JPH08239551A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE: To obtain an ABS-based polymer composition having low-temperature impact strength higher than that of a polymer prepared by emulsion polymerization, consequently capable of providing a thermoplastic resin having excellent moldability and processability without deteriorating polycarbonate. CONSTITUTION: This thermoplastic resin composition is obtained by blending (I) 100 pts.wt. of a thermoplastic polycarbonate with (II) 10-900 pts.wt. of an ABS-based polymer containing 8-23wt.% of an acrylonitrile component in a polymer component (A) from which a component insoluble in a mixed solvent of methyl ethyl ketone and methanol of 7:3 is removed, having 0.2-0.5dl/g reduced viscosity (ηsp/c) of the polymer component A and containing 5-30 pts.wt. of a rubber-like polymer component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition comprising an ABS polymer and a polycarbonate, which is excellent in heat resistance, impact resistance and moldability, and a method for producing the same. More specifically, the present invention relates to a thermoplastic resin composition that does not deteriorate the polycarbonate when mixed with an ABS polymer, further improves moldability, and further has improved impact strength at low temperatures.

[0002]

2. Description of the Related Art Conventionally, a mixture of an ABS polymer and a polycarbonate has been known as a resin composition having excellent heat resistance and impact resistance, and has been used as a molding material. In recent years, as these compositions have been widely used as materials for large-sized / thin-wall molding and high-speed injection molding, conventional compositions have low moldability because of low fluidity during molding.
Molding takes time. Alternatively, as the range of use of the molded product is expanded as the molded product becomes thinner, it is necessary to impart impact properties, especially at low temperatures.

For example, JP-A-62-240352, page 1, left column, line 12 to page 2, upper right column, line 20 improves the impact strength of a molded piece having cracks by reducing the aromatic strength of a rubber-like polymer. The content of the rubber-like polymer obtained by graft-copolymerizing two or more kinds of monomers selected from vinyl monomers, vinyl cyanide monomers and methacrylic acid alkyl ester monomers is 60% by weight or more. , The graft ratio to the rubber-like polymer is 50% or less, and the intrinsic viscosity of the non-grafted resin component is 0.
A method of mixing a graft copolymer of 6 dl / g or less with an aromatic polycarbonate is disclosed.

However, in the above-mentioned method, since the ABS polymer contains a large amount of rubber-like polymer, mechanical strength,
In particular, it is necessary to improve rigidity or heat resistance, and since the polymerization method is emulsion polymerization, auxiliary materials such as emulsifiers are required, wastewater treatment is also required, and the process is complicated and it is still an economical problem. There were some problems left to be solved. Further, the improvement of impact resistance at low temperature was not sufficiently improved.

In addition, from Japanese Patent Publication No. 62-39176, page 2, left column, line 39 to right column, line 42, polycarbonate is mixed with two kinds of ABS polymers having rubber particle diameter and grafting degree in different specific ranges. By doing so, a method of improving impact strength at low temperature is disclosed.

However, even in the above method, two kinds of graft polymers having different compositions are produced separately, and a copolymer obtained from another monomer mixture is produced and mixed with a polycarbonate, resulting in a complicated process. It is industrially disadvantageous. Further, the improvement of the impact resistance at low temperature has not been said to be sufficient.

JP-A-61-148258, page 1, right column 10,
In order to improve the balance of heat resistance / impact resistance and moldability, from line 2 to page 2, lower right column, line 15, two types of ABS polymers having different low rubber content and high rubber content, and A method is also disclosed in which an AS resin is mixed as necessary.

However, AB having a high rubber content and a high graft ratio
In order to produce the S-based polymer, the production method is naturally limited, and it is difficult to apply the bulk polymerization method in particular. Further, this method is also a complicated process because two or three kinds of ABS polymers, AS resins and the like are produced respectively and mixed with polycarbonate as in the above.

[0009]

In the present invention, when blending an ABS polymer and a polycarbonate, which have been difficult to improve by these conventional techniques, the polycarbonate does not deteriorate, and the moldability and the impact at low temperature are improved. A resin composition having improved strength is provided.

[0010]

In the present invention, ABS which contains a rubber-like polymer prepared by a solution polymerization method, which is grafted with styrene, acrylonitrile and other monomers, is completely different from the above conventional method. ABS polymer in which the reduced viscosity and the content of acrylonitrile component of the polymer component (A) excluding the 7: 3 mixed liquid insoluble component of methyl ethyl ketone and ethanol are adjusted to specific ranges The present invention has been completed by finding out that the above problems can be solved by blending with polycarbonate and a product with improved impact strength can be obtained.

What the present inventors have found is, in particular, the reduced viscosity of the polymer component (A) obtained by removing the insoluble component of the mixture of methyl ethyl ketone and methanol 7: 3 from the ABS polymer mixed with the polycarbonate. . A suitable range for the reduced viscosity of the ABS polymer mixed with the polycarbonate is 0.2 to 0.55 dl / g, which is lower than that of the case where the ABS polymer is used alone. ~ 0.45 dl / g is preferred. (Figs. 1, 2,
(3) The reduced viscosity is obtained by precisely weighing 0.25 g of the polymer component (A) and dissolving the solution in 50 ml of dimethylformamide for 2 hours to measure a solution using an Ubbelohde viscometer in an environment of 30 ° C. A viscometer having a solvent flowing time of 20 to 100 seconds is used. The reduced viscosity is determined by the following equation from the solvent flow-down seconds (t ₀ ) and the solution flow-down seconds (t). Reduced viscosity (ηsp / c) = {(t / t ₀ ) −1} /0.5 Further, the content of the acrylonitrile component in the polymer component (A) is also important, in the range of 8 to 23% by weight, With this, a thermoplastic resin having a good balance of physical properties can be obtained when mixed with polycarbonate.

That is, with respect to (I) 100 parts by weight of the thermoplastic polycarbonate, (II) at least a styrene monomer and an acrylonitrile monomer, and if necessary, another monomer copolymerizable with the above monomer. Polymer consisting of a polymer, and at least a styrene-based monomer and an acrylonitrile-based monomer, and if necessary, another monomer copolymerizable with the above-mentioned monomer is grafted and a copolymer of the above-mentioned monomer 8 to 23% by weight of the acrylonitrile component in the polymer component (A) obtained by removing the insoluble component of the mixed solution of methyl ethyl ketone and methanol 7: 3 from the ABS polymer containing the solution-polymerized rubbery polymer occluded And the reduced viscosity (ηsp / c) of the polymer component (A) is 0.2 to 0.55d.
1 / g, the above A containing 5 to 30 parts by weight of a rubbery polymer component
A thermoplastic resin composition obtained by mixing a BS polymer in a proportion of 10 to 900 parts by weight, wherein the ABS polymer (II) obtained by a solution polymerization or a bulk polymerization method is preferable. In addition, the rubber-like polymer used in the ABS polymer (II) is a polymer of a monomer containing at least butadiene, and the ratio of the resin component composed of the monomer bonded to the butadiene portion ( The graft ratio hereinafter) is particularly preferably in the range of 65 to 150%.

In the present invention, the acrylonitrile component in the ABS polymer (II) polymer component (A) has 8 to 23% by weight, preferably 10 to 18% by weight, more preferably 10 to 16% by weight. It is necessary to have When the content of the acrylonitrile component in the product is 23% by weight or more, the fluidity when blended with the polycarbonate decreases,
Affects formability cycle. On the other hand, if it is less than 8% by weight, impact strength is lowered, which is not preferable. Further, the reduced viscosity (ηsp / c) in the polymer component (A) is 0.2 to 0.
55 dl / g, preferably 0.3 to 0.45 dl / g,
More preferably, it should be 0.35 to 0.45 dl / g. When the reduced viscosity is less than 0.2 dl / g, the impact strength is significantly lowered, which is not preferable, and when it is more than 0.55 dl / g, the fluidity is lowered, the impact resistance is lowered, and the hue is also deteriorated, which is preferable. Absent.

That is, in the present invention, it has been found that the combination of polycarbonate and a specific ABS polymer improves impact strength to a degree that cannot be predicted at all, and that extremely high fluidity is obtained.

In the present invention, the reason why the fluidity and low temperature impact resistance are remarkably improved as compared with the conventional method is not clear. Conventionally, as the molecular weight of the resin generally decreases,
Although the fluidity is improved, it is a special property of the mixture of the polycarbonate and the ABS polymer that the impact strength is improved when the molecular weight represented by the reduced viscosity is reduced in the present invention. It is speculated that this is because a rubber-like polymer having an occlude structure is used. As described above, for example, the ABS polymer of the present invention alone is used as a normal AB
Although the impact strength is extremely low because the molecular weight is remarkably lower than that of the S resin, the physical properties of the polycarbonate and ABS polymer mixture are specifically improved by the combination of the present invention.

In the present invention, the compounding ratio of the thermoplastic polycarbonate (I) and the ABS polymer (II) is (I).
(II) is 10 to 900 parts by weight with respect to 100 parts by weight,
Preferably 50 to 600 parts by weight, more preferably 50
~ 350 parts by weight. When (II) is less than 10 parts by weight, impact strength has a large thickness dependency, and when it is more than 900 parts by weight, the inherent properties of polycarbonate are impaired. Further, in addition to (I) and (II), it is also included in the constitution of the present invention to mix other ABS polymers or other polymers, additives, and the like, if necessary. For example, as the other polymer, styrene-acrylonitrile resin, elastomer and the like are preferable.

It is particularly preferable that the ABS polymer (II) is produced by a solution polymerization method or a bulk polymerization method. In the solution polymerization or bulk polymerization method, the rubber-like polymer obtained by the solution polymerization method having a low glass transition point can be used, and an ABS polymer having improved low temperature impact can be obtained. Furthermore, since impurities such as an emulsifier do not remain in the product, the polycarbonate does not deteriorate when mixed with the polycarbonate, and the heat resistance and impact resistance are improved.

The solution polymerization or bulk polymerization method of the ABS polymer in the present invention may be a known method. For example, a rubber-like polymer may be added to a monomer and, if necessary, a solvent such as ethylbenzene, toluene or methylethylketone. The polymer is dissolved, and a monomer solution of the rubber-like polymer is continuously supplied to a stirring reactor with or without addition of a molecular weight regulator, a polymerization initiator, etc. A part or the whole amount is copolymerized to form rubber-like polymer particles. The obtained polymer mixed liquid is introduced into a devolatilization tank, and when unreacted monomers and a solvent are contained, the solvent is separated from the polymer component. After that, a granular resin component is obtained through a granulation step.

An example of preferable production conditions of the ABS polymer used in the present invention is as follows. The content ratio of the rubber-like polymer in the monomer solution of the rubber-like polymer supplied to the polymerization step is 5 to 1
3% and 25% of a 5 wt% styrene solution of a rubber-like polymer
Those having a viscosity at 5 ° C. of 5 to 25 cps are preferably used. The polymerization step preferably has a plurality of polymerization tanks,
Of these, the reduced viscosity of the polymer component (A) in the polymerization machine in which the rubber-like polymer undergoes a phase transition to dispersed particles is 0.4 to 0.55 d.
1 / g, control the polymerization conditions in the machine so that the acrylonitrile content is 10-18%, and proceed with the polymerization,
Perform until the polymer conversion of the monomer is 40 to 60%,
Supply to the devolatilization process. That is, it is controlled by specifying the reduced viscosity and the acrylonitrile content of the polymer component (A) and the conversion rate of the final monomer.

Conventionally, A produced in bulk or in solution
For the mixture of BS polymer and polycarbonate,
It is known that it has excellent fluidity and impact resistance,
The present invention is characterized in that it has a molecular weight, ηsp / c, which is completely different from that of the ABS polymer in the conventional range. For example, JP-A-59-187052 and JP-A-59-193950.
Then, the melt flow rate of the ABS resin is 1.5 to 2.8 in Examples and Comparative Examples, and ηsp / c of these ABS polymers corresponds to 0.6 to 0.7 dl / g. On the contrary, ηsp / c of the ABS polymer of the present invention
Is 0.2 to 0.55 dl / g, preferably 0.3 to
It is 0.45 dl / g, and by this, a much more excellent balance between low temperature impact strength and fluidity is exhibited.

In the present invention, A of ABS polymer (II)
The rubber-like polymer used in the BS polymer is a polymer of a monomer containing at least butadiene, and the graft ratio to the butadiene portion is preferably 65 to 150.
%, More preferably 75 to 130%, particularly preferably 80 to 120%. If it is less than 65%, the proportion of the resin component bonded to the rubber-like polymer is small, so that the rubber particles easily aggregate even after forming the rubber particles, and the impact strength decreases. Further, if it exceeds 150%, the fluidity is deteriorated when mixed with a polycarbonate resin, which is not preferable.

The graft ratio here is a value obtained by the following equation.

[0023]

## EQU1 ## G = 100 (P-B) / B G: Graft ratio (%) P: ABS polymer is immersed in a mixed solution of methyl ethyl ketone and methanol 7: 3 to dissolve soluble components, and then centrifuged. Weight (g) of insoluble matter separated. B: Weight of butadiene part in rubber-like polymer (g) The ABS polymer in the present invention includes the rubber-like polymer, styrene-based monomer, acrylonitrile-based monomer and, if necessary, other monomer. It is a resin composed of a copolymer of a polymer. Here, as the styrene-based monomer, styrene, α-alkylmonovinylidene aromatic monomer (for example, α-methylstyrene; α-ethylenestyrene; α-methylvinyltoluene; α-methyldialkylstyrene; etc.), ring-substituted Alkyl styrenes (eg om- and p-vinyltoluene;
o-ethyl styrene; p-ethyl styrene; 2,4-dimer styrene; p-tertiary butyl styrene; etc.), ring-substituted halostyrenes (eg o-chlorostyrene; p-chlorostyrene; o-promostyrene; 2,4 -Dichlorostyrene; etc.) ring-alkyl, ring halo-substituted styrene (e.g. 2-chloro-4-methylstyrene; 2,6-dichlorostyrene; etc.) vinylnaphthalene, vinylanthracene, or a mixture thereof.

The above substituted alkyl groups have 1 to 4 carbon atoms and include isopropyl and isobutyl groups. Of these, one or a mixture of monovinylidene aromatic monomers is preferably used.

Examples of acrylonitrile-based monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and mixtures thereof.

As the rubbery polymer, those obtained by solution polymerization are used, and preferably polybutadienes such as conjugated 1,3-dienes (eg butadiene; isoprene; etc.) and styrene-butadiene copolymers or Examples thereof include EPDM (ethylene-propylene-diene methylene linkage) and the like or a mixture thereof.

Particularly, it is preferable that the styrene-butadiene block copolymer (SB or SBS type) accounts for 50% by weight or more of the whole rubber-like polymer.

The content of the rubber-like polymer in the ABS polymer in the present invention is 5 to 30% by weight, preferably 10 to
It is preferably 25% by weight, more preferably 15 to 25% by weight. A large amount of a rubber-like polymer is not preferable because it has a low efficiency of improving the impact strength and rather lowers the fluidity after mixing with the polycarbonate. If it is 5% or less, the effect of the present invention cannot be obtained.

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

Examples of the polycarbonate in the present invention include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Generally, 2,2-bis (4-oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4
-Oxyphenyl) sulfone, bis (4-oxyphenyl) flufide or bis (4-oxyphenyl) sulfoxide-based polymers or copolymers of bisphenols, and halogen-substituted bisphenols depending on the purpose. Polymers using the class are also included. The above polycarbonate resins may be used alone or in combination of two or more.

The polymer component (A) of the ABS polymer (II) in the present invention is prepared by dissolving the ABS polymer (II) in a solvent and a mixed solution of methyl ethyl ketone and methanol 7: 3 (for 1 g of resin). 30 g of the solvent is added and the mixture is stirred at room temperature for 2 hours to dissolve it), and is separated into a soluble component and an insoluble component by centrifugation, and the soluble component of the supernatant is reprecipitated in methanol to obtain a polymer component (A).

The method for producing the composition of the present invention includes:
Examples thereof include a method of kneading (I), (II) or, if necessary, another resin with a known mixer such as an extruder.
Further, after (I) and (II) are blended as described above, they are usually used in a thermoplastic polymer composition for the purpose of imparting gloss, flame retardancy, mechanical strength, chemical resistance and other properties to the resin composition. It is also possible to add and use known polymers such as acrylonitrile / styrene copolymer, MBS, styrene / bradiene copolymer, and acrylic rubber-like polymer. Also,
As a merit of the composition of the present invention, in a conventional mixture of a polycarbonate / ABS polymer, there is a problem that a tar-like substance adheres to a mold at the time of molding processing, for example, at the time of injection molding. However, this tar-like adhered substance is greatly reduced, which is also a great effect of the present invention. Although the principle of this effect is not clear, the polymer component (A) of the ABS polymer of the present invention has a low molecular weight, and the use of a specific rubber-like polymer causes the generation amount of such tar-like substance. Is estimated to lead to the reduction of

The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

[0034]

The present invention will be described in more detail with reference to the following examples. The performance evaluation was measured according to the following criteria. (1) Measurement of Impact Strength The impact strength was measured by the Izod impact test method (ASTM D256) using a molded product as a test piece. (2) Measurement of heat resistant temperature Vicat softening point is based on ASTM D 1525,
It evaluated using the sample which cut out the test piece from the molded object. (3) Observation of substances attached to the mold Cylinder temperature of the molding machine is 260 ° C, mold temperature is 50 ° C, 2
After 50 shots, the deposit inside the gas outlet of the mold was visually observed, and if there was no deposit, it was judged as ◯, and if there was, it was judged as x.

Example 1 [a. Production of ABS Polymer] 63 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 20 parts by weight of ethylbenzene, rubber-like polymer (styrene-butadiene block copolymer solution viscosity 11 cst 5% styrene solution 25
C) 9.5 parts by weight, organic peroxide [1,1-bis (t-
0.07 part by weight of butylperoxy) 3,3,5-trimethylcyclohexane] and 0.15 part by weight of tert-lead decyl mercaptan were prepared. This raw material was polymerized in a 3-stage stirring type polymerization tank array reactor.
The raw material solution was continuously supplied from the first-stage tank. The reaction temperature in the first-stage tank was 100 ° C., 110 ° C. in the second-stage tank, and 125 ° C. in the third-stage tank. The polymerization liquid was introduced from the third tank to a separation and recovery process consisting of a preheater and a decompression chamber. The resin discharged from the recovery step was subjected to an extrusion step to obtain an ABS polymer as granular pellets. The polymer component (A) of the obtained ABS polymer had a reduced viscosity of 0.46 dl / g, an acrylonitrile compound content of 13%, and a graft ratio of 93.
%, And the rubbery polymer content was 21.3%. [B. Thermoplastic Polycarbonate] A commercially available polycarbonate polymer was used. The features are shown in the table below.

[0036]

[Table 1] * Measurement conditions: 230 ° C. 2.16 kg 100 parts by weight of polycarbonate, 100 parts by weight of the ABS polymer obtained in a, and 0.2 parts by weight of antioxidant were mixed at 260 ° C. by an extruder. Table 2 shows the results. In addition,
Prior to the extrusion operation, both the ABS polymer and the polycarbonate were dried at 100 ° C. for 12 hours.

Example 2 The same as Example 1 except that 100 parts by weight of polycarbonate and 67 parts by weight of the ABS polymer obtained in a were mixed. Table 2 shows the results.

Example 3 25 parts by weight of ethylbenzene, 10.2 parts by weight of rubber-like polymer (used in Example 1), organic peroxide (Example 1)
0.06 parts by weight, tert-lead decyl mercaptan 0.18 parts by weight, reaction temperature 1 in the first tank
Example 1 except that the temperature of the third stage was set to 130 ° C.
Same as The reduced viscosity of the polymer component (A) of the obtained ABS polymer was 0.38 dl / g, the acrylonitrile compound content was 13%, the graft ratio was 85%, and the rubbery polymer content was 23.0%. there were. The mixing of polycarbonate and ABS polymer was the same as in Example 1. Table 2 shows the results.

Example 4 The result of mixing 500 parts by weight of the ASBS resin obtained in Example 3 with 100 parts by weight of polycarbonate is shown in Table 2.
Shown in

Example 5 60 parts by weight of styrene, 10.5 parts by weight of acrylonitrile, and 0.075 of organic peroxide (used in Example 1).
Parts by weight, tertiary decyl mercaptan 0.17 parts by weight, reaction temperature 100 ° C. in the first tank. 110 ° C in the second tank. The same procedure as in Example 1 was performed except that the temperature in the third tank was 125 ° C. The polymer component (A) of the obtained ABS polymer had a reduced viscosity of 0.4 dl / g, an acrylonitrile compound content of 18%, a graft ratio of 103%, and a rubbery polymer content of 20.1%. there were. The mixing of polycarbonate and ABS polymer was the same as in Example 1. Table 2 shows the results.

Example 6 63.4 parts by weight of styrene, 8.6 parts by weight of acrylonitrile, 20 parts by weight of ethylbenzene, 8 parts by weight of rubber-like polymer (used in Example 1), organic peroxide (Example 1) 0.06 part by weight, tert-lead decyl mercaptan 0.25 part by weight, first stage reaction temperature 10
5 ° C, 110 ° C for the second tank, 125 ° C for the third tank
An ABS polymer was obtained at a temperature of ℃. The reduced viscosity of the polymer component (A) of the obtained ABS polymer is 0.25 dl / g,
The acrylonitrile compound content was 15%, the graft ratio was 118%, and the rubber-like polymer content was 18.5%. The mixing of polycarbonate and ABS polymer was the same as in Example 1. Table 2 shows the results.

Example 7 58.3 parts by weight of styrene, 13.7 parts by weight of acrylonitrile, 20 parts by weight of ethylbenzene, a rubber-like polymer (styrene-bradiene block copolymer, 5% styrene solution, solution viscosity at 25 ° C.) 30 cst) 8 parts by weight and the same as Example 1 except that 0.2 parts by weight of tertiary decyl mercaptan. The polymer component (A) of the obtained ASBS-based polymer had a reduced viscosity of 0.35 dl / g, an acrylonitrile compound content of 21%, and a graft ratio of 120.
%, And the rubbery polymer content was 17%. The mixing of polycarbonate and ABS polymer was the same as in Example 1.
The results are shown in Table 1.

Comparative Example 1 60 parts by weight of styrene, 20 parts by weight of acrylonitrile, 15 parts by weight of ethylbenzene, 9.5 parts by weight of rubbery polymer (used in Example 1), organic peroxide (used in Example 1) 0.05 part by weight, tertiary decyl mercaptan 0.08 part by weight, reaction temperature 105 in the first stage tank
℃, 120 ℃ in the second tank, 130 ℃ in the third tank
The same as Example 3 except that The reduced viscosity of the polymer component (A) of the obtained ABS polymer is 0.68 dl /
g, the acrylonitrile compound content was 24.7%, the graft ratio was 113%, and the rubbery polymer content was 18.3%. The mixing of polycarbonate and ABS polymer was the same as in Example 1. The results are shown in Table 3.

Comparative Example 2 45.8 parts by weight of styrene, 19.7 parts by weight of acrylonitrile, 15 parts by weight of ethylbenzene, 0.05 part by weight of organic peroxide (used in Example 1), tert-lead decyl mercaptan. 2 parts by weight, the reaction temperature of the first tank is 98 ° C, the second tank is 110 ° C, and the third tank is 12 ° C.
Same as Example 1 except that the temperature was 0 ° C. The obtained AB
The reduced viscosity of the polymer component (A) of the S-based polymer is 0.57d.
1 / g, acrylonitrile compound content is 27.8%,
Graft ratio is 128%, rubber-like polymer content is 16.7.
It was part by weight. The mixing of polycarbonate and ABS polymer was the same as in Example 1. The results are shown in Table 3.

Comparative Example 3 Emulsion graft polymerization was carried out at a ratio of 30 parts by weight of polybutadiene latex (solid content), 34.8 parts by weight of styrene and 5.2 parts by weight of acrylonitrile. The obtained graft copolymer latex was coagulated with dilute sulfuric acid, washed, filtered and dried. The reduced viscosity of the obtained copolymer was 0.49 dl /
g, the acrylonitrile polymer component in the polymer component (A) was 18%, and the graft ratio was 45%. The mixing of polycarbonate and ABS polymer was the same as in Example 1. The results are shown in Table 3.

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

The ABS polymer of the present invention has a high low temperature impact strength as compared with emulsion polymerization, and can provide a thermoplastic resin excellent in molding processability without degrading polycarbonate.

[Brief description of drawings]

FIG. 1 ABS with a rubber-like polymer content of 20% by weight
The polymer has a reduced viscosity of ABS polymer of 0.2 to 0.7d.
As I / g, the Izod impact strength was measured when the ABS polymer was used alone and when it was mixed with the polycarbonate (ABS / PC / = 50/50). When the ABS polymer alone is used, the higher the reduced viscosity of the resin is, the higher the Izod impact value (notched 6.4 mm) is, but the reduced viscosity when mixed with the polycarbonate is about 0.3 to 0.45 dl / g.
The od impact value is the highest. At the same time, a comparison with the case of using emulsion-polymerized ABS is also shown.

FIG. 2 shows an Izod impact value (notched 6.4 mm) with 100 parts by weight of polycarbonate and 10 to 900 parts by weight of an ABS polymer having a rubber polymer content of 18% by weight. . It shows a high Izod impact value at 0.45 dl / g as compared to the reduced viscosity of 0.6 dl / g of the ABS polymer mixed with the polycarbonate.

FIG. 3 is an AB having a reduced viscosity of 0.45 dl / g used in FIG.
The S polymer and the emulsion polymerized ABS polymer were mixed with polycarbonate, respectively, and the mixing ratio of the ABS polymer was 10-9.
The Izod impact value (notched 6.4 mm) at a low temperature (−250 ° C.) was measured as 100 parts by weight.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Masato Takahisa 1-6 Takasago, Takaishi, Osaka Prefecture Mitsui Toatsu Kagaku Co., Ltd. (72) Nao Morita 1-6, Takasago Takasashi, Osaka Mitsui Toatsu Kagaku (72) Inventor Koji Kawano 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Takao Kobayashi 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Chemical Co., Ltd.

Claims (7)

[Claims] 1. (I) Thermoplastic polycarbonate 100
With respect to parts by weight, (II) at least a styrene-based monomer and an acrylonitrile-based monomer, if necessary, a polymer composed of another monomer copolymerizable with the monomer, and at least a styrene-based monomer. Monomer and acrylonitrile monomer,
If necessary, another monomer that is copolymerizable with the above-mentioned monomer is grafted, and a solution-polymerized rubber-like polymer obtained by occluding the copolymer of the above-mentioned monomer is used as an essential component, and an ABS polymer is converted into methyl ethyl ketone. The acrylonitrile component in the polymer component (A) excluding the component insoluble in a mixed solution of 7: 3 methanol was 8 to 23% by weight, and the reduced viscosity (ηsp / c) of the polymer component (A) was 0. A thermoplastic resin composition obtained by mixing the ABS polymer containing 2 to 0.5 dl / g and the rubber polymer component in an amount of 5 to 30 parts by weight in an amount of 10 to 900 parts by weight. 2. The thermoplastic resin composition according to claim 1, wherein the ABS polymer (II) is produced by a solution polymerization method or a bulk polymerization method. 3. The rubber-like polymer used in the ABS polymer of (II) is a polymer of a monomer containing at least butadiene, and the graft ratio to the butadiene portion is 65.
The thermoplastic resin composition according to claim 1, which is ˜150%. 4. The thermoplastic resin composition according to claim 1, wherein the polymer component (A) (II) has a reduced viscosity (ηsp / c) of 0.3 to 0.45 dl / g. 5. The thermoplastic resin composition according to claim 1, wherein the acrylonitrile component in the polymer component (A) (II) is 10 to 18% by weight. 6. The thermoplastic resin composition according to claim 1, wherein the rubber polymer of the ABS polymer (II) contains 50% or more of a styrene-butadiene block copolymer. 7. The ABS polymer according to claim 1 for a thermoplastic polycarbonate blend.