described below as a feed solution, and a volume of which the internal temperature was maintained at 108 ° C. 45
of a polymerization reactor with a stirrer. The ratio of toluene in the reaction solution was maintained at 15%, and the polymerization rate was maintained at 55%.

The reaction solution is subjected to a devolatilizer to remove volatile components, thereby obtaining pellets of the acrylic copolymer (B1). On the other hand, the removed volatiles were condensed in a cooler, continuously mixed with the raw material mixture as described above, and reused.
By adjusting the reaction rate according to the amount of benzoyl peroxide and the amount of tertiary decyl mercaptan by this method, an acrylic copolymer (B1) having a melt flow index of 1.0 is produced at a rate of about 12 kg / hr. did.

(Production Example 3) Production of styrene-acrylonitrile copolymer: styrene
A raw material mixture of 76% by weight and acrylonitrile 24% by weight
Ethylene bis stearoamide used at a rate of 12 kg / hr
A styrene-acrylonitrile copolymer having a melt flow index of 1.2 is prepared in the same manner as in Production Example 2 as a feed solution by combining 3.0 kg / hr, benzoyl peroxide, tertiary decyl mercaptan, and a recovery solution described later as a feed solution.

(Example 1) 6 parts by weight of polybutadiene (Asaden 35AS, Asahi Kasei) as a rubber component were mixed with 48.8 parts by weight of styrene, 15.2 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.1 part by weight of tertiary dodecyl mercaptan. It is completely dissolved in a mixture with 0.07 parts by weight of benzoyl peroxide as an agent to obtain a raw material solution (I). 3.7 parts by weight of the rubbery graft copolymer (A1) (the content of rubber is 50% by weight from Production Example 1) and 2.3 parts by weight of the acrylic copolymer (B1) (Production Example 2)
48.8 parts by weight of styrene and acrylonitrile 1
It is completely dissolved in a mixture of 5.2 parts by weight and 30 parts by weight of ethylbenzene to obtain a raw material solution (II). Thereafter, each of the raw material solution (I) and the raw material solution (II)
The first reactor is continuously charged at a rate of hr and 6.8 l / hr. The first reactor has a volume of 44 liters, a reaction temperature of 100 ° C., a stirring speed of a screw-type stirrer provided therein of 300 rpm, and a complete reactor provided with a cooling circulation pipe. This is a mixed polymerization tank. While continuously taking out the mixed solution from the first reactor, the mixture was sequentially passed through second and third reactors having the same arrangement as the first reactor. When the conversion of the mixture reached 57%, the mixture was taken out and introduced into a volatilizer to remove unreacted monomers and volatiles,
Further, it was extruded to produce impact-resistant styrene resin pellets, and a resin having a rubber average particle diameter of 0.8 μm was obtained. The physical properties and gloss were measured, the appearance was visually observed, and the results are shown in Table 1. Incidentally, the rubber average particle diameter indicates a volume average particle diameter (the same applies hereinafter).

Example 2 5.3 parts by weight of the rubber component dissolved in the raw material solution (I), 15 parts by weight of the rubbery graft copolymer (A1) dissolved in the raw material solution (II), and acrylic resin The amount of the base copolymer (B1) was changed to 6.3 parts by weight, and the raw material solution (I) and the raw material solution (II) were continuously fed into the first reactor at a rate of 30.6 liter / hr and 3.4 liter / hr, respectively. Except charging, it carried out similarly to Example 1. Table 1 shows the results of measurement of the finished physical properties, gloss, and appearance.

Example 3 A rubber component dissolved in the raw material solution (I) was added to 5.62 parts by weight, a rubbery graft copolymer (A1) dissolved in the raw material solution (II) was added to 12 parts by weight, and acrylic The amount of the base copolymer (B1) was changed to 10 parts by weight, and the raw material solution (I) and the raw material solution (II) were continuously fed into the first reactor at a rate of 27.2 L / hr and 6.8 L / hr, respectively. The experiment was conducted in the same manner as in Example 1 except for the charging. Table 1 shows the results of measurement of the finished physical properties, gloss, and appearance.

Example 4 An experiment was conducted in the same manner as in Example 1 except that 3 parts by weight of methyl methacrylate was added to each of the raw material solution (I) and the raw material solution (II) and styrene was changed to 45.8 parts by weight. . Table 1 shows the measurement results of the physical properties, gloss, and appearance of this.

Example 5 6 parts by weight of polybutadiene (Asaden 35AS, Asahi Kasei) as a rubber component were mixed with 3 parts by weight of N-phenylmaleimide, 48.8 parts by weight of styrene, 12.2 parts by weight of acrylonitrile, and 30 parts of ethylbenzene.
In a mixed solution of 0.1 part by weight of tertiary dodecyl mercaptan and 0.07 part by weight of benzoyl peroxide, the mixture is completely dissolved to obtain a raw material solution (I). 3.7 parts by weight of rubber-like graft copolymer (A1)
% By weight) and an acrylic copolymer (B).
2.3 parts by weight of a styrene-acrylonitrile copolymer of
A raw material solution (II) is completely dissolved in a mixture of 48.8 parts by weight of styrene, 15.2 parts by weight of acrylonitrile, and 30 parts by weight of ethylbenzene. Thereafter, the raw material solution (I) and the raw material solution (II) are continuously charged into the first reactor at a rate of 27.2 L / hr and 6.8 L / hr, respectively. then,
Through the same manufacturing procedure as in Example 1, an impact-resistant styrene resin was obtained. The physical properties and gloss were measured, the appearance was visually observed, and the results are shown in Table 1.

(Comparative Example 1) The same as Example 1 except that the rate at which the raw material solution (I) was continuously charged into the first reactor was changed to 34 l / hr, and the raw material solution (II) was not used. To obtain a resin having an average rubber particle size of 4 μm. Its physical properties,
The results of measuring the gloss and appearance are shown in Table 1.

Comparative Example 2 Example 2 was repeated except that the acrylic copolymer (B1) dissolved in the raw material solution (II) was not used.
Experimented in the same way as Table 1 shows the measurement results of physical properties, gloss and appearance. In the raw material solution (II), agglomerated particulate rubber-like graft copolymer (A1) can be seen.

Example 6 The rubber component dissolved in the raw material solution (I) was polybutadiene (Asaden Kasei, Asadene).
55AS) An experiment was conducted in the same manner as in Example 1 except that the weight was changed to 6 parts by weight to obtain a resin having a rubber average particle diameter of 4 μm. The physical properties and gloss were measured, the appearance was visually observed, and the results are shown in Table 1.

(Comparative Example 3) The same as Example 6 except that the rate at which the raw material solution (I) was continuously charged into the first reactor was changed to 34 l / hr, and the raw material solution (II) was not used. To obtain a resin having an average rubber particle size of 4 μm. The physical properties and gloss were measured, the appearance was visually observed, and the results are shown in Table 1.

The physical properties, gloss, and appearance of the molded products shown in the above Examples and Comparative Examples were measured based on the following.

Tensile strength: Measured according to ASTM D-638. (Unit: kg / cm ² ) Izod impact strength: Measured according to ASTM D-256. (Unit: kg-cm / cm) ・ Surface gloss (Gardner 60 °, Incidence angle): AS
Measured according to TM D-523. (Unit:%)-Appearance of extruded sheet: Resin raw material is a single screw extruder (L /
D = 28, D = 90mm, US GLOUCESTER ENGINEERING CO.
After extruding a 2.3 mm-thick sheet, the surface of the sheet is observed. When the surface of the sheet has fish eyes, it is indicated by X, and when the surface of the sheet is smooth and has no fish eyes, it is indicated by O. .

[0053]

[Table 1]

[0054]

[Table 2]

Note) [1] "Rubber content in raw material solution (II) / total amount of rubber in raw material solution (I) and raw material solution (II)" in the table
For example, the value of the first embodiment is calculated as follows (the same applies to other examples). Rubber content in raw material solution (I) ... (a) = (6/100) × 80% (charge ratio) = 0.048 Rubber content in raw material solution (II) ... (b) = (3.7 / 100) × 50% (Rubber content in A1) × 20% (feed ratio) = 0.0037 Therefore, the rubber content in the raw material solution (II) / the total amount of rubber in the raw material solution (I) and the raw material solution (II) is (b) / [ (A) + (b)] = 0.0037 / (0.048 + 0.003)
7) ≒ 0.072.

[2] Also, "Total amount of rubber contained in resin"
Is calculated as follows. The following method exemplifies the first embodiment and the fourth embodiment (other examples are similarly calculated). <Example 1> Raw material solution (I): styrene (SM) 48.8 parts Acrylonitrile (AN) 15.2 parts Polybutadiene (BR) 6.0 parts Ethylbenzene (EB) 30.0 parts Total 100.0 parts Raw material solution (II): SM 48.8 parts AN 15.2 parts AN Rubber-like graft copolymer A1 (BP) 3.7 parts Acrylic copolymer B1 (PMMA) 2.3 parts EB 30.0 parts Total 100.0 parts Total amount of rubber contained in resin = (BR / hr + BP / hr) / total amount of resin ) BR / hr = (6/100) x 80% = 0.048 (d) BP / hr = (3.7 / 100) x 50% x 20% = 0.0037 (e) Total amount of resin-Raw material solution (I) (SM + AN ) / Hr = [(48.8 + 15.2) / 100] × 80% = 0.
512 BR / hr = (6/100) × 80% = 0.048 ・ Raw material solution (II) (SM + AN) / hr = [(48.8 + 15.2) / 100] × 20% = 0.
128 PMMA / hr = (2.3 / 100) x 20% = 0.0046 BP / hr = (3.7 / 100) x 50% x 20% = 0.0037 AS / hr = (3.7 / 100) x 50% x 20% = 0.0037 * AS is (AN + S) in A1 obtained by Production Example 1.
M) (BP minus rubber). Also, since the conversion of the mixture is 57%, (e) is
(0.512 + 0.128) × 57% + 0.048 + 0.0046 + 0.0037 + 0.003
7 = 0.4248. Therefore, [(c) + (d)] /
(E) is (0.048 + 0.0037) /0.4248/12.17.

<Embodiment 4> Total rubber content of resin = (BR / hr + BP / hr) / total resin amount (f) BR / hr = (6/100) × 80% = 0.048 (g) BP / hr = (3.7 / 100) × 50 % X 20% = 0.0037 (h) Total resin amount-Raw material solution (I) (SM + AN) / hr = [(45.8 + 15.2) / 100] x 80% = 0.4
88 BR / hr = (6/100) × 80% = 0.048 MMA / hr = (3.0 / 100) × 80% = 0.024 Raw material solution (II) (SM + AN) / hr = [(45.8 + 15.2) / 100 ] X 20% = 0.1
22 PMMA / hr = (2.3 / 100) × 20% = 0.046 MMA / hr = (3.0 / 100) × 20% = 0.006 BP / hr = (3.7 / 100) × 50% × 20% = 0.0037 AS / hr = (3.7 / 100) × 50% × 20% = 0.0037 Also, since the conversion of the mixture is 57%, (h) is
(0.488 + 0.122 + 0.024 + 0.006) × 57% + 0.048 + 0.0046
+ 0.0037 + 0.0037 = 0.4248. Therefore, [(f) +
(G)] / (h) = (0.048 + 0.0037) /0.4248/12.
It becomes 17.

Claims (3)

(57) [Claims] 1. A raw material solution is continuously charged into a reactor and polymerized, and the conversion of all monomers contained in the raw material solution is 40 to 40%.
After reaching 90% by weight, the polymer solution is introduced into a degassing apparatus, and in the continuous production method of an impact-resistant styrenic resin for removing unreacted monomers and volatile components, A raw material solution (I) containing an aromatic vinyl monomer, a vinyl cyanide monomer, and a diene rubber, and optionally containing an ethylene monomer and / or a solvent copolymerizable therewith; ), Including an aromatic vinyl monomer, a vinyl cyanide monomer, a rubbery graft copolymer (A) and an acrylic copolymer (B), and can be copolymerized with these as optional components. Raw material solution (II) containing a suitable ethylene-based monomer and / or solvent, and the rubbery graft copolymer (A) is 0.02 to 20% by weight based on 100% by weight of the raw material solution (II). And the acrylic copolymer (B) is 0.02 to 20% by weight. And the rubber content in the raw material solution (II) satisfies the relationship of 1 to 35% by weight with respect to the total amount of rubber in the raw material solution (I) and the raw material solution (II). Continuous production method of styrene resin. 2. The method according to claim 1, wherein the reactor has two or more reactors, and the first reactor is a complete mixing reactor (CSTR). Continuous manufacturing method. 3. The continuous production method according to claim 1, wherein the rubber component contained in the rubbery graft copolymer (A) is enlarged by a carboxyl group-containing polymer flocculant. .