JP3349859B2 - Thermoplastic resin composition and method for producing the same - Google Patents

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 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 which does not deteriorate 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 are widely used as materials for large-sized, thin-wall molding and high-speed injection molding, conventional compositions have low moldability due to low fluidity during molding.
It takes time for molding. Alternatively, as the range of use of the molded article is expanded as the molded article becomes thinner, it is necessary to impart impact resistance particularly at a low temperature.

For example, Japanese Patent Application Laid-Open No. 62-240352 describes a method of improving the impact strength of a cracked molded piece from page 12, left column, line 12 to page 2, upper right column, line 20 by adding an aromatic compound to the rubber-like polymer. The content of the rubbery polymer obtained by graft copolymerization of two or more monomers selected from vinyl monomers, vinyl cyanide monomers, and alkyl methacrylate monomers is 60% by weight or more. The graft ratio to the rubbery polymer is 50% or less, and the intrinsic viscosity of the non-grafted resin component is 0.1%.
A method of mixing a graft copolymer of 6 dl / g or less with an aromatic polycarbonate is disclosed.

However, in the above method, since the content of the rubbery polymer of the ABS polymer is large, the mechanical strength,
In particular, improvement is required in terms of rigidity or heat resistance. In addition, since the polymerization method is emulsion polymerization, auxiliary materials such as emulsifiers are required, and wastewater treatment is also required. There were problems to be solved. Furthermore, the improvement in impact properties at low temperatures was not sufficient.

[0005] In addition, JP-B-62-39176, page 2, left column, line 39 to right column, line 42, two types of ABS polymers having different rubber particle diameters and graft degrees in different specific ranges are mixed with polycarbonate. A method for improving the impact strength at low temperature by doing so is disclosed.

However, even in the above-mentioned method, two kinds of graft polymers having different compositions are separately produced, and a copolymer obtained from another monomer mixture is produced and mixed with polycarbonate, resulting in a complicated process. Industrially disadvantageous. Further, the improvement of the impact properties at low temperatures has not yet been sufficient.

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

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

[0009]

According to the present invention, when blending an ABS polymer and polycarbonate, which have been difficult to improve with these conventional techniques, the polycarbonate is not degraded, the moldability is improved, and the impact at low temperatures is reduced. The resin composition has improved strength.

[0010]

According to the present invention, ABS which contains a rubber-like polymer produced by a solution polymerization method in which styrene, acrylonitrile and other monomers are grafted is completely different from the above-mentioned conventional method. An ABS polymer in which the reduced viscosity of the polymer component (A) and the content of the acrylonitrile component were adjusted to a specific range, excluding the insoluble component of a 7: 3 mixture of methyl ethyl ketone and ethanol, was used. The present invention has been found to solve the above-mentioned problems and to obtain a product having further improved impact strength by being blended with polycarbonate.

In particular, the inventors have found the reduced viscosity of the polymer component (A) excluding the insoluble component of the mixture of methyl ethyl ketone and methanol 7: 3 from the ABS polymer mixed with the polycarbonate. . An appropriate range for the reduced viscosity of the ABS polymer to be mixed with the polycarbonate is generally lower than that when the ABS polymer is used alone, and is 0.2 to 0.55 dl / g, particularly 0.35 dl / g. ~ 0.45 dl / g is preferred. (FIGS. 1, 2,
The reduced viscosity is measured by precisely measuring 0.25 g of the polymer component (A) and dissolving it in 50 ml of dimethylformamide for 2 hours in a 30 ° C. environment using an Ubbelohde viscometer. Note that a viscometer having a solvent flow time of 20 to 100 seconds is used. The reduced viscosity is determined by the following equation from the number of seconds for the solvent to flow (t ₀ ) and the number of seconds for the solution to flow (t). Reduced viscosity (ηsp / c) = {(t / t ₀ ) −1} /0.5 The content of the acrylonitrile component in the polymer component (A) is also important, and is in the range of 8 to 23% by weight. By doing so, it is possible to obtain a thermoplastic resin having a good balance of physical properties when mixed with polycarbonate.

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

In the present invention, the ABS polymer (II) contains 8 to 23% by weight, preferably 10 to 18% by weight, more preferably 10 to 16% by weight of the acrylonitrile component in the polymer component (A). It is necessary to be. 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, the impact strength is undesirably reduced. Further, the reduced viscosity (ηsp / c) in the polymer component (A) is 0.2 to 0.1.
55 dl / g, preferably 0.3 to 0.45 dl / g,
More preferably, it should be 0.35 to 0.45 dl / g. If the reduced viscosity is less than 0.2 dl / g, the impact strength is remarkably reduced, which is not preferable. If the reduced viscosity is more than 0.55 dl / g, the fluidity is reduced, the impact resistance is reduced, and the hue is also poor. Absent.

That is, in the present invention, it has been found that in the combination of the polycarbonate and the specific ABS polymer, the impact strength is improved so as not to be predicted at all, and the performance with extremely high fluidity can be obtained.

In the present invention, it is not clear why the fluidity and low-temperature impact resistance are remarkably improved as compared with the conventional method. Conventionally, as the molecular weight of 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. This is presumed to be because a rubbery polymer having an occluded structure was used. As described above, for example, when the ABS polymer of the present invention is used alone, ordinary AB polymer is used.
Although the impact strength is extremely low because the molecular weight is significantly 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 mixing ratio of the thermoplastic polycarbonate (I) to 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
３５０350 parts by weight. If (II) is less than 10 parts by weight, the thickness dependency of impact strength becomes large, and if it is more than 900 parts by weight, the inherent properties of polycarbonate are impaired. Further, in addition to (I) and (II), mixing of other ABS-based polymers or other polymers, additives, or the like as necessary is also included in the configuration of the present invention. For example, as another polymer, a styrene-acrylonitrile resin, an elastomer or the like is preferable.

It is particularly preferred that the ABS polymer (II) is produced by solution polymerization or bulk polymerization. In the solution polymerization or bulk polymerization, a rubbery polymer obtained by a solution polymerization 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, there is no deterioration of the polycarbonate when mixed with the polycarbonate, and heat resistance and impact resistance are improved.

The solution polymerization or bulk polymerization 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, to a solvent such as ethylbenzene, toluene or methyl ethyl ketone. Dissolve the coalescing, with or without the addition of a molecular weight regulator, polymerization initiator, etc., and continuously supply a monomer solution of the rubbery polymer to a stirred reactor, Part or all are copolymerized to form rubbery polymer particles. The obtained polymer mixture is introduced into a devolatilization tank, and the solvent is separated from the polymer component when the solvent contains an unreacted monomer and a solvent. Thereafter, 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 of the rubbery polymer in the monomer solution of the rubbery polymer supplied to the polymerization step is 5 to 1%.
3% and 25% of a 5% by weight styrene solution of a rubbery 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 where the rubbery polymer undergoes phase transition to dispersed particles is 0.4 to 0.55 d.
1 / g, controlling the polymerization conditions in the apparatus so that the acrylonitrile content is 10 to 18%, and proceeding with the polymerization,
Performed until the polymer conversion of the monomer becomes 40 to 60%,
Feed to devolatilization process. That is, it is controlled by specifying the reduced viscosity and acrylonitrile content of the polymer component (A) and the conversion of the final monomer.

Conventionally, A produced in a lump or solution form
For the mixture of BS polymer and polycarbonate,
It is known that fluidity and impact resistance are excellent,
The present invention is characterized in that it has a completely different molecular weight, ηsp / c, from the ABS polymer in the conventional range. For example, JP-A-59-187052 and JP-A-59-193950
In Examples and Comparative Examples, the melt flow rate of the ABS resin is 1.5 to 2.8, and the ηsp / c of these ABS polymers corresponds to 0.6 to 0.7 dl / g. On the other hand, ηsp / c of the ABS polymer in the present invention
Is from 0.2 to 0.55 dl / g, preferably from 0.3 to 0.5 dl / g.
0.45 dl / g, thereby exhibiting a much more excellent balance between low-temperature impact strength and fluidity.

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

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

[0023]

## EQU1 ## G = 100 (P-B) / B G: Graft ratio (%) P: The ABS polymer is immersed in a mixed solution of methyl ethyl ketone and methanol 7: 3 to dissolve soluble components, and centrifuged. Weight (g) of separated insoluble matter. B: Weight (g) of butadiene part in rubber-like polymer The ABS-based polymer referred to in the present invention is composed of a rubber-like polymer, a styrene-based monomer, an acrylonitrile-based monomer and, if necessary, another monomer. It is a resin composed of a monomeric copolymer. Here, styrene-based monomers include styrene, α-alkylmonovinylidene aromatic monomers (for example, α-methylstyrene; α-ethylenestyrene; α-methylvinyltoluene; αmethyldialkylstyrene; etc.), ring substitution Alkylstyrenes (eg, om- and p-vinyltoluene;
o-ethylstyrene; p-ethylstyrene; 2,4-dimerstyrene; p-tert-butylstyrene; etc.), ring-substituted halostyrenes (eg, o-chlorostyrene; p-chlorostyrene; o-bromostyrene; 2,4) -Dichlorostyrene; etc.) One or a mixture of ring-alkyl, ring-halo-substituted styrenes (eg, 2-chloro-4-methylstyrene; 2,6-dichlorostyrene; etc.) vinylnaphthalene and vinylanthracene are used.

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

Examples of the acrylonitrile monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and mixtures thereof.

As the rubbery polymer, those obtained by solution polymerization are used. Preferably, polybutadienes such as conjugated 1,3-diene (for example, butadiene; isoprene; etc.), styrene-butadiene copolymer or EPDM (ethylene-propylene-diene methylene linkage) and the like or a mixture thereof are mentioned.

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

The content of the rubbery polymer in the ABS polymer in the present invention is 5 to 30% by weight, preferably 10 to 30% by weight.
It is preferably 25% by weight, more preferably 15 to 25% by weight. A large amount of the rubbery polymer is not preferable because the efficiency of improving the impact strength is low and the fluidity after mixing with the polycarbonate is rather lowered. In addition, the effect of the present invention is not obtained at 5% or less.

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

The polycarbonate in the present invention includes aromatic polycarbonate, aliphatic polycarbonate and aliphatic-aromatic polycarbonate. Generally, 2,2-bis (4-oxyphenyl) alkane, bis (4-oxyphenyl) ether, bis (4
Bisphenols such as -oxyphenyl) sulfone, bis (4-oxyphenyl) sulfide or bis (4-oxyphenyl) sulfoxide, or a copolymer thereof, and bisphenol substituted with halogen according to the purpose. And polymers using the same. The above polycarbonate resins can 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, a mixed solution of methyl ethyl ketone and methanol 7: 3 (per 1 g of resin). 30 g of a solvent and dissolved at room temperature with stirring for 2 hours), and separated into a soluble component and an insoluble component by centrifugation, and the soluble component in the supernatant is reprecipitated in methanol to obtain a polymer component (A).

The method for producing the composition of the present invention includes:
A method of kneading (I), (II) or, if necessary, another resin with a known mixer such as an extruder may be used.
After blending (I) and (II), the resin composition is 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. Known polymers such as acrylonitrile-styrene copolymer, MBS, styrene-bradiene copolymer, and acrylic rubbery polymer can be added for use. Also,
As a merit of the composition of the present invention, the conventional polycarbonate / ABS polymer mixture has a problem that, during molding, for example, a dent-like substance adheres to a mold at the time of injection molding. This greatly reduces the amount of the tan-like deposits, which is also a great effect of the present invention. Although the principle of this effect is not clear, the fact that 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 is required to reduce the amount of such tan-like substances generated. It is estimated that this will lead to a reduction in

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. However, the present invention is not limited by 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 according to the Izod impact test method (ASTM D256) by cutting a molded product into a test piece. (2) Measurement of heat resistance temperature Vicat softening point is based on ASTM D 1525,
Evaluation was performed using a sample obtained by cutting a test piece from a molded product. (3) Observation of the substance adhering to the mold The cylinder temperature of the molding machine was 260 ° C.
Deposits inside the gas vent of the mold after 50 shots were visually observed.

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, rubbery polymer (styrene-butadiene block copolymer solution viscosity 11 cst 5% styrene solution 25
9.5 parts by weight, organic peroxide [1,1-bis (t-
(Butyl peroxy) 3,3,5-trimethylcyclohexane] and 0.15 parts by weight of tertiary decyl mercaptan. This raw material was subjected to polymerization in a three-stage stirred polymerization tank array reactor.
The raw material solution was continuously supplied from the first tank. The reaction temperature in the first tank was 100 ° C., the temperature in the second tank was 110 ° C., and the reaction temperature in the third tank was 125 ° C. From the third tank, the polymerization liquid was led to a separation and recovery step comprising 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 reduced viscosity of the polymer component (A) of the obtained ABS polymer was 0.46 dl / g, the acrylonitrile compound content was 13%, and the graft ratio was 93.
%, And the rubbery polymer content was 21.3%. [B. Thermoplastic polycarbonate] A commercially available polycarbonate polymer was used. The following table shows the features.

[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 part by weight of an antioxidant were mixed at 260 ° C by an extruder. Table 2 shows the results. In addition,
Before the extrusion operation, both the ABS polymer and the polycarbonate were dried at 100 ° C. for 12 hours.

Example 2 The procedure of Example 1 was repeated except that 100 parts by weight of the 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 a rubbery polymer (used in Example 1), and an organic peroxide (Example 1)
0.06 parts by weight, 0.18 parts by weight of tertiary decyl mercaptan, reaction temperature of the first stage tank 1
Example 1 except that the temperature was set to 130 ° C in the third tank at 05 ° C.
And the same. 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 the polycarbonate and the ABS polymer was the same as in Example 1. Table 2 shows the results.

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

Example 5 60 parts by weight of styrene, 10.5 parts by weight of acrylonitrile, 0.075 of an organic peroxide (used in Example 1)
Parts by weight, 0.17 parts by weight of tertiary decyl mercaptan, and the reaction temperature of the first stage tank is 100 ° C. 110 ° C in the second tank. The third tank was the same as Example 1 except that the temperature was set to 125 ° C. The reduced viscosity of the polymer component (A) of the obtained ABS polymer was 0.4 dl / g, the acrylonitrile compound content was 18%, the graft ratio was 103%, and the rubbery polymer content was 20.1%. there were. The mixing of the polycarbonate and the 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 a rubbery polymer (used in Example 1), organic peroxide (Example 1) 0.06 parts by weight, 0.25 parts by weight of tertiary decyl mercaptan, reaction temperature of first-stage tank 10
5 ° C., 110 ° C. in the second tank, 125 ° C. in the third tank
By setting the temperature to ° C, an ABS polymer was obtained. 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 rubbery polymer content was 18.5%. The mixing of the polycarbonate and the 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, rubber-like polymer (styrene-bradiene block copolymer, 5% styrene solution, solution viscosity at 25 ° C.) 30 cst) Same as Example 1 except that 8 parts by weight and 0.2 parts by weight of tertiary decyl mercaptan were used. The reduced viscosity of the polymer component (A) of the obtained ASBS polymer is 0.35 dl / g, the acrylonitrile compound content is 21%, and the graft ratio is 120.
%, And the rubbery polymer content was 17%. The mixing of the polycarbonate and the ABS polymer was the same as in Example 1.
Table 1 shows the results.

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 a rubber-like polymer (used in Example 1), and an organic peroxide (used in Example 1) 0.05 parts by weight, 0.08 parts by weight of tertiary decyl mercaptan, reaction temperature of first tank 105
120 ° C in the second tank, 130 ° C in the third tank
It was the same as Example 3 except for the above. The reduced viscosity of the polymer component (A) of the obtained ABS polymer was 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 the polycarbonate and the ABS polymer was the same as in Example 1. Table 3 shows the results.

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), 0.1 part by weight of tertiary decyl mercaptan. 2 parts by weight, reaction temperature of 98 ° C. in the first tank, 110 ° C. in the second tank, 12 ° C. in the third tank
It was the same as Example 1 except that the temperature was set to 0 ° C. AB obtained
The reduced viscosity of the polymer component (A) of the S-based polymer is 0.57 d
1 / g, acrylonitrile compound content 27.8%,
The graft ratio is 128%, and the rubbery polymer content is 16.7.
Parts by weight. The mixing of the polycarbonate and the ABS polymer was the same as in Example 1. Table 3 shows the results.

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 latex of the graft copolymer 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 the polycarbonate and the ABS polymer was the same as in Example 1. Table 3 shows the results.

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

As described above, the ABS polymer of the present invention has a higher low-temperature impact strength than emulsion polymerization, and can provide a thermoplastic resin excellent in moldability without deteriorating polycarbonate.

[Brief description of the drawings]

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

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

FIG. 3 shows an AB having a reduced viscosity of 0.45 dl / g used in FIG.
The S polymer and the emulsion polymerized ABS polymer were each mixed with polycarbonate, and the mixing ratio of the ABS polymer was 10 to 9
The Izod impact value (6.4 mm with notch) at a low temperature (−250 ° C.) was measured as 00 parts by weight.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masato Takaku 1-6-6 Takasago, Takaishi City, Osaka Prefecture Inside Mitsui East Pressure Chemical Co., Ltd. Inside (72) Inventor Koji Kawano 1-6-6 Takasago, Takaishi-shi, Osaka Prefecture Inside Mitsui East Pressure Chemical Co., Ltd. (72) Inventor Takao 1-6-6 Takasago, Takaishi-shi, Osaka Prefecture Mitsui East Pressure Chemical Co., Ltd. ( 56) References JP-A-63-241015 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 55/02 C08F 2/02 C08F 2/06 C08F 279/04 C08L 69 / 00

Claims (6)

(57) [Claims] (I) Thermoplastic polycarbonate 100
(II) at least a styrene monomer and an acrylonitrile monomer, if necessary, a polymer comprising another monomer copolymerizable with the monomer, and at least a styrene monomer. Monomer and acrylonitrile monomer,
If necessary, a solution-polymerized rubbery polymer obtained by grafting another monomer copolymerizable with the monomer and occluding the copolymer of the monomer as an essential component , and a solution polymerization method or
Is an ABS polymer produced by a bulk polymerization method,
Methyl ethyl ketone and methanol 7 from BS polymer:
The acrylonitrile component in the polymer component (A) excluding the mixed solution insoluble component of No. 3 is 8 to 23% by weight, and the reduced viscosity (ηsp / c) of the polymer component (A) is 0.2 to 0 %. .
A thermoplastic resin composition comprising 55 dl / g and 5 to 30 parts by weight of a rubber-like polymer component and 10 to 900 parts by weight of the ABS polymer. 2. The rubbery polymer used in the ABS polymer (II) is a polymer of a monomer containing at least butadiene, and has a graft ratio of 65 to butadiene.
The thermoplastic resin composition according to claim 1, wherein the content of the thermoplastic resin is from about 150% to about 150%. 3. The thermoplastic resin composition according to claim 1, wherein the reduced viscosity (ηsp / c) of the polymer component (A) (II) is 0.3 to 0.45 dl / g. 4. The thermoplastic resin composition according to claim 1, wherein the acrylonitrile component in the polymer component (A) is 10 to 18% by weight. 5. The thermoplastic resin composition according to claim 1, wherein the rubbery polymer of the ABS polymer (II) contains 50% or more of a styrene-butadiene block copolymer. 6. The ABS polymer according to claim 1, which is for a thermoplastic polycarbonate blend.