JP3329157B2 - 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 a polycarbonate resin composition comprising a polycarbonate and a rubber-reinforced resin, and more particularly, to a polycarbonate resin having less corrosion of a mold and a molding machine and less coloring at the time of molding. Composition.

[0002]

2. Description of the Related Art A resin composition comprising a polycarbonate and a rubber-reinforced resin, particularly a polycarbonate / ABS alloy, can improve the molding fluidity and the thickness dependency of impact strength, which are disadvantages of the polycarbonate, and are therefore widely used at present. In recent years, housing applications for notebook computers, mobile phones, and the like have been increasing. However, a resin composition comprising polycarbonate and a rubber-reinforced resin is
When used in housing applications where the appearance is important, the color tone of the product fluctuates and the product yield decreases. Since corrosion occurs in the degassing portion, there has been a problem that the surface gloss of the product is reduced and the product dimensions are changed.

[0003] Therefore, many attempts have been made to improve the thermal stability of a resin composition comprising a polycarbonate and a rubber-reinforced resin, particularly a polycarbonate / ABS alloy. For example, a method has been proposed in which various antioxidants are added during extrusion or molding of the resin composition to improve coloring due to thermal degradation (Japanese Patent Laid-Open No. 61-23640, etc.). There was no solution.

[0004] Further, from the polycarbonate side, most of them only propose improvement of mechanical properties of the resin composition by copolymerization of polycarbonate or the like. At present, few attempts have been made to solve the above problems. An alloy of a transesterification polycarbonate and a rubber-reinforced resin is described in, for example, Japanese Patent Application Laid-Open No. 5-239.
Japanese Patent No. 331 proposes a resin composition having excellent thermal stability by mixing ABS in a polycarbonate in a molten state after polymerization to prevent thermal degradation during melt mixing, but it is not necessarily the above problem. Could not be resolved.

[0005] 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 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. Emulsion graft polymerization of the polymer by batch polymerization, semi-batch polymerization, or continuous polymerization,
After that, they are often made through coagulation, dehydration, drying, and extrusion processes.

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, the use of a non-polymerizable emulsifier causes foaming in the residual monomer recovery step, so the use of an antifoaming agent is inevitable, and when processing a composition with polycarbonate, the residual emulsifier or defoaming agent is used. It is known that the heat stability is reduced by the influence of the 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 In accordance with the present invention, there is provided a polycarbonate resin composition comprising a polycarbonate and a rubber-reinforced resin, which is less corroded by a mold and a molding machine and has less coloring during molding. The purpose is to provide.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that a polycarbonate having a chlorine atom content of a specific amount or less and a radical polymerizable radically in a molecule can be obtained. The present inventors have found the surprising fact that the above problem can be solved by combining with a rubber reinforced resin composed of a graft polymer produced using a specific emulsifier having a heavy bond, and reached the present invention.

That is, the present invention relates to (A) 5 to 98 parts by weight of a substantially chlorine-free polycarbonate produced by transesterification of an aromatic dihydroxy compound and a carbonic acid diester, and (B) a rubbery weight. In the process of producing a graft polymer obtained by graft-polymerizing one or more vinyl compounds copolymerizable with the rubber-like polymer to the coalesced polymer, at least one of the vinyl compounds graft-polymerized to the rubber-like polymer is used. A polycarbonate resin composition comprising a graft polymer, one of which is an emulsifier having a double bond capable of undergoing radical polymerization in a molecule, and 95 to 2 parts by weight of a rubber reinforced resin comprising a vinyl polymer. It is.

Hereinafter, the present invention will be described in detail.
The polycarbonate (A) used in the present invention is a polycarbonate substantially containing no chlorine atom, which is produced by transesterification from an aromatic dihydroxy compound and a carbonic acid diester.

In the present invention, the aromatic dihydroxy compound is a compound represented by HO-Ar-OH (wherein Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene, pyridylene Or -Ar
¹ -Y-Ar ² - is a divalent aromatic group represented by. A
r ¹ and Ar ² each independently have 5 to 70 carbon atoms
Represents a divalent carbocyclic or heterocyclic aromatic group having
Y represents a divalent alkane group having 1 to 30 carbon atoms. )

In the divalent aromatic groups Ar ¹ and Ar ² ,
One or more hydrogen atoms having no adverse effect on the reaction, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group,
It may be substituted by a phenoxy group, vinyl group, cyano group, ester group, amide group, nitro group, or the like.

Preferred specific examples of the heterocyclic aromatic group include an aromatic group having one or more ring-forming nitrogen, oxygen or sulfur atoms. The divalent aromatic groups Ar ¹ and Ar ² represent groups such as substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, and substituted or unsubstituted pyridylene. The substituent here is as described above. The divalent alkane group Y is, for example, an organic group represented by the following formula 1.

[0014]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms,
10 alkoxy groups, a cycloalkyl group having 5 to 10 ring carbon atoms, a carbocyclic aromatic group having 5 to 10 ring carbon atoms,
Represents a carbocyclic aralkyl group having 6 to 10 carbon atoms. k is 3
And R ⁵ and R ⁶ are independently selected for each X and independently of one another, hydrogen or C 1
And X represents an alkyl group, and X represents carbon. Also,
In R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ , other substituents such as a halogen atom and an alkyl having 1 to 10 carbon atoms are used as long as one or more hydrogen atoms do not adversely affect the reaction. It may be substituted by a group, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group, or the like. Examples of such a divalent aromatic group Ar include those represented by the following formula (2).

[0016]

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(Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl having 5 to 10 ring carbon atoms) An alkyl group or a phenyl group, m and n
Is an integer of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and n is 2 to 4
In this case, each R ⁸ may be the same or different. ) Furthermore, the divalent aromatic group Ar is -Ar ¹ -Z-Ar ²
-May be indicated. (Wherein, Ar ¹ , A
r ² is defined above, Z is a single bond or -O -, - CO
-, - S -, - SO 2 -, - SO -, - COO -, - C
Represents a divalent group such as ON (R ¹ ) —. Here, R ₁ is as described above. Examples of such a divalent aromatic group Ar include those represented by the following formula (3).

[0018]

Embedded image (In the formula, R ⁷ , R ⁸ , m and n are as described above.)

The aromatic dihydroxy compound used in the present invention may be a single kind or two or more kinds. A typical example of the aromatic dihydroxy compound is bisphenol A. It is preferable that these aromatic dihydroxy compounds have a small content of a chlorine atom and an alkali or alkaline earth metal, and it is preferable that they are not substantially contained if possible. The carbonic acid diester used in the present invention is represented by the following chemical formula 4.

[0020]

Embedded image (In the formula, Ar ³ and Ar ⁴ each represent a monovalent aromatic group.)

Ar ³ and Ar ^{4 each} represent a monovalent carbocyclic or heterocyclic aromatic group. In Ar ³ and Ar ⁴ , one or more hydrogen atoms have no adverse effect on the reaction. Substituents, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group,
It may be substituted by an amide group, a nitro group or the like. Ar ³ and Ar ⁴ may be the same or different.

Representative examples of the monovalent aromatic groups Ar ³ and Ar ⁴ include a phenyl group, a naphthyl group, a biphenyl group and a pyridyl group. These may be substituted with one or more substituents described above. Preferred Ar ³
Examples of Ar ⁴ and Ar ⁴ include, for example,

[0023]

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Representative examples of the carbonic acid diester include substituted or unsubstituted diphenyl carbonates represented by the following formula (6).

[0025]

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(Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
An alkoxy group having 10; a cycloalkyl group having 5 to 10 ring carbon atoms; or a phenyl group;
When p is 2 or more, each R ⁹ may be different, and when q is 2 or more,
Each R ¹⁰ may be different. ).

Among the diphenyl carbonates,
Unsubstituted diphenyl carbonate, ditolyl carbonate, symmetric diaryl carbonates such as lower alkyl-substituted diphenyl carbonates such as di-t-butylphenyl carbonate are preferred, and diphenyl carbonate which is a diaryl carbonate having the simplest structure is particularly preferred. It is.

These carbonic diesters may be used alone or in combination of two or more. Further, it is preferable that these diaryl carbonates have a small content of a chlorine atom and an alkali or alkaline earth metal, and it is preferable that they are substantially not contained if possible.

The ratio of the aromatic dihydroxy compound to the carbonic acid diester (the charge ratio) depends on the types of the aromatic dihydroxy compound and the diaryl carbonate, the polymerization temperature and other polymerization conditions, and the molecular weight and terminal ratio of the polycarbonate to be obtained. It is not particularly limited. The diaryl carbonate is used in an amount of usually from 0.9 to 2.5 mol, preferably from 0.95 to 2.0 mol, more preferably from 0.98 to 1 mol, per 1 mol of the aromatic dihydroxy compound.
It is used in a proportion of 1.5 mol. Further, in the present invention, an aromatic polyhydroxy compound for introducing a branched structure may be used in combination, or an aromatic monohydroxy compound for terminal conversion or molecular weight control, as long as the object of the present invention is not impaired. Compounds may be used in combination.

Although the molecular weight of the polycarbonate of the present invention is not particularly limited, it is generally 1000 in weight average molecular weight.
~ 300000, preferably 5000 ~ 1
00000, particularly preferably 12000 to 12,000.
In the range of 80,000. Also, the terminal structure is not particularly limited.

The polycarbonate (A) of the present invention does not substantially contain chlorine atoms. Specifically, the chlorine ion is measured by a potentiometric titration method using a silver nitrate solution or a chloride ion measuring method by ion chromatography. Is 0.5p
pm or less, and at the same time, the chlorine atom is less than the detection limit of 10 ppm in a method for measuring chlorine atoms by a combustion method.
Preferably, the chlorine ion is 0.1 ppm or less, which is below the detection limit of the above measurement method, and at the same time, the chlorine atom is 1 ppm or less.
It is 0 ppm or less. If the chlorine atom is more than the above range, the molding machine material tends to corrode easily, and therefore iron ions are mixed into the resin composition of the present invention, and the coloring during melting tends to increase, which is not preferable.

In the present invention, the transesterification means that the above compound is polycondensed by transesterification in a molten state while heating under reduced pressure and / or under an inert gas flow in the presence or absence of a catalyst. This refers to a method, and there is no limitation on the polymerization method, apparatus, and the like. For example, a stirred tank reactor, a thin-film reactor, a centrifugal thin-film evaporation reactor, a surface-renewal twin-screw kneading reactor, a twin-screw horizontal stirring reactor, a wet-wall reactor,
It can be easily produced by using a perforated plate reactor which polymerizes while freely falling, a perforated plate reactor with a wire which polymerizes while being dropped along a wire, or the like, alone or in combination.

Alternatively, a prepolymer may be produced by performing a transesterification reaction in a molten state, and then may be produced by a solid phase polymerization method in which the degree of polymerization is increased in a solid state under reduced pressure or / and under an inert gas flow. The temperature of the transesterification reaction is usually 5
The temperature is selected within the range of 0 to 350 ° C, preferably 100 to 300 ° C, and is not particularly limited. In general, at a temperature higher than the above range, the obtained polycarbonate tends to be greatly colored and have poor thermal stability. If the temperature is lower than the above range, the polymerization reaction is slow and not practical. The reaction pressure also depends on the molecular weight of the polycarbonate during melt polymerization.
The range of 0 mmHg to normal pressure is generally used, and when the number average molecular weight is in the range of 1000 to 2000, 3 mmHg to 80 mm is used.
When the range of mmHg is in the range of a number average molecular weight of 2,000 or more, 10 mmHg or less, particularly 5 mmHg or less is used.

The polymerization by the transesterification method can be carried out without adding a catalyst. However, in order to increase the polymerization rate, the polymerization is carried out in the presence of a catalyst if necessary. The polymerization catalyst is not particularly limited as long as it is used in this field, and hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide are used. Alkali metal salts, alkaline earth metal salts, quaternary ammonium salts of hydrides of boron and aluminum such as lithium aluminum hydride, sodium borohydride, tetramethylammonium borohydride; lithium hydride, sodium hydride ,
Alkali metal and alkaline earth metal hydrides such as calcium hydride;

Alkoxides of alkali metals and alkaline earth metals such as lithium methoxide, sodium ethoxide and calcium methoxide; lithium phenoxide, sodium phenoxide, magnesium phenoxide, LiO-Ar-OLi, NaO-Ar-ONa (A
r is an aryl group) aryloxy such as alkali metal and alkaline earth metal; organic acid salts of alkali metal and alkaline earth metal such as lithium acetate, calcium acetate and sodium benzoate; zinc oxide, zinc acetate, zinc phenoxide and the like Zinc compounds; boron oxide, boric acid,
Sodium borate, trimethyl borate, tributyl borate, triphenyl borate, (R ₁ R ₂ R ₃ R ₄ ) NB
_{(R 1 R 2 R 3 R} 4) or _{(R 1 R 2 R 3 R} 4) PB
Ammonium borates represented by (R ₁ R ₂ R ₃ R ₄ ) or phosphonium borates (R ₁ , R ₂ ,
R ₃ and R ₄ are the same as those described in Chemical formula 3), and boron compounds;

Silicon compounds such as silicon oxide, sodium silicate, tetraalkylsilicon, tetraarylsilicon and diphenyl-ethyl-ethoxysilicon; germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide and germanium phenoxide Tin compounds such as tin compounds, organotin compounds, and tin compounds bonded to alkoxy or aryloxy groups such as tin oxide, dialkyltin oxide, dialkyltin carboxylate, tin acetate, ethyltin tributoxide;

Lead oxide, lead acetate, lead carbonate, basic carbonate,
Lead compounds such as alkoxides or aryloxides of lead and organolead; onium compounds such as quaternary ammonium salts, quaternary phosphonium salts and quaternary arsonium salts; antimony compounds such as antimony oxide and antimony acetate; acetic acid Manganese compounds such as manganese, manganese carbonate and manganese borate; titanium compounds such as titanium oxide, titanium alkoxide or aryloxide; zirconium compounds such as zirconium acetate, zirconium oxide, zirconium alkoxide or aryloxide, zirconium acetylacetone And the like.

When a catalyst is used, these catalysts may be used alone or in combination of two or more. The amount of these catalysts to be used is generally selected in the range of 10 ^-8 to 1% by weight, preferably 10 ^-7 to 10 ^-1 % by weight, based on the aromatic dihydroxy compound as the raw material.

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%.
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 rubber-like polymer in the rubber-reinforced thermoplastic resin composition is not particularly limited because it differs depending on the type of the vinyl polymer serving as the matrix.
50-600 nm, preferably 200-500 nm,
More preferably, it is 250 to 450 nm. If the particle diameter is smaller than 150 nm, impact resistance cannot be obtained.
If it exceeds 0 nm, the gloss value decreases.

Examples of the vinyl compound which can be 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 mentioned here is not limited to amorphous or crystalline, but preferably contains at least one kind of the above-mentioned aromatic vinyl compound, vinyl cyanide compound, acrylate or methacrylate. .

The method for producing the rubber-reinforced thermoplastic resin composition of the present invention is not particularly limited, but an emulsion graft polymerization system in which a vinyl compound is graft-polymerized to a rubber-like 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, but are not limited to, the following. A polymerizable emulsifier represented by Chemical formula 7.

[0047]

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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 8 is shown. R1 is an alkyl group having 1 to 18 carbon atoms;
An alkenyl group or an aralkyl group, R2 is hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aralkyl group, R3 is a hydrogen or propenyl group, A is an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms, and m is 1 Shows an integer of ~ 200. )

[0049]

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Specific examples of the polymerizable emulsifier represented by Chemical formula 7 include Chemical formulas 9 and 10.

[0051]

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[0052]

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

[0054]

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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 8, or a compound represented by Chemical formula 12 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; )

[0056]

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Examples of Chemical formula 11 include Chemical formulas 13 and 14.

[0058]

Embedded image (In the formula, Y represents Chemical formula 15.)

[0059]

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[0060]

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A succinic acid derivative represented by the following formula:

[0062]

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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. A specific example of Chemical Formula 16 is Chemical Formula 17.

[0064]

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A compound represented by the following formula:

[0066]

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(Wherein, X represents (meth) allyl or (meth) acryloyl. 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 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. As a specific example of the chemical formula 18,
Chemical formula 19 is given.

[0068]

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

[0070]

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(Wherein, X represents a (meth) allyl group or a (meth) acryloyl group; Y represents hydrogen or a methyl group, or —SO ₃ M (M represents 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 the formula (8). Z represents an alkyl group having 8 to 30 carbon atoms. A
Represents an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms, m represents an integer of 0 to 20, and n represents an integer of 0 to 50. A specific example of Chemical Formula 20 is Chemical Formula 21.

[0072]

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A diol compound represented by the following formula:

[0074]

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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. ) A specific example of Chemical Formula 22 is Chemical Formula 23.

[0076]

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A compound represented by the following formula:

[0078]

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(Wherein X is a (meth) allyl group, (meth)
Allyloxy group or (meth) acryloyl group, (meth)
And an acryloyloxy group or 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 -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkyl ammonium having from 1 to 4 carbon atoms) phosphoric acid monoester represented by the carboxylic acid salt or of 8, represented by, Alternatively, it represents a sulfosuccinic acid monoester salt represented by Chemical formula 12. 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; ).

[0080]

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A specific example of Chemical Formula 24 is Chemical Formula 26.

[0082]

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Among these polymerizable emulsifiers, preferred are the polymerizable emulsifiers represented by Chemical Formula 7, Chemical Formula 11, Chemical Formula 16, and Chemical Formula 18, and particularly preferred are the polymerizable emulsifiers represented by Chemical Formula 7. Among the polymerizable emulsifiers represented by Chemical formula 11, a preferred structure is the polymerizable emulsifier represented by Chemical formula 13, and a more preferable specific example is Chemical formula 27.

[0084]

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The polymerizable emulsifier represented by the formula (7) is particularly preferred, and specific examples thereof include the following.

[0086]

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The polymer latex obtained according to the present invention is usually coagulated with an inorganic salting-out agent and then dehydrated and recovered. 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 polycarbonate resin composition of the present invention comprises 2 to 98 parts by weight of the polycarbonate (A) and 98 to 2 parts by weight of the rubber reinforced resin (B). Preferably, (a) is in the range of 5 to 95, (B) is in the range of 95 to 5 parts by weight, more preferably (A) is in the range of 10 to 90,
(B) is in the range of 90 to 10 parts by weight. When the amount of the polycarbonate (A) is less than the above range, the heat resistance of the rubber-reinforced resin is not sufficiently improved, and when the amount is more than the above range, the improvement in the molding fluidity of the polycarbonate and the thickness dependence of the impact strength are obtained. Improvement is not enough. 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 polycarbonate (A) and the rubber-reinforced resin (B) can be performed by a conventionally known method, and is not particularly limited. For example, after uniformly mixing each component with a Henschel mixer, super mixer, turn bull mixer, ribbon blender, etc., melt-kneading with a single-screw extruder, twin-screw extruder, Banbury mixer, etc., or polycarbonate or rubber in a molten state There is a method of mixing a rubber-reinforced resin or polycarbonate with a 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 polycarbonate resin composition of the present invention is suitably used for applications in which a polycarbonate resin composition comprising a polycarbonate and a rubber-reinforced resin, for example, a polycarbonate / ABS alloy, is used. Suitable for a wide range of applications, such as housing applications for notebook PCs and mobile phones, where the appearance of molded products is important because of little corrosion of the machine and coloring during molding. Can be

[0091]

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) Evaluation of Corrosion of Die Using a die in which a metal test piece for corrosion evaluation was installed in the degassing portion, continuous molding of 70,000 shots was performed at a molding temperature of 260 ° C. and a die temperature of 65 ° C. did. The metal test piece was observed using a metal microscope, and the presence or absence of corrosion was confirmed. ：: Almost no corrosion was observed. ×: Corrosion is observed.

(2) Evaluation of coloring during molding process The pellets were molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C.
A test piece having a size of 16 mm x 12.6 mm in width x 3.2 mm in thickness was continuously molded, and the coloring (YI) during the continuous molding was evaluated. Thereafter, the sample was retained in a molding machine at 260 ° C. for 25 minutes, then molded in the same manner to obtain a test piece after the retention, and the increase in color from the color tone during continuous molding (ΔYI) was evaluated. Was. Note that Y
For the measurement of I, an SM color computer, model SM-5 manufactured by Suga Test Instruments Co., Ltd. was used.

Reference Example 1 Production of Polycarbonate (PC-1) Bisphenol A containing substantially no chlorine atom as an aromatic dihydroxy compound and diphenyl carbonate containing substantially no chlorine atom as a carbonic acid diester (vs. bisphenol A) (Molar ratio 1.10), and a polycarbonate was produced by a melt transesterification method using a disodium salt of bisphenol A (a molar ratio to bisphenol A 2.8.times.10@-8) as a catalyst. The production was carried out using a continuous polymerization apparatus comprising three stirred tank reactors and two perforated plate reactors with wires, while gradually increasing the temperature and the degree of pressure reduction. The maximum polymerization temperature was 250 ° C. The obtained aromatic polycarbonate contained substantially no chlorine atom, both the chlorine ion and the chlorine atom were below the detection limit, and the weight average molecular weight was 25,100.

Reference Example 2 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-dodecyl mercaptan 0.2 parts Potassium rosinate 0.7 parts Tallow fossil fossil ken 0.3 parts Sodium persulfate 0.25 parts Sodium hydroxide 0.1 Parts sodium hydrogen carbonate 0.35 parts 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 saponified fossil ken 0.1 part Sodium persulfate 0.1 part Sodium hydroxide 0.05 part Sodium hydrogen carbonate 0.15 part Deionized water 50.0 parts.

After the completion of the continuous addition, the 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 3 Production of Conjugated Diene Rubber Latex (S-2, S-3) The same procedure as in Reference Example 2 was carried out except as described in Table 1. The results are summarized in Table 1.

[0099]

[Table 1]

Reference Example 4 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 (1) in Table 2 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 for coagulation, 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 5 Production of Rubber Reinforced Resin (R2) The same procedure as in Reference Example 4 was carried out except that the polymerizable emulsifier contained in the aqueous solution (D) was changed to that shown in Table 2 in Reference Example 4. ,
A rubber reinforced resin was obtained.

Reference Example 6 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 7 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 4 to obtain a rubber-reinforced resin. This graft copolymer latex was treated in the same manner as in Reference Example 4 to obtain a rubber-reinforced resin.

(Reference Example 8) 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 4 to obtain a rubber-reinforced resin. Was.

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[Table 2]

[0110]

Examples 1 to 6, Comparative Examples 1 and 2 As the polycarbonate (A), the polycarbonate (P) produced in the reference example was used.
C-1) and commercially available phosgene method polycarbonate (PC
-2) and R-1 to R-5 produced in Reference Example as the rubber-reinforced resin (B) were blended with the compositions (units by weight) shown in Table 3, and the cylinder temperature was set to 240 ° C. The mixture was kneaded and granulated by a twin-screw extruder (ZSK-25, manufactured by W & P) to obtain pellets, which were evaluated. Table 3 shows the evaluation results.
Shown in The polycarbonate resin composition of the present invention is excellent in mold corrosiveness and coloring stability during molding.

[0111]

[Table 3]

[0112]

Industrial Applicability The polycarbonate resin composition of the present invention is excellent in mold corrosiveness and coloring stability at the time of molding, and is used for housings of notebook personal computers, cellular phones, etc. in which the appearance of molded articles is important. It can be suitably used in a wide range of application fields such as applications, automotive applications, electric and electronic applications.

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Claims (1)

(57) [Claims] 1. A rubber-like polymer comprising: (A) 2 to 98 parts by weight of a substantially chlorine-free polycarbonate produced from an aromatic dihydroxy compound and a carbonic acid diester by a transesterification method; In the process of producing a graft polymer obtained by graft-polymerizing one or more vinyl compounds copolymerizable with the rubber-like polymer, at least one of the vinyl compounds graft-polymerized to the rubber-like polymer is used. A polycarbonate-based resin composition comprising: a graft polymer which is an emulsifier having a double bond capable of radical polymerization in a molecule; and 98 to 2 parts by weight of a rubber-reinforced resin comprising a vinyl polymer.