JP3390529B2 - Continuous production method of rubber-modified 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 producing a rubber-modified styrenic resin, more specifically, it has excellent impact resistance,
In addition, the present invention relates to a method for producing a rubber-modified styrene resin that gives a molded article having high surface gloss.

[0002]

2. Description of the Related Art Rubber-modified styrenic resins are produced by emulsion polymerization, continuous block or solution polymerization. Emulsion polymerization rubber-modified styrene resin has a good balance of impact resistance and surface gloss, but it contains a lot of impurities such as emulsifiers and dispersants, so the hue is poor and the manufacturing cost is high. There are problems such as producing waste water and adversely affecting the environment. On the other hand, the rubber-modified styrenic resin obtained by continuous bulk or solution polymerization method has the advantages of low impurities, low production cost, and no waste water, but the balance between impact resistance and surface gloss is insufficient.

The following methods are known as methods for improving the balance of physical properties in the continuous bulk or solution polymerization method.

Japanese Patent Publication No. 49-7343 (corresponding to US
P. No. 3,658,946), a method of preliminarily polymerizing the rubber-like polymer in the first polymerization tank in a state where it does not transfer to the dispersed phase, and then transferring the rubber-like polymer to the dispersed phase by polymerization in the second polymerization tank ( A prepolymerization method) is disclosed. However, in this method, the diameter of the rubber particles that can be controlled is originally large, and when acrylonitrile is added to the polymerization system, the rubber particles become larger and the physical properties deteriorate. The reason why the physical properties are lowered is that the surface gloss of the styrene resin is higher as the rubber particle diameter is smaller, and the impact resistance is specifically expressed in the optimum particle diameter range peculiar to the resin.

As a method for solving such a problem, in JP-A-63-118315, the conversion rate in each tank is adjusted so that the proportions of the solid contents in the polymerization solution in the prepolymerization tank and the phase inversion tank are close to each other. It is proposed to control. However, this method is not only poor in operability as a practical plant because it is a method consisting of complicated steps, but also when rubber particles are copolymerized with acrylonitrile, the rubber particle diameter cannot be sufficiently controlled, and large rubber particles are generated, resulting in physical properties. Is reduced.

Further, Japanese Patent Laid-Open No. 3-7708 (corresponding to US.
P. No. 5,244,977), a high-viscosity rubber having a viscosity of a 5 wt% styrene solution at 25 ° C. of 400 to 2000 centipoise at 25 ° C. while controlling the solid content in the polymerization liquid in a prepolymerization tank and a phase inversion tank. A method of using a linear polymer is disclosed. In this method, there are problems in operation such that the rubber-like polymer is difficult to dissolve in the monomer when the polymerization raw material is prepared, and stirring of the polymerization liquid is difficult because the viscosity of the polymerization system is high. Further, extremely large rubber particles are generated and physical properties cannot be improved.

[0007] In EP-47764, a plug flow type polymerization tank is used and the polymerization temperature up to phase inversion is 90
Polymerization in the presence of polybutadiene by using an organic peroxide having a high graft activity, which has a half-life at 90 ° C. of 20 minutes or less at 90 ° C. or below, gives a rubber particle size of 0.5 μm.
The following is a method of producing a resin having a high graft ratio. However, in this method, since the plug flow type polymerization tank is used at the phase inversion stage, it is not possible to strictly control the rubber particle size, and a large amount of large rubber particles are partially generated, so that the surface gloss is sufficiently improved. Absent.

As described above, in the above-mentioned conventional technique,
Adopting a multi-tank polymerization method of two or more tanks, polymerization is carried out in the first tank in a state where the rubber-like polymer does not transfer to the dispersed phase, and then transfer of the rubber-like polymer to the dispersed phase in the second tank and thereafter. Although the method is disclosed, the method of adding the polymerization raw material to the polymerization system after the second tank is not adopted.

[0009]

DISCLOSURE OF THE INVENTION The present invention is to produce a rubber-modified styrene resin by continuous bulk and / or solution polymerization to obtain a rubber-modified styrene resin which is excellent in impact resistance and gives a molded article having high surface gloss. It is to provide a manufacturing method.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when a rubber-modified styrenic resin is produced by continuous bulk and / or solution polymerization, At the same time as or after the addition of the polymerization raw material such as a monomer used in the polymerization reaction, a rubber-like polymer, an inert organic solvent, etc. The present invention was completed by finding the surprising fact that a rubber-modified styrenic resin capable of giving a molded article with significantly improved impact resistance and surface gloss can be obtained by transferring a polymer in the dispersed phase. It was

That is, the continuous production method of the rubber-modified styrene resin of the present invention uses a continuous polymerization apparatus consisting of two or more reaction tanks in the presence of a polymerization initiator to obtain a continuous lump and / or solution weight. the presence of a rubbery polymer by legal, all single
Styrene-based monomer 25 to 9 per 100 parts by weight of the monomer
3 to 45 parts by weight of 7 parts by weight and acrylonitrile-based monomer
Parts , or styrene-based monomers, acrylonitrile-based monomers and unsaturated compound monomers copolymerizable with these monomers (all of these monomers are simply monomers)
0-30 parts by weight are polymerized so that the styrene-acrylonitrile-based copolymer forms a continuous phase and the rubber-like polymer particles form a dispersed phase. In the method for producing a rubber-modified styrene resin as a polymerization raw material containing an inert organic solvent, (1) the polymerization raw material is supplied to the first reaction tank (hereinafter referred to as the first polymerization raw material), and the rubber-like polymer is substantially A first step of polymerizing the monomer in a state where it does not transfer to the dispersed phase in
The second step comprises adding a polymerization raw material after the reaction tank (hereinafter referred to as a second polymerization raw material) and continuously polymerizing the monomer to transfer the rubber-like polymer to the dispersed phase. (2) Second The ratio of the polymerization raw material to the first polymerization raw material is 10
It is a continuous method for producing a rubber-modified styrenic resin, which is characterized in that the content is in the range of 220 wt%.

The styrenic monomer in the present invention is represented by the general formula (I)

[0013]

[Chemical 1] (In the above formula, R ¹ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, halogen, R ² represents hydrogen, an alkyl group having 1 to 5 carbon atoms, halogen, an unsaturated hydrocarbon having 1 to 5 carbon atoms, R ² may be the same or different), especially styrene and derivatives thereof, such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene. , One or more of halogenated styrene, t-butylstyrene, vinylxylene, divinylbenzene, etc. are used,
Styrene, α-methylstyrene and p-methylstyrene are preferred, and styrene and α-methylstyrene are particularly preferred. You may use these individually or in mixture of 2 or more types.

The styrenic monomer is used in an amount of usually 25 to 97 parts by weight, preferably 50 to 95 parts by weight, based on 100 parts by weight of the total amount of various monomers in the polymerization raw material.

The acrylonitrile-based monomer is represented by the general formula (II)

[0016]

[Chemical 2] (R ¹ is the same as defined above.) An unsaturated compound having a nitrile group represented by the following is used, and for example,
One or more of acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like are used, and acrylonitrile and methacrylonitrile are particularly preferable. You may use these individually or in mixture of 2 or more types. These are usually 3 to 100 parts by weight of the total amount of various monomers in the polymerization raw material.
A range of 45 parts by weight is used, preferably 10 to 35 parts by weight.

As the unsaturated compound copolymerizable with the styrene-based monomer and / or the acrylonitrile-based monomer in the present invention, a known unsaturated compound which can be generally copolymerized with styrene and acrylonitrile can be used. , (Meth) acrylic acid alkyl ester monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate and n-butyl acrylate, n-phenylmaleimide, n-methylphenylmaleimide, n-cyclohexylmaleimide, n- Examples thereof include maleimide-based monomers such as ethylmaleimide, unsaturated carboxylic acid derivatives such as maleic anhydride, acrylic acid and methacrylic acid. These monomers may not be used, and one kind or a combination of two or more kinds can be used.

It is particularly preferable to use methyl methacrylate, n-phenylmaleimide or maleic anhydride. When methyl methacrylate is used, the hardness of the resin is improved,
When n-phenylmaleimide is used, heat resistance is improved, and when maleic anhydride is used, heat resistance and weather resistance are improved. These are the total amount of various monomers in the polymerization raw material 100
It is usually used in the range of 0 to 30 parts by weight with respect to parts by weight.

The rubber-like polymer used in the present invention includes polybutadiene, isoprene-butadiene copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene. Copolymers and the like are preferable. More preferably, polybutadiene and styrene-butadiene copolymer are used. With respect to the styrene-butadiene copolymer, it is particularly preferable to use a styrene-butadiene block copolymer in which the styrene portion and the butadiene portion are separated. The solution viscosity of the rubber-like polymer is in the range of 3 to 200 centipoise, particularly 3 to 100 centipoise, and further 5 to 50 centipoise when the styrene solution having a rubbery polymer concentration of 5% by weight is measured at 25 ° C. Preferably there is. These are the total amount of various monomers in the polymerization raw material 1
The amount is usually 4 to 50 parts by weight, preferably 4 to 20 parts by weight, based on 00 parts by weight.

In the present invention, a polymerization initiator is preferably used. Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxyoctoate, cumylperoxyoctoate. Ate, 1,1-bis (t-butylperoxy) 3,3,5
-Organic peroxides such as trimethylcyclohexane, 2,
Azo compounds such as 2-azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile) and 2,2-azobis (2,4-dimethylvaleronitrile) can be used. However, the use of an organic peroxide is preferable because high grafting efficiency can be easily obtained.
Further, the polymerization initiator to be used can be selected depending on the temperature of the reaction tank to which the polymerization initiator is added, the average residence time of the polymerization liquid, and the target polymerization conversion rate. For example, when an organic peroxide is used as a polymerization initiator, it can be selected based on its half-life. 90 ° C when the polymerization is carried out at 50 to 100 ° C
Of organic peroxide having a half-life of 1 minute to 2 hours is 70 to 14
When performed at 0 ° C., an organic peroxide having a 90 ° C. half-life of 10 minutes to 20 hours is performed at 120 to 180 ° C.
It is preferable to use an organic peroxide having a half-life at 0 ° C. of 5 hours or more. Preferably, t-butylperoxypivalate, t-butylperoxy (2-ethylhexaate), 1,1-bis (t-butylperoxy) 3,3.
5-trimethylcyclohexane, particularly preferably t-butylperoxy (2-ethylhexaate), 1,1-
Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane is used. These are usually 0.001 to 100 parts by weight of various monomers in the polymerization raw material.
5.0 parts by weight, preferably 0.001 to 3.5 parts by weight,
More preferably, it is used in the range of 0.001 to 2.0. In the present invention, the polymerization initiator is preferably supplied separately in the first step and the second step, and in this case, 0.001 to 2.0 parts by weight relative to 100 parts by weight of the monomer in the first step. And preferably 0.001 to 1.0 part by weight, and in the second step, 0 to 1.5 parts by weight, preferably 0 to 1.0 parts by weight, of organic peroxide is added to 100 parts by weight of the monomer. Is preferred.

The inert organic solvent used in the present invention means a compound having no polymerizable unsaturated bond, and examples thereof include benzene, toluene, xylene, ethylbenzene, acetone, isopropylbenzene and methylethylketone. It is particularly preferable to use ethylbenzene or toluene. When a large amount of an inert organic solvent is used, the polymerization rate is suppressed, the productivity is lowered, and when the rubbery polymer is transferred to the dispersed phase, the rubbery polymer particles are likely to aggregate during the polymerization. Further, due to the chain transfer property of the inert organic solvent, when a large amount of the inert organic solvent is used, polymerization of the monomer to the rubber-like polymer, that is, graft polymerization is hindered. Therefore, the inert organic solvent in the reaction vessel for granulating the rubber is usually 5 to 50 parts by weight, preferably 1 to 100 parts by weight of the total amount of various monomers in the polymerization raw material.
It is used in an amount of 0 to 30 parts by weight, more preferably 18 to 30 parts by weight. It is not necessary to add an inert solvent in the first step, but it is particularly preferable to add it to the second step. The addition facilitates the control of the polymerization reaction and lowers the viscosity of the polymerization solution. Facilitates the operability of the manufacturing process and also makes it possible to control the molecular weight.

In the present invention, various known chain transfer agents can be used for controlling the molecular weight of the styrene-acrylonitrile copolymer. For example, known chemical substances such as t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan and α-styrene dimer are used. The chain transfer agent may be added separately in the first step and the second step. The amount of chain transfer agent added depends on its chain transfer ability and the molecular weight of the target product,
It is usually used in an amount of 0.01 to 2.0 parts by weight based on 100 parts by weight of the total amount of various monomers in the polymerization raw material.

The reaction tank referred to in the present invention is not limited to a specified type of reaction tank, but for example, a complete mixing type reaction tank, a tubular type or a tower type reaction tank and the like can be used. As the reaction tank at the phase inversion stage, a complete mixing type reaction tank is preferable because it is easy to control the diameter of the generated rubber particles and has a high ability to uniformly mix the polymerization liquid. The number of reaction vessels used in the present invention is preferably 2 or more, particularly 2 to 5 in the first step and the second step.

Stirring of the main polymerization reaction is performed by paddle blades, turbine blades, propeller blades, Faudler blades, lattice blades, gate blades,
Known stirring blades such as a helical ribbon blade are used, and these may be used alone or in combination of two or more. It can also be used with single-stage or multi-stage blades. The rotation speed of the stirring blade varies depending on the volume of the reaction tank, the viscosity of the polymerization solution, the required shearing force, etc., but normally 10 rpm to 600 r
pm.

The temperature of the first step is 50 to 140 ° C., preferably 50 to 110 ° C., and the second step is 50 to 180 ° C.
C, preferably 50 to 140C. When two or more polymerization machines are used as the transfer tank and the post-polymerization tank in the second step,
The temperature of the first transfer tank is 50 to 140 ° C., preferably 80 to 120 ° C. for controlling the rubber particles produced, and the temperature of the post polymerization tank is 50 to 180 ° C., preferably 100 to 140 ° C.

The average residence time in each step in the present invention is usually 0.2 to 5 hours. If the average residence time is shorter than 0.2 hours, a phenomenon occurs in which the polymerization raw material passes through the reaction tank without being sufficiently polymerized, and the physical properties of the product deteriorate. If the average residence time is longer than 5 hours,
Production volume will decrease, resin production cost will increase, and productivity will decrease.

In the first step, the monomers are polymerized in a state where the rubbery polymer does not substantially transfer to the dispersed phase. In the present invention, the state in which the rubber-like polymer does not substantially transfer to the dispersed phase means that the rubber-like polymer forms a continuous phase in the polymerization liquid and the styrene-acrylonitrile-based copolymer forms the dispersed phase. That is, it can be easily confirmed by observing the polymerization solution with an optical microscope or the like. An example of a method for keeping the rubber-like polymer in a state where it does not substantially transform into the dispersed phase will be described below.

Generally, the main factor causing the rubbery polymer to transform into the dispersed phase is the volume ratio of the rubbery polymer to the styrene-acrylonitrile-based copolymer produced. For example, when the amount of the styrene-acrylonitrile-based copolymer is Phase transition occurs when the amount exceeds 2.3 times the amount of the rubber-like polymer in the polymerization solution.
The polymerization of the monomer in the step is within the range of 0.1 to 2.3 times the amount of the rubber-like polymer in the polymerization liquid, preferably 0.5 to 2.0.
It is preferable to suppress the time by a factor of 1, more preferably 1 to 1.5. However, since it is not practical to determine the volume ratio of the rubber-like polymer and the styrene-acrylonitrile-based copolymer, the weight ratio of the rubber-like polymer and the styrene-acrylonitrile-based copolymer is generally controlled. It is considered that the range of this weight ratio is almost the same as the case of the volume ratio.

The polymerization temperature in the first step is 50 to 140 ° C.,
It is preferably carried out in the range of 50 to 110 ° C. When the polymerization temperature is lower than 50 ° C, the polymerization rate is suppressed and the productivity is lowered, and when it is higher than 140 ° C, graft polymerization is less likely to occur and the impact resistance is lowered. The average residence time in the first step is suitably 0.2 to 5 hours as in the method usually used.

The method of suppressing the polymerization of the monomer in the first step within the range of not exceeding 0.1 to 2.3 times the amount of the rubber-like polymer in the polymerization liquid is as follows. The polymerization temperature and the type and concentration of the polymerization initiator are adjusted by a known method for controlling the polymerization rate to maintain the volume ratio of the rubber-like polymer in the above range and the produced styrene-acrylonitrile-based copolymer. Control is performed.

A method for controlling the polymerization rate is described in P.
J. Flory's "Principles of Po"
Japanese Chemistry of “lyer Chemistry”
Edition 101-125, Chapter 4, "Polymerization of unsaturated monomers by free radical mechanism", especially 10
As described on page 8, the polymerization rate R _p is calculated by the following formula.

The polymerization reaction proceeds according to the following reaction formula. k _p: rate constant k _d: Initiator decomposition constant k _t: stop rate constant [I]: Initiator concentration f: Initiator efficiency [M]: When the monomer concentration, polymerization rate is determined by the following equation. R _p = k _p [M ·] [M] = k _p (fk _d [I] / k _t ) ^1/2
[M] For these, k _p (t), k _d (t), and f with respect to the used monomer and initiator can be obtained by an experiment, or the polymerization rate can be obtained from literature values. Once the target conversion rate and average residence time are determined, it is possible to calculate a suitable combination of initiator concentration and polymerization temperature, which makes it possible to set conditions that do not transfer in the first tank. Can be easily calculated by those skilled in the art.

The polymerization liquid continuously withdrawn from the first step is continuously supplied to the first reaction tank constituting the second step.

In the method of the present invention, the above-mentioned polymerization raw material is supplied to the first reaction tank (hereinafter referred to as the first polymerization raw material), and the rubber-like polymer is not substantially transferred to the dispersed phase. A first step of carrying out polymerization, and a step of transferring a rubbery polymer to a dispersed phase by continuously adding a polymerization raw material (hereinafter referred to as a second polymerization raw material) after the second reaction tank and polymerizing the monomer It consists of two steps.

In the second step, at least one kind of polymerization raw material selected from an inert organic solvent, a monomer and a rubber-like polymer, and if necessary, a polymerization initiator and a chain transfer agent are the same as those in the polymerization solution from the first step. Add to the first reaction vessel that constitutes the second step with a pipe or another pipe. At that time, the first of the second polymerization raw materials
It is important to set the ratio to the polymerization raw material in the range of 10 to 220% by weight.

The ratio of the second polymerization raw material to the first polymerization raw material is in the range of 10 to 220% by weight, preferably 25 to 220% by weight, more preferably 25 to 160% by weight.

When the above-mentioned ratio exceeds 10% by weight, the shape of the rubber-like polymer particles in the second step can be easily controlled, and the surface gloss of the molded article becomes high, which is preferable. In addition, the ratio is 220
If it is less than 10% by weight, the amount of the polymerization liquid extracted from the first step is sufficient, and the concentration of the graft polymer produced in the first step is appropriately high, so that the effect of the graft polymer produced in the first step is sufficient. It is useful to be used.

The second polymerization raw material to be added is at least one or more of an inert organic solvent, a monomer and a rubbery polymer. Particularly, when the (A) second raw material is composed of an inert organic solvent and a monomer, the concentration of the rubber-like polymer in the first step is high and the concentration of the inert organic solvent is low, so that the first step The graft reaction proceeds in step (1) to obtain a resin having high gloss and high impact resistance. (B) When the second raw material is composed of a monomer and a rubbery polymer, the molecular weight of the copolymer produced in the first step is low because the concentration of the inert organic solvent in the first step is high. As a result, a resin having good fluidity can be obtained. (C) When the second raw material is composed of an inert organic solvent and a rubber-like polymer, the concentration of the inert organic solvent in the first step becomes low, so that the graft inhibition reaction by the inert solvent in the first step And a resin with high impact strength can be obtained. (D) When the second raw material is composed of a monomer, an inert organic solvent, and a rubbery polymer, it exhibits intermediate performance between the above (A) to (C) depending on its composition, and the desired impact. The balance of strength, surface gloss, and fluidity can be controlled arbitrarily. The additional amount is not limited as long as the ratio to the first polymerization raw material is in the range of 10 to 220% by weight, and there are various expression methods for defining the additional amount, but the ratio to the first polymerization raw material is 10 to 10. There is no contradiction because it may be in the range of 220% by weight.

The additional amount of the second polymerization raw material of the present invention will be specifically described below. (1) When a monomer is added as the second polymerization raw material, the ratio of the rubber-like polymer to the polymerization liquid in the first step is X% by weight, and the ratio of the rubber-like polymer to the polymerization liquid in the second step is Y% by weight. Where, the range satisfying the following formula VIII (formula 8), preferably the following formula IX (formula 9)
Will be added within the range that satisfies.

[0040]

(8) 0.3 ≦ Y / X ≦ 0.9 VIII

[0041]

## EQU9 ## 0.4 ≦ Y / X ≦ 0.75 IX In this case, the rubber-like polymer is not added to the second step, and the additional amount is defined based on the rubber-like polymer. The same applies when only the inert organic solvent is added, or when the monomer and the inert organic solvent are added. Of course, it is also possible to add the rubbery polymer at the same time. (2) When a monomer is added as the second polymerization raw material The ratio of the inert organic solvent to the polymerization liquid in the first step is S% by weight, and the ratio of the inert organic solvent to the polymerization liquid in the second step is T% by weight. Then, the following formula X (Equation 10),
Preferably, it is added in a range satisfying the following formula XI (formula 11), and more preferably the following formula XII (formula 12).

[0042]

[Equation 10] 1.1 ≦ S / T ≦ 2.5 X

[0043]

(11) 1.18 ≦ S / T ≦ 2.5 XI

[0044]

1.25 ≦ S / T ≦ 2.5 XII In this case, without adding an inert organic solvent in the second step,
In case of this formula, the second
This is the case when a monomer or a monomer and a rubber-like polymer are added to the process. Compared with the case of (1), it has a characteristic that the fluidity is particularly good. (3) When adding an inert organic solvent When the ratio of the inert organic solvent to the polymerization liquid in the first step is S% by weight and the weight of the inert organic solvent to the polymerization liquid in the second step is T% by weight, Formula XIII (number 1
3), preferably in a range satisfying the following formula XIV (formula 14), and more preferably the following formula XV (formula 15).

[0045]

[Equation 13] 0 ≦ S / T ≦ 0.6 XIII

[0046]

[Expression 14] 0 ≦ S / T ≦ 0.5 XIV

[0047]

0 ≦ S / T ≦ 0.4 XV The addition of the second raw material of the present invention is carried out by adding the inert organic solvent in the second step to adjust the concentration of the inert organic solvent in the second step to that in the first step. It is higher than the concentration of the inert organic solvent. In the first step, a styrene-based monomer, an acrylonitrile-based monomer, a vinyl-based monomer copolymerizable with these monomers, and a rubber-like polymer are used, if necessary, in an inert organic solvent, polymerization. It is continuously supplied together with the initiator and the chain transfer agent. Here, the ratio of the inert organic solvent to the polymerization liquid in the first step is S% by weight. The value of S is usually 0 ≦
It satisfies S ≦ 20, preferably 0 ≦ S ≦ 15, and more preferably 0 ≦ S ≦ 10. Second here
The ratio of the inert organic solvent to the polymerization liquid in the step is T
Weight% In the present invention, the ratio of S to T is set to 0 by controlling the amounts of the inert organic solvent, the monomer, the rubbery polymer, the polymerization initiator and the chain transfer agent, which are added in the second step.
It is necessary to satisfy the range of ≦ S / T ≦ 0.6, preferably 0 ≦ S / T ≦ 0.5, more preferably 0 ≦ S / T ≦ 0.4. If this value exceeds 0.6, huge rubber particles will be generated in the rubber particles, and the surface gloss will be significantly reduced. Although the cause of this phenomenon is not clear,
It is estimated that the difference in the graft polymerizability with respect to the rubber-like polymer in the first step and the second step has an influence.

The ratio T weight% of the inert organic solvent to the polymerization liquid in the second step is usually 5 ≦ T ≦ 50, preferably 1
It satisfies the range of 0 ≦ T ≦ 30, more preferably 15 ≦ T ≦ 25. When T is 50% by weight or more, huge rubber particles are generated due to aggregation of the rubber-like polymer particles once dispersed, and the surface gloss is lowered. Moreover, the monomer content of the polymerization system is small and the productivity is low. On the other hand, when T is small, it is difficult to control the polymerization rate. If the polymerization cannot be controlled, the viscosity of the polymerization liquid becomes too high, and the shape of the rubber-like polymer particles cannot be controlled. On the other hand, when the polymerization does not proceed, on the contrary, the viscosity of the polymerization solution is too low and the diameter of the rubber particles produced becomes large. As described above, there is a close relationship between the polymerization rate and the rubber particle size, and it is difficult to control the polymerization rate due to ABS.
It is not preferable as a resin manufacturing process. (4) When adding the monomer and the inert organic solvent, the ratio of the rubber-like polymer to the polymerization liquid in the first step is X.
%, And Y is the weight ratio of the rubber-like polymer to the polymerization liquid in the second step, the following formula XVI (Equation 1)
6), preferably satisfying the following formula XVII (formula 17), more preferably the following formula, XVIII (formula 18),
And

[0049]

(16) 0.3 ≦ Y / X ≦ 0.9 XVI

[0050]

[Expression 17] 0.3 ≦ Y / X ≦ 0.8 XVII

[0051]

0.4 ≦ Y / X ≦ 0.75 XVIII The ratio of the inert organic solvent to the polymerization liquid in the first step is S% by weight, and the ratio of the inert organic solvent to the polymerization liquid 100 in the second step is T. Assuming weight%, the following formula X
IX (Equation 19), preferably the following formula XX (Equation 20),
More preferably, the following formula XXI (Equation 21) is added within a range satisfying the condition.

[0052]

[Formula 19] 0 ≦ S / T ≦ 0.6 XIX

[0053]

[Equation 20] 0 ≦ S / T ≦ 0.5 XX

[0054]

[Expression 21] 0≤S / T≤0.4 XXI When the monomer and the inert organic solvent are added, the surface gloss and impact resistance are particularly excellent, and an extremely well-balanced resin is obtained.

As described above, various methods other than the above can be applied to the method for adding the second polymerization raw material. The addition of the second polymerization raw material can be performed by measuring the concentration of each raw material and the like. It can also be used for confirmation of means and control for adjusting the ratio of the raw material to the first polymerization raw material in the range of 10 to 220% by weight.

In the method of the present invention, the rubber-like polymer is transferred to the dispersed phase by shearing the polymerization liquid accompanying the polymerization and stirring of the monomer in the second step. This transition phase can be generated in any reaction tank constituting the second step based on the control of the polymerization conversion rate of the monomer and the stirring rotation speed of the reaction tank which are usually performed in the continuous bulk or solution polymerization method. . Polymerization in the second step is 80 to 180 ° C., preferably 80 to 140 ° C.
It is done in the range of. When the polymerization temperature is lower than 80 ° C., the polymerization rate is low and the productivity is poor, and when it is higher than 180 ° C., a large amount of low molecular weight styrene-acrylonitrile-based copolymer is produced and the heat resistance of the product is lowered, which is not preferable. The desired polymerization conversion rate in the reaction vessel for phase inversion, preferably 25 to
The polymerization is continued until it reaches 42% by weight, more preferably 35 to 42%, and the polymerization is continued in the reaction vessel thereafter to 42 to 42% by weight.
Polymerization is continued to 70%, preferably 50 to 65%.

The subsequent steps are not particularly limited, but the rubber-modified styrenic resin is subjected to a devolatilization step for removing residual monomers, solvents and the like which are usually carried out in a continuous bulk or solution polymerization method, and an extrusion step. Is manufactured. In the present invention, the average particle size of the rubber-like polymer particles contained in the obtained rubber-modified styrenic resin is usually 0.2-2.
The thickness is controlled to 5 μm, preferably 0.2 to 1.4 μm, more preferably 0.2 to 0.9 μm. The method for measuring the rubber-like polymer particle size is described in Example 1. When the average particle size of the rubber-like polymer particles is smaller than 0.2 μm, the surface gloss is high but the impact resistance is low, and when it is larger than 2.5 μm, both the impact resistance and the surface gloss are low.

By using the rubber-modified styrenic resin of the present invention, it is possible to produce a molded article having impact resistance and surface gloss significantly improved as compared with conventional products. In the present invention, the reason why both the impact resistance and the surface gloss are improved is not clear, but the graft amount in the rubber-modified styrene resin, that is, the rubber-like polymer contained in the rubber-modified styrene resin, or the rubber-like polymer Since the amount of styrene-acrylonitrile-based copolymer bound to the coalescence is increased, the interfacial tension between the rubber-like polymer and the styrene-acrylonitrile-based copolymer is reduced by the graft chain, and the rubber-like polymer particles are It is presumed that the particle size is reduced and the surface gloss of the molded article is improved, while the graft chain increases the adhesive strength between the rubber-like polymer and the styrene-acrylonitrile-based copolymer to improve the impact resistance. Furthermore, according to this method, a large amount of the second polymerization raw material can be added to the polymerization system.
Polymerization after the process can be suppressed, and the rubber concentration in the product can be increased.

The rubber-modified styrenic resin according to the present invention is
Home appliances such as washing machines, air conditioners, refrigerators and AV equipment; O
General machinery such as A equipment, telephones, musical instruments; toys, cosmetic containers,
Miscellaneous goods such as seats; used as structural materials for automobiles, housing materials, etc., and have an extremely high industrial utility value.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0061]

【Example】

Example 1 In the experiments up to Examples 1 to 3, an example of an experiment was shown in which the monomer and ethylbenzene were added to the second polymerization tank, but the rubbery polymer was not added.

A rubber-modified styrenic resin was produced by using a continuous polymerization apparatus in which three completely mixed reaction vessels each having a capacity of about 15 liters were connected in series. The first reaction tank performs the first step,
The second reaction tank or the third reaction tank constitutes the second step. Styrene 48 parts by weight, acrylonitrile 16 in the first reaction tank
Parts by weight, 20 parts by weight of ethylbenzene, rubber-like polymer 16
Parts by weight, 0.15 parts by weight of t-dodecyl mercaptan,
The first raw material consisting of 0.03 parts by weight of 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane was continuously supplied at 5.0 kg / h by using a plunger pump. Polymerization of the monomer is carried out, and the polymerization temperature is adjusted so that the solid content at the outlet of the first reaction tank, that is, the amount of the rubber-like polymer and the styrene-acrylonitrile copolymer in the polymerization solution is 32% by weight based on the polymerization solution. I chose The polymerization temperature at this time was 90 ° C. The stirring speed of the reaction tank is 1
The polymerization temperature was 00 rpm, and the polymerization temperature was measured by inserting thermocouples at the upper, middle, and lower portions of the reaction tank. The temperatures at the three locations were controlled to an average value ± 0.2 ° C. Are considered to be uniformly mixed. As the rubbery polymer, a styrene-butadiene block copolymer was used in which the viscosity of a 5% by weight concentration styrene solution at 25 ° C. was 11 centipoise. (Nippon Zeon Co., Ltd., trade name NIPOL: NS310S) Rubber-like polymer particles were not formed in the first reaction tank.
The weight ratio of the rubber-like polymer to the styrene-acrylonitrile-based copolymer in the first tank was 16:16.

The polymerization liquid was continuously taken out from the first reaction tank and continuously supplied to the second reaction tank. Further, 60 parts by weight of styrene, 20 parts by weight of acrylonitrile, 20 parts by weight of ethylbenzene, 0.1 part of t-dodecyl mercaptan.
5 parts by weight, 1,1-bis (t-butylperoxy) 3,3
Using a plunger pump, 5.0 kg of a second raw material consisting of 0.03 part by weight of 3,5-trimethylcyclohexane.
/ H was continuously fed to the second reaction tank. Note that only 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane was supplied from another line. Here, the ratio of the amount of ethylbenzene in the first reaction tank and the second reaction tank (S /
T) is 1. The ratio (Y / X) of the rubber-like polymer in the second reaction tank to the first reaction tank was 0.5. The polymerization of the monomer is continued in the second reaction tank and the polymerization temperature is adjusted to the second
The solid content at the outlet of the reaction tank was set to 36% by weight based on the polymerization liquid. The polymerization temperature at this time was 90 ° C. In the second reaction tank, the rubber-like polymer was transferred to the dispersed phase, and rubber-like polymer particles were formed. The polymerization liquid continuously withdrawn from the second reaction tank was supplied to the third reaction tank, and the solid content at the outlet of the third reaction tank was adjusted to 50% by weight by the polymerization in the third reaction tank.
Next, pelletization was performed through a devolatilization step and an extrusion step.

Tables 1 and 2 show the results of the polymerization conditions, analysis and performance evaluation of the rubber-modified styrene resin thus produced. This resin is superior in surface gloss and practical impact strength in the parts A and B of the molded product shown in FIG. 1 as compared with the results of comparative examples described later.

The resin analysis and performance evaluation were carried out by the following methods. (A) Rubber amount of resin: The amount of rubber dissolved in the first raw material was calculated from the supply amount of the first raw material, the supply amount of the second raw material, and the mass balance of the solid content in the third reaction tank. (B) Average rubber particle diameter: An electron micrograph of a resin taken by an ultra-thin section method, the particle diameters of 500 to 700 rubber particles in the photograph were measured, and averaged by the following formula XXII (Equation 22). Is.

[0066]

## EQU22 ## Average rubber particle diameter = ΣnD ⁴ / ΣnD ³ ... XXII where n is the number of rubber particles having a particle diameter D. (C) Preparation of test piece: The obtained resin was dried at 90 ° C. for 3 hours, then injection-molded at a molding temperature of 240 ° C. and a mold temperature of 40 ° C., and a test piece for measuring Izod impact strength and shown in FIG. A test piece for practical impact strength measurement having a shape was prepared.

In FIG. 1, the gate portion, that is, the inlet through which the molten resin flows into the mold is represented by G, and the portion A is the portion where the thickness changes due to the influence of the position of the gate portion, and the portion B is near the corner. Part and part C are standard parts. In general, the impact strength tends to increase in the order of part A, part B, and part C. (D) Izod impact strength: Measured according to JIS K-6871. (E) Practical impact strength: A drop weight impact strength test was conducted on three sites (site A, site B, site C) having the shape shown in FIG. The tip of the falling weight R was 6.4 mm, and the inner diameter of the bed was 25 mm. (F) Surface gloss: Measured according to JIS Z-8741. An incident angle of 60 at the site C of the molded product having the shape shown in FIG.
It was irradiated with light at °.

Examples 2 to 3 First polymerization raw material, its supply amount, polymerization temperature, solid content at the outlet of the first reaction tank, second polymerization raw material supply amount, composition, polymerization temperature,
A rubber-modified styrenic resin was produced in the same manner as in Example 1, except that the solid content at the outlet of the second tank and the solid content at the outlet of the third reaction tank were changed. In both cases, rubber particles were formed in the second reaction tank. The polymerization conditions and the results of performance evaluation are shown in Tables 1 and 2.

Comparative Examples 1 and 2 First polymerization raw material, its supply amount, polymerization temperature, solid content at the outlet of the first reaction tank, second polymerization raw material supply amount, composition, polymerization temperature,
A rubber-modified styrene-based resin was produced in the same manner as in Example 1, except that the solid content at the outlet of the second reaction tank and the solid content at the outlet of the third reaction tank were changed. In both cases, rubber particles were formed in the second reaction tank. The polymerization conditions and the results of performance evaluation are shown in Tables 1 and 2. In Comparative Example 1, the rubber particle size was large and the impact resistance and surface gloss were inferior to those of Example 1. In Comparative Example 2, since the concentration of the rubber-like polymer in the first reaction tank was too high, the viscosity in the first reaction tank was high, and a large burden was imposed on the raw material supply and the stirring of the polymerization solution, which was a practical problem. . Moreover, the variation in impact resistance was very large.

Example 4 In the experiments of Examples 4 to 6, an example of an experiment in which a monomer and a rubbery polymer were added to the second polymerization tank but ethylbenzene was not added was shown.

A rubber-modified styrenic resin was produced using a continuous polymerization apparatus in which three completely mixed reaction vessels each having a capacity of about 15 liters were connected in series. The first reaction tank performs the first step,
The second reaction tank or the third reaction tank constitutes the second step. Styrene 43 parts by weight, acrylonitrile 14 in the first reaction tank
Parts by weight, ethylbenzene 35 parts by weight, rubbery polymer 8 parts by weight, t-dodecyl mercaptan 0.15 parts by weight, 1,
Monomer was obtained by continuously supplying the first raw material consisting of 0.03 parts by weight of 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane at 5.7 kg / h using a plunger pump. The polymerization is performed and the polymerization temperature is adjusted to
The solid content at the outlet of the reaction tank, that is, the amount of the rubber-like polymer and the styrene-acrylonitrile-based copolymer in the polymerization solution was set to 22% by weight based on the polymerization solution. The polymerization temperature at this time was 90 ° C. The stirring speed of the reaction tank is 100.
The temperature was rpm, and the polymerization temperature was measured by inserting thermocouples in the upper, middle, and lower parts of the reaction tank, but the temperatures at the three parts were controlled to an average value ± 0.2 ° C. Are considered to be uniformly mixed. The same rubber-like polymer as in Example 1 was used.

No rubber-like polymer particles were formed in the first reaction tank. The weight ratio of the rubber-like polymer to the styrene-acrylonitrile-based copolymer in the first tank was 8:14.

The polymerization liquid was continuously taken out from the first reaction tank and continuously supplied to the second reaction tank. Further, 69 parts by weight of styrene, 23 parts by weight of acrylonitrile, 8 parts by weight of a rubber-like polymer, 0.15 parts by weight of t-dodecyl mercaptan, 1,1-bis (t-butylperoxy) 3,3,3.
A second raw material consisting of 0.03 parts by weight of 5-trimethylcyclohexane was used in an amount of 4.3 kg / h by using a plunger pump.
Was continuously supplied to the second reaction tank. Polymerization of the monomer was continued in the second reaction tank, and the polymerization temperature was adjusted so that the solid content at the outlet of the second reaction tank was 36% by weight based on the polymerization liquid. The polymerization temperature at this time was 100 ° C. In the second reaction tank, the rubber-like polymer was transferred to the dispersed phase, and rubber-like polymer particles were formed. The polymerization liquid continuously withdrawn from the second reaction tank is the third
The solid content at the outlet of the third reaction tank was adjusted to 50% by weight by being supplied to the reaction tank and polymerized in the third reaction tank. Next, pelletization was performed through a devolatilization step and an extrusion step.

Tables 1 and 2 show the polymerization conditions, analysis and performance evaluation results of the rubber-modified styrene resin thus produced.

Examples 5-6 First polymerization raw material, supply amount thereof, polymerization temperature, solid content at the outlet of first reaction tank, supply amount of second polymerization raw material, composition, polymerization temperature,
A rubber-modified styrene-based resin was produced in the same manner as in Example 4 by changing the solid content at the outlet of the second tank and the solid content at the outlet of the third reaction tank.

However, in Example 6, the composition of the second raw material was 67.5 parts by weight of styrene, 22.5 parts by weight of acrylonitrile, 10 parts by weight of a rubber-like polymer, 0.15 parts by weight of t-dodecyl mercaptan, and 1,1. -Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 0.03 part by weight.

Comparative Example 3-4 First polymerization raw material, its supply amount, polymerization temperature, solid content at the outlet of the first reaction tank, second polymerization raw material supply amount, composition, polymerization temperature,
A rubber-modified styrene-based resin was produced in the same manner as in Example 1, except that the solid content at the outlet of the second reaction tank and the solid content at the outlet of the third reaction tank were changed. In both cases, rubber particles were formed in the second reaction tank. The polymerization conditions and the results of performance evaluation are shown in Tables 1 and 2. In Comparative Example 3, since the concentration of ethylbenzene in the second reaction tank is low, the polymerization rate is high, and it is difficult to adjust the solid content in the polymerization liquid in the second reaction tank. Moreover, impact resistance, surface gloss, and resin fluidity were also inferior to those in Example 6. In Comparative Example 4, the polymerization rate was low because the concentration of ethylbenzene in the first and second reaction tanks was high, and it was difficult to adjust the solid content in the polymerization liquid in the second reaction tank, and the fluidity of the resin was high. Was higher than that of Example 5, but impact resistance, surface gloss, and resin fluidity were also inferior to those of Example 5 due to aggregation of rubber particles generated in the second reaction tank.

Example 7 In the experiments of Examples 7 to 8, an example of an experiment in which the monomer and ethylbenzene were added to the second polymerization tank but the rubbery polymer was not added was shown.

A rubber-modified styrenic resin was produced using a continuous polymerization apparatus in which three completely mixed reaction vessels each having a capacity of about 15 liters were connected in series. The first reaction tank performs the first step,
The second reaction tank or the third reaction tank constitutes the second step. 69 parts by weight of styrene, 23 acrylonitrile in the first reaction tank
Parts by weight, 8 parts by weight of rubbery polymer, 0.15 parts by weight of t-dodecyl mercaptan, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 0.03
The first raw material consisting of parts by weight is continuously fed at 7.0 kg / h using a plunger pump to polymerize the monomer, and the polymerization temperature is adjusted to adjust the solid content at the outlet of the first reaction tank, that is, The amount of the rubber-like polymer and the styrene-acrylonitrile-based copolymer in the polymerization liquid was set to 19% by weight based on the polymerization liquid. The polymerization temperature at this time was 85 ° C. The stirring speed of the reaction tank was 100 rpm, and the polymerization temperature was measured by inserting thermocouples at the upper, middle, and lower portions of the reaction tank. It is considered that the polymerization liquid is uniformly mixed because it is controlled within the range. The same rubbery polymer as in Example 1 was used.

No rubbery polymer particles were formed in the first reaction tank. The weight ratio of the rubber-like polymer to the styrene-acrylonitrile-based copolymer in the first tank was 8:11.

The polymerization liquid was continuously taken out from the first reaction tank and continuously supplied to the second reaction tank. Further, 18.7 parts by weight of styrene, 6.3 parts by weight of acrylonitrile,
67 parts by weight of ethylbenzene, 8 parts by weight of rubbery polymer, t
-A second raw material consisting of 0.15 parts by weight of dodecyl mercaptan and 0.03 parts by weight of 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane was used in an amount of 3.0 kg / using a plunger pump. It was continuously fed to the second reaction tank at h. Note that only 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane was supplied from another line. Here, the ratio (S / T) of the amount of ethylbenzene in the first reaction tank and the second reaction tank is 0. The polymerization of the monomer is continued in the second reaction tank and the polymerization temperature is adjusted to the second
The solid content at the outlet of the reaction tank was set to 36% by weight based on the polymerization liquid. The polymerization temperature at this time was 100 ° C. In the second reaction tank, the rubber-like polymer was transferred to the dispersed phase, and rubber-like polymer particles were formed. The polymerization liquid continuously withdrawn from the second reaction tank was supplied to the third reaction tank, and the solid content at the outlet of the third reaction tank was adjusted to 50% by weight by the polymerization in the third reaction tank.
Next, pelletization was performed through a devolatilization step and an extrusion step.

The results of polymerization conditions, analysis and performance evaluation of the rubber-modified styrene resin thus produced are shown in Tables 1 and 2.

Example 8 Example 7 was repeated except that the composition of the first raw material, the polymerization temperature in the first reaction tank and the composition of the second raw material were changed as shown in Table 1.
A rubber-modified styrenic resin was produced in exactly the same manner as.
Ratio of the amount of ethylbenzene in the first reaction tank and the second reaction tank (S
/ T) was 0.5 and rubber particles were formed in the second reaction vessel. The results of analysis and performance evaluation of the obtained resin are shown in Table 2. The weight ratio of the rubber-like polymer to the styrene-acrylonitrile copolymer in the first tank of this example was 8:11.

Example 9 In the experiments of Examples 9 to 12, an example of the experiment was shown in which a monomer and ethylbenzene were added to the second polymerization tank.

A rubber-modified styrenic resin was produced using a continuous polymerization apparatus in which three completely mixed reaction vessels were connected in series. The first reaction tank constitutes the first step and the second to third reaction tanks constitute the second step. Styrene 6 in the first reaction tank
6.4 parts by weight, acrylonitrile 22.2 parts by weight, rubbery polymer 11.4 parts by weight, t-dodecyl mercaptan 0.15 parts by weight, 1,1-bis (t-butylperoxy) 3,3,5 -The first raw material consisting of 0.03 parts by weight of trimethylcyclohexane was continuously fed at 7.0 kg / h to polymerize the monomer, and the polymerization temperature was adjusted to control the solid content at the outlet of the first reaction tank, that is, the polymerization. The amount of the rubber-like polymer and the styrene-acrylonitrile-based copolymer in the liquid was adjusted to 22.9% by weight based on the polymerization liquid. At this time, the polymerization temperature is 8
It was 1 ° C. As the rubbery polymer, a styrene-butadiene block copolymer having a viscosity of a styrene solution having a concentration of 5% by weight at 25 ° C. of 15 centipoise was used. No rubbery polymer particles were formed in the first reactor.

The polymerization liquid was continuously taken out from the first reaction tank and continuously supplied to the second reaction tank. Further, 25 parts by weight of styrene, 8.3 parts by weight of acrylonitrile, 66.7 parts by weight of ethylbenzene, 0.15 parts by weight of t-dodecylmercaptan, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane. The second raw material consisting of 0.03 parts by weight was continuously supplied to the second reaction tank at 3.0 kg / h. Here, the ratio (Y / X) of the amount of the rubber-like polymer in the first reaction tank and the second reaction tank was 0.7, and the ratio of the amount of the organic solvent in the first reaction tank and the second reaction tank (S / T) ) Is 0.0. Polymerization of the monomer is continued in the second reaction tank, the polymerization temperature is adjusted, and the solid content at the outlet of the second reaction tank is adjusted to 36% with respect to the polymerization liquid.
It was made into the weight%. The polymerization temperature at this time was 100 ° C. In the second reaction tank, the rubber-like polymer was transferred to the dispersed phase and rubber-like polymer particles were formed. The polymerization liquid continuously extracted from the second reaction tank was supplied to the third reaction tank, and the solid content at the outlet of the third reaction tank was adjusted to 50% by weight by the polymerization in the third reaction tank. Next, pelletization was performed through a devolatilization step and an extrusion step. The results of the polymerization conditions, analysis and performance evaluation of the rubber-modified styrene resin thus produced are shown in Tables 1 and 2. This resin is superior in surface gloss and impact strength, especially in practical impact strength in the parts A and B of the molded product shown in FIG. 1, as compared with the results of the comparative example described later.
The weight ratio of the rubber-like particles to the styrene-acrylonitrile copolymer in the first step of the main polymerization reaction was 11.4:
It was 11.5.

Example 10 Example 9 was repeated except that the composition of the first raw material, the polymerization temperature in the first reaction tank and the composition of the second raw material were changed as shown in Table 1.
A rubber-modified styrenic resin was produced in exactly the same manner as.
Ratio of the amount of the rubber-like polymer in the first reaction tank and the second reaction tank (Y /
X) is 0.7, and the ratio (S / T) of the amounts of organic solvent in the first reaction tank and the second reaction tank is 0.5. Rubber particles were formed in the second reaction vessel. The results of analysis and performance evaluation of the obtained resin are shown in Table 2. The weight ratio of the rubber-like particles to the styrene-acrylonitrile copolymer in the first step in the main polymerization reaction was 11.4: 11.5.

Example 11 The composition of the first raw material, the supply amount of the first raw material, the polymerization temperature in the first reaction tank, the composition of the second raw material, and the supply amount of the second raw material were changed as shown in Table 1. Except for the above, a rubber-modified styrenic resin was produced in the same manner as in Example 1. The ratio (Y / X) of the amount of the rubber-like polymer in the first reaction tank and the second reaction tank is 0.5,
Ratio (S / T) of the amount of organic solvent in the first reaction tank and the second reaction tank
Is 0.0. Rubber particles were formed in the second reaction vessel. The results of analysis and performance evaluation of the obtained resin are shown in Table 2. The weight ratio of the rubber-like particles to the styrene-acrylonitrile copolymer in the first step in the main polymerization reaction is 1
It was 6.0: 16.0.

Example 12 The composition of the first raw material, the supply amount of the first raw material, the polymerization temperature in the first reaction tank, the composition of the second raw material, and the supply amount of the second raw material were changed as shown in Table 1. Except for the above, a rubber-modified styrenic resin was produced in exactly the same manner as in Example 9. The ratio (Y / X) of the amount of the rubber-like polymer in the first reaction tank and the second reaction tank is 0.5,
Ratio (S / T) of the amount of organic solvent in the first reaction tank and the second reaction tank
Is 0.5. Rubber particles were formed in the second reaction vessel. The results of analysis and performance evaluation of the obtained resin are shown in Table 2. The weight ratio of the rubber-like particles to the styrene-acrylonitrile copolymer in the first step in the main polymerization reaction is 1
It was 6.0: 16.0.

Comparative Example 5 Using the same polymerization apparatus as in Example 1, a rubber-modified styrenic resin was produced without prepolymerization. 54 parts by weight of styrene, 18 parts by weight of acrylonitrile, 20 parts by weight of ethylbenzene, 8 parts by weight of rubbery polymer, 0.15 parts by weight of t-dodecyl mercaptan, 1,1-bis (t-butylperoxy) in the first reaction tank. A raw material consisting of 0.03 parts by weight of 3,3,5-trimethylcyclohexane was continuously supplied at 10 kg / h to carry out polymerization at 110 ° C., and the solid content at the outlet of the first reaction tank was 28% by weight with respect to the polymerization liquid. I chose The composition of the first reaction vessel was the same as in Example 1 except for the monomers and copolymers formed.
It has the same composition as the reaction tank. Rubber particles were formed in the first reaction tank. The surface gloss was lower than that of Example 1, and it was confirmed that the impact resistance, particularly the impact resistance at the site A and the site B shown in FIG. 1, was low. The polymerization conditions, analysis and results of performance evaluation of the obtained resin are shown in Tables 1 and 2. The weight ratio of the rubber-like particles to the styrene-acrylonitrile copolymer in the first step in the main polymerization reaction was 8.0: 20.0.

Comparative Example 6 Polymerization temperature in the first reaction tank, solid content at the outlet of the first reaction tank,
A rubber-modified styrenic resin was produced in exactly the same manner as in Comparative Example 6 except that the polymerization temperature in the second reaction tank was changed as shown in Tables 1 and 2. Using the same polymerization raw material as in Comparative Example 6, the monomers were polymerized at 98 ° C. in the first reaction tank to make the solid content at the outlet of the first reaction tank 16% by weight with respect to the polymerization liquid. In 100 ° C., the monomer was polymerized to make the solid content at the outlet of the second reaction tank 36% by weight based on the polymerization liquid. No rubber particles were formed in the first reaction tank, and rubber particles were formed in the second reaction tank. The diameter of the produced rubber particles was as large as 1.45 μm, and both the impact resistance and the surface gloss were inferior to those of Example 1. The polymerization conditions of the obtained resin are shown in Table 1, and the results of analysis and performance evaluation are shown in Table 2.
The weight ratio of the rubber-like particles to the styrene-acrylonitrile copolymer in the first step of the main polymerization reaction was 8.0:
It was 8.0. Example 13 The initiator of Example 9 was changed to 2,2-azobis (2-methylbutyronitrile), and 0.018 parts by weight of the initiator was charged to the first reaction tank and the second reaction tank. Except for this, the same procedure as in Example 9 was performed. The experimental results are shown in Tables 1 and 2.

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

[Table 3]

[0095]

[Table 4]

EFFECT OF THE INVENTION A rubber-modified styrenic resin having greatly improved impact resistance and surface gloss can be produced.

[Brief description of drawings]

FIG. 1 is a view showing a shape of a test piece used for evaluation of surface gloss of a molded article in evaluation of physical properties of a rubber-modified styrene resin obtained in the present invention, (a) is a plan view, b)
Is a sectional view.

─────────────────────────────────────────────────── ─── Continuation of front page (31) Priority claim number Japanese Patent Application No. 6-75812 (32) Priority date April 14, 1994 (April 14, 1994) (33) Priority claim country Japan (JP) (72) Masato Takahisa 1-6 Takasago, Takaishi, Osaka Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Nao Morita 1-6 Takasago, Takaishi City Osaka Prefecture Mitsui Toatsu Chemical (72) Invention Takao Kobayashi, 1-6 Takasago, Takaishi-shi, Osaka, Mitsui Toatsu Kagaku Co., Ltd. (72) Inventor Toshihiko Ando 1-6, Takasago, Takaishi-shi, Osaka, Mitsui Toatsu Kagaku Co., Ltd. (56) 4-366116 (JP, A) JP-A-4-255705 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 279/02-279/06 C08F 287/00

Claims (16)

(57) [Claims] 1. A styrene-based polymer based on 100 parts by weight of all monomers in the presence of a rubber-like polymer by a continuous bulk and / or solution polymerization method using a continuous polymerization apparatus comprising two or more reaction tanks. 25 monomers
~ 97 parts by weight and 3 to 4 parts of acrylonitrile monomer.
5 parts by weight , or a styrene-based monomer, acrylonitrile-based monomer and an unsaturated compound monomer copolymerizable with these monomers (all of these monomers are simply monomers) 0-30 parts by weight are polymerized so that the styrene-acrylonitrile-based copolymer forms a continuous phase and the rubber-like polymer particles form a dispersed phase. In the method for producing a rubber-modified styrene resin as a polymerization raw material containing an inert organic solvent, (1) the polymerization raw material is supplied to the first reaction tank (hereinafter referred to as the first polymerization raw material), and the rubber-like polymer is substantially A first step of polymerizing the monomer in a state where it does not transfer to the dispersed phase in
The second step comprises adding a polymerization raw material after the reaction tank (hereinafter referred to as a second polymerization raw material) and continuously polymerizing the monomer to transfer the rubber-like polymer to the dispersed phase. (2) Second The ratio of the polymerization raw material to the first polymerization raw material is 10
The method for continuously producing a rubber-modified styrenic resin is characterized in that the range is from 220 to 220% by weight. 2. The method for continuously producing a rubber-modified styrenic resin according to claim 1, wherein the ratio of the second polymerization raw material to the first polymerization raw material is 25 to 220% by weight. 3. The second polymerization raw material added to the second step is a styrene monomer and an acrylonitrile monomer, or a styrene monomer, an acrylonitrile monomer and a copolymer with these monomers. The method for continuously producing a rubber-modified styrenic resin according to claim 1, which is at least one kind of a monomer selected from possible unsaturated compound monomers, a rubber-like polymer, or an inert organic solvent. 4. The second polymerization raw material added to the second step is a styrene monomer and an acrylonitrile monomer, or a styrene monomer, an acrylonitrile monomer, and a copolymer with these monomers. The method for continuously producing a rubber-modified styrenic resin according to claim 1, which is at least one kind of monomers selected from possible unsaturated compound monomers. 5. The continuous method for producing a rubber-modified styrenic resin according to claim 1, wherein the second polymerization raw material added to the second step is an inert organic solvent. 6. The continuous method for producing a rubber-modified styrenic resin according to claim 3, wherein the second polymerization raw material added to the second step contains a rubber-like polymer. 7. A continuous polymerization apparatus comprising two or more reaction tanks, and a continuous polymer and / or solution polymerization method in the presence of a rubber-like polymer to 100 parts by weight of all monomers. /> 3-45 parts by weight of 25 to 97 parts by weight acrylonitrile monomer and styrene monomer or styrene monomer, an acrylonitrile monomer and with these monomers copolymerizable unsaturated 0 to 30 parts by weight of a saturated compound monomer (all of these monomers are simply monomers) is polymerized to form a continuous phase of styrene-acrylonitrile-based copolymer and rubber-like polymer particles. In the method for producing a rubber-modified styrenic resin as a polymerization raw material, which comprises the above-mentioned rubber-like polymer, a monomer, and an inert organic solvent optionally added to form a dispersed phase, (1) in a first reaction tank Supplying the first polymerization raw material, rubbery polymerization The first step of polymerizing the monomer in a state where the body does not substantially transfer to the dispersed phase, and adding the monomer as the second polymerization raw material after the second reaction tank to polymerize the monomer. The second step is to continuously carry out the transition of the rubber-like polymer to the dispersed phase, and (2) the ratio of the rubber-like polymer to the polymerization liquid in the first step is X% by weight, to the polymerization liquid in the second step. The method for continuously producing a rubber-modified styrenic resin according to claim 1, wherein the following formula I (Equation 1) is satisfied when the proportion of the rubber-like polymer is Y% by weight. ## EQU1 ## 0.3 ≦ Y / X ≦ 0.9 I 8. A continuous polymerization apparatus comprising two or more reaction tanks, and a continuous polymer and / or solution polymerization method in the presence of a rubbery polymer , based on 100 parts by weight of all monomers. /> 3-45 parts by weight of 25 to 97 parts by weight acrylonitrile monomer and styrene monomer or styrene monomer, an acrylonitrile monomer and with these monomers copolymerizable unsaturated 0 to 30 parts by weight of a saturated compound monomer (all of these monomers are simply monomers) is polymerized to form a continuous phase of styrene-acrylonitrile-based copolymer and rubber-like polymer particles. In the method for producing a rubber-modified styrenic resin as a polymerization raw material, which comprises the above-mentioned rubber-like polymer, a monomer, and an inert organic solvent optionally added to form a dispersed phase, (1) in a first reaction tank Supplying the first polymerization raw material, rubbery polymerization The first step of polymerizing the monomer in a state where the body does not substantially transfer to the dispersed phase, and adding the monomer as the second polymerization raw material after the second reaction tank to polymerize the monomer. The second step is to continuously carry out the transition of the rubbery polymer to the dispersed phase, and (2) the ratio of the inert organic solvent to the polymerization solution in the first step is S% by weight, and the ratio to the polymerization solution in the second step is When the proportion of the inert organic solvent is T% by weight, the following formula I
The method for continuously producing a rubber-modified styrenic resin according to claim 1, wherein I (equation 2) is satisfied. [Equation 2] 1.1 ≦ S / T ≦ 2.5 II 9. A continuous polymerization apparatus comprising two or more reaction tanks, and a continuous polymer and / or solution polymerization method in the presence of a rubbery polymer , based on 100 parts by weight of all monomers. /> 3-45 parts by weight of 25 to 97 parts by weight acrylonitrile monomer and styrene monomer or styrene monomer, an acrylonitrile monomer and with these monomers copolymerizable unsaturated 0 to 30 parts by weight of a saturated compound monomer (all of these monomers are simply monomers) is polymerized to form a continuous phase of styrene-acrylonitrile-based copolymer and rubber-like polymer particles. In the method for producing a rubber-modified styrenic resin as a polymerization raw material, which comprises the above-mentioned rubber-like polymer, a monomer, and an inert organic solvent optionally added to form a dispersed phase, (1) in a first reaction tank Supplying the first polymerization raw material, rubbery polymerization Polymerization of the monomer in a state where the body does not substantially transfer to the dispersed phase, and polymerization of the monomer by adding an inert organic solvent as a second polymerization raw material after the second reaction tank. The second step of continuously transferring the rubbery polymer to the dispersed phase, and (2) the ratio of the inert organic solvent to the polymerization liquid in the first step is S% by weight, and the polymerization liquid in the second step is The ratio of the inert organic solvent to
The method for continuously producing a rubber-modified styrenic resin according to claim 1, wherein I (equation 3) is satisfied. [Formula 3] 0 ≦ S / T ≦ 0.6 III 10. A continuous polymerization apparatus comprising two or more reaction vessels is used, and in the presence of a rubbery polymer by a continuous bulk and / or solution polymerization method, relative to 100 parts by weight of all monomers.
Styrene and monomer 25-97 parts by weight 3 to 45 parts by weight acrylonitrile monomer, or a styrene monomer, acrylonitrile monomer and these monomers can be copolymerized with unsaturated Te Polymerizing 0 to 30 parts by weight of compound monomers (all of these monomers are simply monomers), the styrene-acrylonitrile copolymer is a continuous phase, and the rubber-like polymer particles are dispersed. In the method for producing a rubber-modified styrenic resin as a polymerization raw material, which comprises the above-mentioned rubber-like polymer, a monomer, and an inert organic solvent optionally added to form a phase, (1) 1) a first step of supplying a polymerization raw material and polymerizing the monomer in a state where the rubber-like polymer is not substantially transferred to the dispersed phase; and a second polymerization raw material after the second step, wherein the monomer is used as the second polymerization raw material. And an inert organic solvent to add the unit amount. The second step of continuously polymerizing the body to transfer the rubber-like polymer to the dispersed phase, and (2) the ratio of the rubber-like polymer to the polymerization liquid in the first step is X% by weight, the second step When the ratio of the rubber-like polymer to the polymerization liquid in
(Equation 4) is satisfied and [Equation 4] 0.3 ≦ Y / X ≦ 0.9 IV (3) The ratio of the inert organic solvent to the polymerization liquid in the first step is S% by weight, and in the second step When the ratio of the inert organic solvent to the polymerization liquid is T% by weight, the following formula V
The method for continuously producing a rubber-modified styrenic resin according to claim 1, wherein (Equation 5) is satisfied. [Formula 5] 0 ≦ S / T ≦ 0.6 V 11. The continuous rubber-modified styrenic resin according to claim 7, wherein the proportion Y of rubber-like polymer in the second step satisfies the following formula VI (equation 6). Manufacturing method. (6) 4 ≦ Y ≦ 20 VI 12. The ratio T of the inert organic solvent in the second step
The method for continuously producing a rubber-modified styrenic resin according to claim 8, 9 or 10, wherein the weight percentage satisfies the following formula VII (Equation 7). [Formula 7] 5 ≦ T ≦ 50 VII 13. The continuous production of a rubber-modified styrenic resin according to claim 1, 7, 8, 9 or 10, wherein a rubbery polymer having a viscosity of a 5 wt% styrene solution at 25 ° C. of 3 to 200 centipoise is used. Method. 14. The continuous production of a rubber-modified styrenic resin according to claim 1, 7, 8, 9 or 10, wherein a rubber-like polymer having a viscosity of a 5 wt% styrene solution at 25 ° C. of 3 to 100 centipoise is used. Method. 15. The continuous method for producing a rubber-modified styrenic resin according to claim 1, 7, 8, 9, or 10, wherein the continuous polymerization is carried out in the presence of a polymerization initiator. 16. In the first step, 0.0 is used as a polymerization initiator based on 100 parts by weight of the monomer.
01 to 2.0 parts by weight of organic peroxide is added, and 0 to 1.5 parts by weight of organic peroxide is added to 100 parts by weight of the monomer in the second step. Item 11. A continuous method for producing a rubber-modified styrenic resin according to item 1, 7, 8, 9, or 10.