JP3329156B2 - Aromatic polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polycarbonate resin composition comprising an aromatic polycarbonate and a rubber reinforced resin, and more particularly, to an excellent color tone and impact resistance and excellent stability during molding. And an aromatic polycarbonate resin composition.

[0002]

2. Description of the Related Art A resin composition comprising an aromatic polycarbonate and a rubber-reinforced resin, particularly an aromatic polycarbonate /
ABS alloy has been known for a long time (Japanese Patent Publication No. 38-1).
No. 5225), which is currently used for a wide range of applications. In recent years, the impact resistance of the composition has been required to be improved, and some studies have been made. As one of them,
Aromatic polycarbonate / ABS alloys using high molecular weight aromatic polycarbonates have been proposed. For example, in JP-A-2-129260, by using an aromatic polycarbonate having a weight average molecular weight of 35,000 or more as an aromatic polycarbonate, the impact resistance of a composition comprising an aromatic vinyl compound-based resin can be reduced. Improved compositions have been proposed.

However, since this composition uses a high molecular weight aromatic polycarbonate, it requires a higher temperature at the time of production as compared with the case where an aromatic polycarbonate having a normal molecular weight is used, and as a result, the color tone deteriorates. There was a problem. In addition, even during molding by the user, there is also a problem that coloring occurs due to molding conditions and residence in the molding machine, and low-temperature impact resistance and coating resistance fluctuate due to a decrease in the molecular weight of the aromatic polycarbonate. .

[0004] Many attempts have been made to improve the color tone and the molding stability of a resin composition comprising an aromatic polycarbonate and a rubber-reinforced resin, particularly an aromatic polycarbonate / ABS alloy. No improvement has been made on compositions using high molecular weight aromatic polycarbonates. For example, a method in which various antioxidants are added during extrusion or molding of the resin composition using a normal molecular weight aromatic polycarbonate to improve coloring due to thermal deterioration (Japanese Patent Application Laid-Open No. Sho 61-23640). However, the above-mentioned problem in the composition using a high molecular weight aromatic polycarbonate has not been solved.

On the other hand, from the side of the rubber reinforced resin, attempts have been made to solve the above problem of the resin composition comprising the aromatic polycarbonate and the rubber reinforced resin. In general, ABS resins and the like, which are representatives of rubber-reinforced resins, are used in the presence of a conjugated diene rubber latex such as polybutadiene, and a vinyl cyanide monomer such as acrylonitrile and an aromatic vinyl monomer such as styrene. Batch polymerization of the body,
In many cases, emulsion graft polymerization is performed by either semi-batch polymerization or continuous polymerization, followed by coagulation, dehydration, drying, and extrusion steps.

In this emulsion graft polymerization, an emulsifier comprising a non-polymerizable metal salt of a carboxylic acid, a metal sulfate or the like is generally used in the emulsion graft polymerization step in order to increase the stability of the latex and suppress the generation of coagulated products. The method of adding is taken. However, since the use of a non-polymerizable emulsifier causes foaming in the residual monomer recovery step, the use of a defoamer is inevitable, and when processing a composition with an aromatic polycarbonate, the residual emulsifier or It is known that the heat stability decreases due to the influence of an antifoaming agent. Therefore, a method has been proposed in which an emulsifier having a specific structure is used at the time of emulsion graft polymerization (JP-A-3-2204).
However, even with this method, the above problem could not be solved. As described above, the above problems have not been solved yet, and improvement has been strongly desired.

[0007]

SUMMARY OF THE INVENTION The present invention is directed to an aromatic polycarbonate comprising an aromatic polycarbonate and a rubber reinforced resin which is excellent in color tone and impact resistance and which is excellent in stability during molding. An object is to provide a resin composition.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of a resin composition comprising an aromatic polycarbonate and an ABS resin. Found that the above problem can be solved by combining an aromatic polycarbonate with a rubber reinforced resin composed of a graft polymer produced using a specific emulsifier having a double bond capable of radical polymerization in the molecule. The present invention has been reached.

That is, the present invention relates to (A) 2 to 98 parts by weight of an aromatic polycarbonate having a weight average molecular weight of 35,000 to 300,000 and (B) a rubbery polymer, which is copolymerized with the rubbery polymer. In the process of producing a graft polymer obtained by graft-polymerizing one or more kinds of possible vinyl compounds, at least one of the vinyl compounds graft-polymerized to the rubbery polymer has a radical polymerizable in its molecule. An aromatic polycarbonate-based resin composition comprising a graft polymer which is an emulsifier having a heavy bond, and 98 to 2 parts by weight of a rubber reinforced resin comprising a vinyl polymer is provided.

Hereinafter, the present invention will be described in detail.
The polycarbonate used in the present invention has a main chain composed of a repeating unit represented by the following formula 1.

[0011]

Embedded image (In the formula, Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene, pyridylene,
And those represented by Chemical Formula 2. )

[0012]

Embedded image (Wherein, Ar ¹ and Ar ² are each an arylene group. For example, phenylene, naphthylene, biphenylene,
Represents a group such as pyridylene, and Y is an alkylene group or a substituted alkylene group represented by Chemical Formulas 3 and 4. )

[0013]

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[0014]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, optionally substituted with a halogen atom or an alkoxy group). K may be 3 to 1
And a hydrogen atom represented by Chemical Formula 4 is a lower alkyl group,
It may be substituted with an aryl group, halogen, or the like. ) Further, a divalent aromatic residue represented by Chemical formula 5 may be contained as a copolymer component.

[0016]

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(Wherein, Ar ¹ and Ar ² are the same as in Chemical formula 2. Z
Is a mere bond, or -O-, -CO-, -S-,-
It is a divalent group such as SO ₂ —, —CO ₂ —, —CON (R ¹ ) —, (R ¹ is as defined above). Examples of these divalent aromatic residues include those represented by the following chemical formulas (6) and (7).

[0018]

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[0019]

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Wherein R ⁵ and R ⁶ are hydrogen, halogen, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₁₀ cycloalkyl group or a phenyl group, respectively. m and n are integers of 1 to 4; when m is 2 to 4, each R ⁵ may be the same or different; and when n is 2 to 4, each R ⁶ is the same. However, it may be different.) Among them, a compound represented by the following formula 8 is a preferable example. In particular, those containing 85 mol% or more of a repeating unit in which the above-mentioned chemical formula 8 is Ar are preferable.

[0021]

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The polycarbonate used in the present invention may contain a trivalent or higher aromatic residue as a copolymer component. Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a hydroxy group, an aryl carbonate group, and an alkyl carbonate group can be bonded. The aryl carbonate end group is
It is represented by the following chemical formula 9, and specific examples include chemical formula 10.

[0023]

Embedded image (In the formula, Ar ³ is a monovalent aromatic residue, and the aromatic ring may be substituted.)

[0024]

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The alkyl carbonate terminal group is represented by the following formula:
And specific examples thereof include, for example,

[0026]

Embedded image (Wherein, R ⁷ is a linear or branched alkyl group having 1 to 20 carbon atoms)

[0027]

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Among them, a phenyl carbonate group,
A pt-butylphenyl carbonate group, p-cumylphenyl carbonate and the like are preferably used. In addition, the ratio between the hydroxy group terminal and the other terminal is not particularly limited, and is used in the range of 1: 1000 to 1000: 1 depending on the use.

The aromatic polycarbonate used in the present invention has a molecular weight of 35,000 to 30 by weight average molecular weight.
It must be in the range of 0000. Preferably, it is in the range of 40,000 to 150,000, more preferably in the range of 45,000 to 100,000. When the weight average molecular weight is smaller than the above range, the impact resistance is not sufficiently improved, which is not preferable. From the above range,
If it is large, the fluidity of the composition is undesirably reduced.

In the present invention, the weight average molecular weight (Mw) is measured using GPC, and the measurement conditions are as follows. Using a tetrahydrofuran solvent and a polystyrene gel, it was determined from a constitutive curve of a standard monodisperse polystyrene using a reduced molecular weight calibration curve according to the following equation.

[0031]

(Equation 1) ( _MPC is the molecular weight of polycarbonate, _MPS is the molecular weight of polystyrene).

These polycarbonates can be produced by a known method. Specifically, a known method for reacting an aromatic dihydroxy compound with a carbonate precursor, for example, an interfacial polymerization method (phosgene method) in which an aromatic dihydroxy compound is reacted with phosgene in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. , An ester exchange method (melting method) of reacting an aromatic dihydroxy compound with diphenyl carbonate, and a method of solid-phase polymerization of a crystallized carbonate prepolymer (JP-A-1-158033, 1-2714)
26, 3-68627).

Next, the composition and production method of the rubber-reinforced thermoplastic resin (B) of the present invention will be described. Examples of the rubbery polymer used in the present invention include conjugated diene rubbers such as polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene rubber, ethyl acrylate, and acrylic. Acrylic rubbers such as butyl acid are preferred, but conjugated diene rubbers such as polybutadiene, butadiene-styrene copolymer and butadiene-acrylonitrile copolymer are preferred. These can be used in combination of two or more.

The content of the rubbery polymer in the rubber-reinforced thermoplastic resin composition is 5 to 60% by weight, preferably 10 to 5% by weight.
0% by weight. If it is less than 5% by weight, impact resistance cannot be obtained, and if it exceeds 60% by weight, the fluidity and gloss during molding are lowered, which is not preferable.

The preferred particle size of the rubbery polymer in the rubber-reinforced thermoplastic resin composition is not particularly limited because it differs depending on the type of the vinyl polymer used as the matrix. 600
nm, preferably 200-500 nm, more preferably 250-450 nm. If the particle diameter is smaller than 150 nm, impact resistance cannot be obtained, and if it exceeds 600 nm, the gloss value decreases.

Examples of the vinyl compound capable of being graft-polymerized to the rubber-like polymer particles used in the present invention include aromatic vinyl compounds such as styrene, main chain or side chain substituted styrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and acrylic compounds. Acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and the like, and methacrylates of similar substituents; acrylics such as acrylic acid and methacrylic acid; and maleimides such as N-phenylnaleimide and N-methylmaleimide Monomer,
A glycidyl group-containing monomer such as glycidyl methacrylate can also be used. These can be used in combination. Of these monomers, preferred are aromatic vinyl compounds and vinyl cyanide compounds. The vinyl polymer referred to here is not limited to amorphous or crystalline, but preferably includes at least one of the above-mentioned aromatic vinyl compound, vinyl cyanide compound, acrylate ester and methacrylate ester.
Includes types.

The method for producing the rubber-reinforced thermoplastic resin composition of the present invention is not particularly limited, but an emulsion graft polymerization method in which a vinyl compound is graft-polymerized to a rubbery polymer latex produced by emulsion polymerization, There is a solution polymerization method in which a polymer and a vinyl compound are dissolved in a solvent and graft polymerization is performed, and any of a continuous system, a batch system, and a semi-batch system is possible. In addition, a graft polymer having a high rubber content is prepared in advance by the above-described method, and later, bulk polymerization,
There is also a method in which a thermoplastic resin containing a vinyl compound as a main component used in graft polymerization produced by emulsion polymerization or suspension polymerization is blended to obtain a target rubber content. In the present invention, an emulsion grafting method in which a vinyl compound is continuously added to a rubber-like polymer produced by emulsion polymerization together with an initiator, a molecular weight regulator and the like is preferable.

The emulsifier having a double bond capable of radical polymerization in a molecule (hereinafter referred to as a polymerizable emulsifier) used in the present invention is a compound having a hydrophilic group and a hydrophobic group in a compound, Among the compounds capable of lowering the liquid-liquid or solid-liquid interfacial tension, the compound has at least one double bond in the compound, and has a conjugated diene rubber, an aromatic vinyl compound, a vinyl cyanide compound and / or ( A compound capable of undergoing radical polymerization with a (meth) acrylate compound. The hydrophilic group of the polymerizable emulsifier may be anionic, nonionic or cationic, but preferably has anionic properties, more preferably has both nonionic and anionic properties.

A non-polymerizable emulsifier may be used together with the polymerizable emulsifier during the emulsion graft polymerization, but the amount of the non-polymerizable emulsifier derived from the rubber is 4.0 parts by weight or less based on 100 parts by weight of the conjugated diene rubber. Should be. If the amount exceeds 4.0 parts by weight, the impact resistance of the rubber-reinforced thermoplastic resin composition, the rigidity, the gloss at the time of high-temperature molding, the contamination of the mold at the time of molding, and the coloring of the resin become unfavorable. . The non-polymerizable emulsifier referred to here may be an emulsifier generally used for emulsion polymerization, and may be a rosinate, a higher fatty acid salt,
Alkyl sulfates, alkyl benzene sulfonates, alkyl diphenyl ether disulfonates,
Polyoxyethylene alkyl phenyl ether sulfate,
Examples include anionic emulsifiers such as dialkyl sulfosuccinates, and nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers.

Examples of the polymerizable emulsifier used in the present invention include the following, but are not limited thereto. A polymerizable emulsifier represented by Chemical formula 13.

[0041]

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(Wherein X is a (meth) allyl group, (meth)
It represents an acryloyl group or a (1-propenyl) vinyl group. Y is hydrogen or —SO ³ M (M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or
Sulfate represented by ~ 4 hydroxyalkyl ammonium) or -CH ² COOM (M is hydrogen, a carboxylic represented by an alkali metal, alkaline earth metal, ammonium or hydroxyalkyl ammonium having from 1 to 4 carbon atoms), An acid salt or a phosphoric acid monoester salt represented by Chemical formula 14 is shown. R ¹ is an alkyl group, alkenyl group or aralkyl group having 1 to 18 carbon atoms, R ² is hydrogen or an alkyl group, alkenyl group or aralkyl group having 1 to 18 carbon atoms, R ³ is hydrogen or propenyl group, A is carbon number 2-4 alkylene groups or substituted alkylene groups,
n shows the integer of 1-200. )

[0043]

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Specific examples of the polymerizable emulsifier represented by Chemical formula 13 include Chemical formulas 15 and 16.

[0045]

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[0046]

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A (meth) allyl glycidyl ether derivative and a (meth) acryl glycidyl ester derivative represented by the formula:

[0048]

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(In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. Y represents hydrogen or —SO ₃
A sulfate ester salt represented by M (M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or —CH ₂
A carboxylic acid salt represented by COOM (M is hydrogen, an alkali metal, an alkaline earth metal), a phosphoric acid monoester represented by Chemical Formula 14, or a compound represented by Chemical Formula 18 is shown. Z represents an alkyl group having 8 to 30 carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkylaryl group, a substituted alkylaryl group, an aralkylaryl group, a substituted aralkylaryl group, an acyl group or a substituted acyl group. A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group; m represents an integer of 0 to 100; )

[0050]

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Examples of Chemical formula 17 include Chemical formulas 19 and 20.

[0052]

Embedded image (Wherein, Y ₁ represents Chemical Formula 21)

[0053]

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[0054]

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A succinic acid derivative represented by the following formula:

[0056]

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(In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. B ₁ and B ₂ represent Y or Z shown below, and B ₁ and B ₂ are different. .Y
Is, M or -SO ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkyl ammonium having from 1 to 4 carbon atoms). Z represents an alkyl group or an alkenyl group having 8 to 30 carbon atoms. A is an alkylene group having 2 to 4 carbon atoms or an alkylene group having a substituent, and m and n are integers of 0 to 50. As a specific example of Chemical formula 22, Chemical formula 23 is given.

[0058]

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A compound represented by the following formula:

[0060]

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(Wherein X represents (meth) allyl or (meth) acryloyl. Y is hydrogen or —SO ₃
A sulfate ester salt represented by M (M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or —CH ₂
A carboxylate represented by COOM (M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) is shown. R
₁ and R ₃ may be hydrogen or an alkyl group having 1 to 25 carbon atoms, which may be the same or different, and R ₂ and R ₄ may be an alkyl group having 1 to 25 carbon atoms, a benzyl group, or a styryl group. And p may be the same or different, and p represents an integer of 0 to 2. A is an alkylene group having 2 to 4 carbon atoms or an alkylene group having a substituent, and m and n
Represents an integer of 0 to 50. A specific example of Chemical Formula 24 is Chemical Formula 25.

[0062]

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A (meth) allyl ether derivative and a (meth) acrylic ester derivative represented by the following formula:

[0064]

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(Wherein, X represents a (meth) allyl group or a (meth) acryloyl group; Y is hydrogen or a methyl group, or —SO ₃ M (M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or sulfate represented by hydroxyalkyl ammonium) of 1 to 4 carbon atoms or -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or carbon atoms 1,
A hydroxyalkylammonium 4) or a phosphoric acid monoester salt represented by Chemical Formula 14. Z represents an alkyl group having 8 to 30 carbon atoms.
A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group; m represents an integer of 0 to 20; A specific example of Chemical Formula 26 is Chemical Formula 27.

[0066]

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A diol compound represented by the following formula:

[0068]

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Wherein A is an alkylene group having 2 to 4 carbon atoms, R ₁ is a hydrocarbon group having 8 to 24 carbon atoms,
₂ is hydrogen or a methyl group, m and n are each a number from 0 to 100 such that m + n is a value between 0 and 100, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or Hydroxyalkylammonium having 1 to 4 carbon atoms. As a specific example of Chemical formula 28, Chemical formula 29 is given.

[0070]

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A compound represented by the following formula:

[0072]

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(Wherein X is a (meth) allyl group, (meth)
Allyloxy group or (meth) acryloyl group, (meth)
An acryloyloxy group or Formula 31 is shown. Y is hydrogen,
Or -SO ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkyl ammonium having from 1 to 4 carbon atoms) sulfate represented by,
Or a carboxylate represented by —CH ₂ COOM (M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or a phosphoric acid monoester represented by the following formula: Or a sulfosuccinic acid monoester salt represented by Chemical Formula 18. Z represents an alkylene group which may have a substituent having 6 to 30 carbon atoms. A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group; n and m each represent an integer of 0 to 50; )

[0074]

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A specific example of Chemical Formula 30 is Chemical Formula 32.

[0076]

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Among these polymerizable emulsifiers, preferred are the polymerizable emulsifiers represented by Chemical Formulas 13, 17, 22, and 24, and particularly preferred are the polymerizable emulsifiers represented by Chemical Formula 13. Among the polymerizable emulsifiers represented by Chemical formula 17, a preferred structure is the polymerizable emulsifier represented by Chemical formula 19, and a more preferred specific example is Chemical formula 33.

[0078]

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The polymerizable emulsifier represented by Chemical formula 13 is particularly preferable, and specific examples thereof are particularly preferably Chemical formula 34 below.

[0080]

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The polymer latex obtained according to the present invention is usually coagulated with an inorganic salting-out agent and recovered by dehydration. The salting-out agent used is not limited, but specific examples include aluminum sulfate, magnesium sulfate, calcium chloride, sulfuric acid and the like. It is preferable that the amount of the component derived from the residual salting-out agent contained in the resin after the dehydration and recovery be smaller.

The aromatic polycarbonate resin composition of the present invention has a compounding ratio of 2 to 98 parts by weight of the aromatic polycarbonate (A) and 98 to 2 parts by weight of the rubber reinforced resin (B). Preferably, (a) is 5-95, (B) is 95
To 5 parts by weight, and more preferably (A) is 1 part by weight.
0 to 90 and (B) are in the range of 90 to 10 parts by weight. When the amount of the aromatic polycarbonate (A) is less than the above range, the improvement of the heat resistance of the rubber-reinforced resin is not sufficient. Is not sufficiently improved. Finally, the mixing ratio is determined according to the physical properties required for the composition.

The method for producing the resin composition of the present invention from the aromatic polycarbonate (A) and the rubber-reinforced resin (B) can be carried out by a conventionally known method, and is not particularly limited. For example, after uniformly mixing each component with a Henschel mixer, a super mixer, a turn bull mixer, a ribbon blender, and the like, melt-kneading with a single-screw extruder, a twin-screw extruder, a Banbury mixer, or the like, or a molten aromatic polycarbonate. Alternatively, there is a method of mixing a rubber-reinforced resin or an aromatic polycarbonate with a rubber-reinforced resin using a mixing tank, a static mixer, a single-screw extruder, a twin-screw or multi-screw extruder, or the like. At that time, the weight of heat stabilizers, antioxidants, weathering agents, ultraviolet absorbers, mold release agents, lubricants, antistatic agents, plasticizers, and other resins and rubbers is not impaired within the scope of the present invention. A coalescence, a pigment, a dye, a filler, a reinforcing agent, a flame retardant and the like may be added and used.

The aromatic polycarbonate resin composition of the present invention is generally suitable for applications where an aromatic polycarbonate resin composition comprising an aromatic polycarbonate and a rubber-reinforced resin, for example, an aromatic polycarbonate / ABS alloy is used. It is suitable for use in a wide range of applications, such as housing applications for notebook computers and mobile phones, as well as automotive applications and electrical and electronic applications. Among them, it is suitably used for applications requiring impact resistance, goodness, and color tone.

[0085]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples. The present invention is not limited by the embodiments. Parts used below are parts by weight. The evaluation of each item was measured by the following method.

(1) IZOD Impact Strength A pellet was molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C. to obtain a test piece. The test was performed on a 1/2 inch x 1/4 inch x 5/2 inch notched test piece based on ASTM-D256. (Unit kg · cm / cm) (2) Retentive IZOD Impact Strength The pellet was retained in a molding machine at 260 ° C. for 40 minutes, and then molded at a mold temperature of 65 ° C. to obtain a test piece. The test is A
Based on STM-D256, the test was performed on a test piece having a notch of １ ／ inch × １ ／ inch × 5/2 inch.

(3) Degree of Stay Color The pellets were molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C., and the initial coloring YI was measured. Subsequently, the sample was retained at 240 ° C. for 40 minutes in a molding machine, and molded in the same manner to obtain a test piece.
(ΔYI = YI of sample after staying−initial colored YI) was measured. Test piece: 216 mm long x 12.6 mm wide x 3.2 m thick
The measurement of mYI was performed using a SM color computer, model SM-5 manufactured by Suga Test Instruments Co., Ltd., and the measurement position was set at the center of the sample.

Reference Example 1 Production of Conjugated Diene Rubber Latex (S-1) A substance having the following composition (based on solid content) was charged into a 50-liter autoclave whose inside was evacuated to a vacuum, and heated at 65 ° C. Polymerization was performed. 1,3-butadiene 97.0 parts Acrylonitrile 3.0 parts t-dodecylmercaptan 0.2 parts Potassium rosinate 0.7 parts Tallow fossil fossil ken 0.3 parts Sodium persulfate 0.25 parts Sodium hydroxide 0.1 Part sodium hydrogen carbonate 0.35 part deionized water 60.0 parts

Between 10 hours and 20 hours after the start of the polymerization, the polymerization was continued while continuously adding a solution having the following composition to the autoclave. Potassium rosinate 0.3 part Tallow fossil fossil sapon 0.1 part Sodium persulfate 0.1 part Sodium hydroxide 0.05 part Sodium bicarbonate 0.15 part Deionized water 50.0 parts After continuous addition, polymerization system Was heated to 80 ° C., and cooled 26 hours after the start of the polymerization to terminate the polymerization. After the polymerization, unreacted butadiene was removed. The weight average particle diameter of the latex determined by electron micrograph was 0.28 microns.
The latex had a pH of 10.1.

(Reference Example 2) Production of conjugated diene rubber latex (S-2, S-3) The same procedure as in Reference Example 1 was carried out except as described in Table 1. The results are summarized in Table 1.

[0091]

[Table 1]

Reference Example 3 Production of Rubber Reinforced Resin (R1) 40 parts of conjugated diene rubber latex S-1 (solid content)
100 parts of ion-exchanged water and 0.3 part of potassium rosinate
After putting in a 0 liter reactor and replacing the gas phase with nitrogen, the initial solution was heated to 70 ° C. Next, an aqueous solution (C) having the following composition and a monomer mixture (E) were prepared.
The aqueous solution (D) containing the polymerizable emulsifier represented by the formula (1) was continuously added to the reactor over 5 hours. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction.

The composition of the aqueous solution (C) is as follows. Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Disodium ethylenediaminetetraacetate (EDTA) 0.04 part Ion exchange water 50 parts The composition of aqueous solution (D) is as follows is there. Polymerizable emulsifier Formula (37) 1.0 part Deionized water 20 parts The composition of the monomer mixture (E) is as follows. Acrylonitrile 24 parts Styrene 36 parts t-Dodecyl mercaptan (t-DM) 0.6 parts Cumene hydroperoxide (CHP) 0.1 parts.

Next, an antioxidant was added to the produced graft polymer latex, aluminum sulfate was added to coagulate, washed with water, dehydrated, and dried by heating to obtain a graft copolymer powder. 75 parts of the graft copolymer powder, 25 parts of an acrylonitrile / styrene copolymer, and 1.0 part of ethylenebisstearylamide were treated at a cylinder temperature of 24 parts.
The mixture was kneaded and granulated with a twin-screw extruder (ZSK-25, manufactured by W & P) set at 0 ° C. to obtain a rubber-reinforced resin having a rubber content of 30 parts.

Reference Example 4 Production of Rubber Reinforced Resin (R2) The same procedure as in Reference Example 3 was carried out except that the polymerizable emulsifier contained in the aqueous solution (D) in Reference Example 3 was changed as shown in Table 2. ,
A rubber reinforced resin was obtained.

Reference Example 5 Production of Rubber Reinforced Resin (R3) 40 parts (solid content) of conjugated diene rubber latex S-2 and 100 parts of ion-exchanged water were placed in a 10 liter reactor, and then carbon dioxide gas was added. Bubbled in the reactor and the pH was adjusted to about 7. After the gas phase was replaced with nitrogen, the initial solution was heated to 70 ° C. Next, an aqueous solution (C) having the following composition, a monomer mixture (E), and an aqueous solution (D) containing a polymerizable emulsifier represented by the formula (37) were continuously fed into a reactor for 5 hours. Was added. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction.

The composition of the aqueous solution (C) is as follows. Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Disodium ethylenediaminetetraacetate (EDTA) 0.04 part Ion exchange water 50 parts The composition of aqueous solution (D) is as follows is there. Polymerizable emulsifier Table 2 (1) 1.0 part Deionized water 20 parts.

The composition of the monomer mixture (E) is as follows. Acrylonitrile 24 parts Styrene 36 parts t-dodecyl mercaptan (t-DM) 1.0 part cumene hydroperoxide (CHP) 0.1 part This graft copolymer latex was treated in the same manner as R1, to obtain a rubber-reinforced resin. .

Reference Example 6 Production of Rubber Reinforced Resin (R4) 40 parts of conjugated diene rubber latex S-3 (solid content)
And the other conditions were described in Table 2 in the same manner as in Reference Example 3 to obtain a rubber-reinforced resin. This graft copolymer latex was treated in the same manner as in Reference Example 3 to obtain a rubber-reinforced resin.

(Reference Example 7) Production of rubber reinforced resin (R5) 40 parts of conjugated diene rubber latex S-1 (solid content)
100 parts of ion-exchanged water and 0.3 part of potassium rosinate
After putting in a 0 liter reactor and replacing the gas phase with nitrogen, the initial solution was heated to 70 ° C. Next, an aqueous solution (C), a monomer mixture (E), and an aqueous solution (D) each having the following composition were continuously added to the reactor over 5 hours. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction.

The composition of the aqueous solution (C) is as follows. Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Disodium ethylenediaminetetraacetate (EDTA) 0.04 part Ion exchange water 50 parts The composition of aqueous solution (D) is as follows is there. Potassium rosinate 2.0 parts Deionized water 20 parts

The composition of the monomer mixture (E) is as follows. Acrylonitrile 24 parts Styrene 36 parts t-dodecylmercaptan (t-DM) 0.6 parts cumene hydroperoxide (CHP) 0.1 parts This graft copolymer latex is treated in the same manner as in Reference Example 3 to obtain a rubber-reinforced resin. Was.

[0103]

[Table 2]

[0104]

Examples 1-4, Comparative Example 1 Polycarbonate (PC-1) having a weight average molecular weight of 55,000 as an aromatic polycarbonate (A) and R-R produced in Reference Example as a rubber-reinforced resin (B). 1 to R-5 were blended in the composition (parts by weight) shown in Table 3, and a twin-screw extruder (ZSK-25, W &
(Manufactured by P Company) to obtain pellets, and evaluated. Table 3 shows the evaluation results.

[0105]

Comparative Example 2 As an aromatic polycarbonate (A), polycarbonate having a weight average molecular weight of 31,000 (PC
-2) and R-1 produced in Reference Example as a rubber-reinforced resin (B) are blended in the composition (unit: parts by weight) shown in Table 3, and the twin-screw extrusion in which the cylinder temperature is set to 240 ° C. The mixture was kneaded and granulated by using a machine (ZSK-25, manufactured by W & P) to obtain pellets, which were evaluated. Table 3 shows the evaluation results.

[0106]

Examples 5 and 6 As the aromatic polycarbonate (A), the weight average molecular weight was 87,000 (PC-3) and 4
The procedure was performed in the same manner as in Example 1 except that 2,000 (PC-4) polycarbonate and R-1 produced in Reference Example were used as the rubber-reinforced resin (B). Table 3 shows the evaluation results.

[0107]

[Table 3]

[0108]

Industrial Applicability The polycarbonate resin composition of the present invention is excellent in color tone and impact resistance, and is excellent in stability at the time of molding, and is used for housings such as notebook computers and mobile phones, as well as for automobiles. Suitable for a wide range of application fields such as electrical and electronic applications. Among them, it can be suitably used for applications requiring impact resistance, goodness, and color tone.

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Claims (1)

(57) [Claims] (A) a weight average molecular weight of 35,000 to
2 to 98 parts by weight of 300,000 aromatic polycarbonate and (B) one or more vinyl compounds copolymerizable with the rubbery polymer to the rubbery polymer. In the production process, at least one of the vinyl compounds graft-polymerized to the rubber-like polymer is a graft polymer which is an emulsifier having a double bond capable of radical polymerization in a molecule, and a rubber comprising a vinyl polymer An aromatic polycarbonate resin composition comprising 98 to 2 parts by weight of a reinforced resin.