JPH09137053A - Antistatic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic resin composition, comprising a polycarbonate and a rubber-reinforced thermoplastic resin, having a persistent antistatic ability and excellent in thermal stability. SOLUTION: This antistatic resin composition comprises (A) 5-98 pts. by wt. polycarbonate, produced from an aromatic dihydroxy compound and a carbonic acid diester by a transesterification method and substantially without containing chlorine atom, (B) 95-2 pts. by wt. rubber-reinforced thermoplastic resin containing a graft copolymer prepared by carrying out the graft polymerization of one or more vinyl compounds copolymerization with a rubber-like polymer thereonto and a rubber-reinforced thermoplastic resin containing the vinyl polymer and (C) one or more selected from a polyether amide, a polyether ester, a polyether ester amide and a polyamide-imide elastomer in an amount of 0.5-30 pts. by wt. based on 100 pts. by wt. total amount of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic resin composition comprising polycarbonate and a rubber-reinforced thermoplastic resin, having a persistent antistatic property and excellent in thermal stability.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting an antistatic ability to a resin composition, a method of kneading a water-absorbing compound such as polyalkylene oxide or an antistatic agent into a thermoplastic resin, a surfactant or the like. Generally, a method of coating the surface of the molded product is performed. However, sufficient antistatic performance has not been realized by any of the methods.

Further, a resin composition comprising polycarbonate and a rubber-reinforced thermoplastic resin, particularly polycarbonate /
ABS alloy can improve the molding fluidity and thickness dependence of impact strength, which are the disadvantages of polycarbonate, and is currently used in a wide range of applications. In recent years, housing applications for laptop computers and mobile phones have increased. . However, since a resin composition composed of polycarbonate and a rubber-reinforced thermoplastic resin has a large coloring during molding, when it is used in a housing application where appearance is important, the color tone of the product varies and the product yield decreases. When performing continuous molding for a long period of time, there is a problem that the surface gloss of the product is reduced or the product dimension is changed because corrosion occurs in the degassing part of the mold.

In order to deal with this, many attempts have been made to improve the thermal stability of a resin composition comprising polycarbonate and a rubber-reinforced thermoplastic resin, particularly a polycarbonate / ABS alloy. For example, a method of adding various antioxidants at the time of extrusion or molding of the resin composition to improve coloration due to heat deterioration (JP-A-61-2).
No. 3640 gazette) has been proposed, but the above problems have not been solved.

Most of the solutions from the side of polycarbonate merely propose the improvement of the mechanical properties of the resin composition by copolymerization of the polycarbonate or the like, and the polycarbonate and the rubber-reinforced thermoplastic resin are combined with each other. At present, almost no attempts have been made to solve the above problems of the resin composition comprising Regarding the alloy of transesterified polycarbonate and rubber-reinforced resin, for example, in JP-A-5-239331, by mixing ABS with polycarbonate in a molten state after polymerization, thermal deterioration during melt mixing is prevented. Although a resin composition having excellent thermal stability has been proposed, the above problems have not always been solved.

On the other hand, from the rubber-reinforced thermoplastic resin side, attempts have been made to solve the above problems of a resin composition comprising a polycarbonate and a rubber-reinforced resin. In general, ABS resin, which is a typical rubber-reinforced resin, is used in the presence of a conjugated diene rubber latex typified by polybutadiene.
Emulsion graft polymerization of vinyl cyanide monomer represented by acrylonitrile and aromatic vinyl monomer represented by styrene by either batch polymerization, semi-batch polymerization or continuous polymerization, followed by coagulation, dehydration, drying and extrusion steps. It is often made through. In this emulsion graft polymerization,
In order to increase the stability of the latex and suppress the generation of coagulated substances, a method of adding an emulsifier composed of a non-polymerizable carboxylic acid metal salt, sulfate metal salt or the like is generally used in the emulsion graft polymerization step.

However, since the use of a non-polymerizable emulsifier causes foaming in the step of recovering the residual monomer, it is inevitable to use an antifoaming agent and, at the time of processing a composition with polycarbonate, residual emulsifier is used. It is known that the heat resistance stability is lowered due to the influence of the defoaming agent. Therefore, a method of using an emulsifier having a specific structure during emulsion graft polymerization (JP-A-3-2204) has been proposed. However, even this method could not solve the above problem. As described above, the above problems have not yet been solved, and there is a strong demand for improvement.

[0008]

In contrast to the present situation, the present invention is directed to an antistatic resin comprising a polycarbonate and a rubber-reinforced thermoplastic resin which are less likely to corrode in a mold or a molding machine and less colored during molding. It is intended to provide a composition.

[0009]

That is, the present invention provides:
(A) 5 to 98 parts by weight of a substantially chlorine-free polycarbonate produced by an ester exchange method from an aromatic dihydroxy compound and a carbonic acid diester, and (B) a rubber-like polymer, and the rubber-like polymer Graft polymer obtained by graft-polymerizing one or more vinyl compounds copolymerizable with and a rubber-reinforced thermoplastic resin containing a vinyl polymer 95-
2 parts by weight, and one or two or more selected from (C) polyether amide, polyether ester, polyether ester amide, and polyamide imide elastomer based on 100 parts by weight of (A) and (B) in total. .5-3
It relates to an antistatic resin composition consisting of 0 parts by weight.

Hereinafter, the present invention will be described in detail.
The polycarbonate (A) used in the present invention is a substantially chlorine-free polycarbonate produced by an ester exchange method 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 represents a divalent aromatic group).

The aromatic group Ar is preferably, for example, -A.
A divalent aromatic group represented by r ¹ -Y-Ar ^2- (wherein Ar ¹ and Ar ² are each independently a divalent carbocyclic or heterocyclic ring having 5 to 70 carbon atoms). Represents a formula aromatic group, and 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 adversely affect the reaction. Other substituents that do not affect, for example, halogen atom, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, phenyl group, phenoxy group, vinyl group, cyano group, ester group, amide group, nitro group It may be replaced by, for example.

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 general formula.

[0013]

Embedded image (In the formula, R ¹ , R ² , R ³ , and R ⁴ are each independently hydrogen,
Alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 5 to 10 ring carbon atoms, carbocyclic aromatic group having 5 to 10 ring carbon atoms, and 6 to 1 carbon atoms
Represents a carbocyclic aralkyl group of 0. k represents an integer of 3 to 11, R ⁵ and R ⁶ are individually selected for each X, and independently of each other represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and X represents carbon. In addition, R ¹ , R ² ,
^{R 3, R 4, R 5} , in R ^6, other substituents within the range in which one or more hydrogen atoms do not adversely affect the reaction, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, atoms 1
It may be substituted with an alkoxy group, 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 general formula.

[0014]

Embedded image (In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 ring-constituting carbon atoms, or A phenyl group, m and n are integers of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and when n is 2 to 4 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 general formula.

[0015]

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 one 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 general formula.

[0018]

Embedded image (Wherein, Ar ^3, Ar ⁴ represents a monovalent aromatic group, respectively.) Ar ³ and Ar ⁴ represent a monovalent carbocyclic or heterocyclic aromatic group, this Ar ^3, Ar ^{In 4} , one or more hydrogen atoms are other substituents that do not adversely affect the reaction,
For example, a halogen atom, an alkyl group having 1 to 10 carbon atoms,
It may be substituted by 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. A
r ³ and Ar ⁴ may be the same or different. Typical 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 types of the above-mentioned substituents. Preferred Ar ³ and Ar ⁴ include, for example, the following general formulas.

[0019]

Embedded image

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

[0021]

[Chemical 6] (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 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 ring carbon atoms, or phenyl Represents a group, p and q are integers of 1 to 5,
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 these 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 acid 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 usage ratio (charge ratio) of the aromatic dihydroxy compound and the carbonic acid diester is determined by the kind of the aromatic dihydroxy compound and the diaryl carbonate used, the polymerization temperature and other polymerization conditions, and the molecular weight and terminal ratio of the polycarbonate to be obtained. It differs depending on the type and 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 within a range not impairing the object of the present invention, or an aromatic monohydroxy compound for terminal conversion or molecular weight adjustment. You may use a compound together.

The molecular weight of the polycarbonate of the present invention is not particularly limited, but it is generally 1000 in terms of weight average molecular weight.
To 300000, preferably 5000 to 1
It is in the range of 00000, particularly preferably 12000 to
It is in the range of 80,000. Moreover, the terminal structure is not particularly limited.

The polycarbonate (A) of the present invention contains substantially no chlorine atom, and specifically, it can be measured by a potentiometric titration method using a silver nitrate solution or an ion chromatography method for measuring a chloride ion. Is 0.5p
It is pm or less, and at the same time, the chlorine atom is 10 ppm or less, which is the detection limit, in the method for measuring chlorine atom by the combustion method.
Preferably, the chlorine ion content is 0.1 ppm or less, which is less than the detection limit of the above measurement method, and at the same time, the chlorine atom content 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 method means polycondensation in the transesterification reaction in a molten state while heating the above compound in the presence or absence of a catalyst under reduced pressure and / or under an inert gas flow. It means a method, and there is no limitation on the polymerization method, apparatus, etc. 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,
A perforated plate type reactor that polymerizes while freely falling, a perforated plate type reactor with wire that polymerizes while falling along a wire, and the like can be easily manufactured by using these alone or in combination. Further, after the transesterification reaction is performed in a molten state to produce a prepolymer, the prepolymer can 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 50 to
It is selected in the temperature range of 350 ° C., preferably 100 to 300 ° C., and there is no particular limitation. 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 is
Depending on the molecular weight of the polycarbonate being melt-polymerized, the number average molecular weight is 50 m in the range of 1000 or less.
The range of mHg to normal pressure is generally used, and in the range of number average molecular weight of 1000 to 2000, 3 mmHg to 80 mm.
When the Hg range is a number average molecular weight of 2000 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, but it is carried out in the presence of a catalyst, if necessary, in order to increase the polymerization rate. 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;

Alkali metal and alkaline earth metal alkoxides such as lithium methoxide, sodium ethoxide and calcium methoxide; lithium phenoxide, sodium phenoxide, magnesium phenoxide, LiO-Ar-OLi, NaO-Ar-ONa (A
(where r is an aryl group) and the like, aryloxy compounds of alkali metals and alkaline earth metals; organic acid salts of alkali metals and alkaline earth metals such as lithium acetate, calcium acetate, sodium benzoate; zinc oxide, zinc acetate, zinc phenoxide, etc. Zinc compounds of 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 as described above) such as boron compounds;

Silicon compounds such as silicon oxide, sodium silicate, tetraalkyl silicon, tetraaryl silicon, diphenyl-ethyl-ethoxy silicon; germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide, germanium phenoxide. Compounds of tin such as tin oxide, dialkyltin oxide, dialkyltin carboxylate, tin acetate, a tin compound bonded to an alkoxy group such as ethyltin tributoxide or an aryloxy group, an organic tin compound;

Lead oxide, lead acetate, lead carbonate, basic carbonate,
Lead compounds such as lead and organic lead alkoxides or aryloxides; 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 acetate, zirconium oxide, zirconium alkoxide or aryloxide, zirconium acetylacetone and other zirconium compounds. Such catalysts can be mentioned.

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.

The composition and production method of the rubber-reinforced thermoplastic resin (B) of the present invention will be described. The rubber-reinforced thermoplastic resin can be obtained by graft-polymerizing a vinyl compound capable of being graft-polymerized with a rubber-like polymer, but a vinyl polymer which is simultaneously polymerized in this polymerization process may be contained. Further, the vinyl polymer may be simultaneously or separately polymerized and blended.

The rubber-like polymer used in the present invention includes:
Polybutadiene, polyisoprene, polychloroprene,
Conjugated diene rubbers such as butadiene-styrene copolymer and butadiene-acrylonitrile copolymer, ethylene-
Acrylic rubbers such as propylene rubber, ethyl acrylate, and butyl acrylate are preferable, and polybutadiene of a conjugated diene rubber, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer are preferable. These can be used in combination of two or more.

The content of the rubber-like polymer in the rubber-reinforced thermoplastic resin is 5 to 60% by weight, preferably 10 to 50% 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 varies depending on the type of vinyl polymer used as a matrix, but in the case of ABS resin, the particle size is 150-6.
00 nm, preferably 200 to 500 nm, more preferably 250 to 450 nm. Particle size is 150n
If it is less than m, impact resistance cannot be obtained, and if it exceeds 600 nm, the gloss value is lowered.

As the vinyl compound which can be graft-polymerized to the rubber-like polymer particles used in the present invention, aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate. Alkyl (meth) acrylates such as, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acids such as maleic anhydride, N Examples include maleimide-based monomers such as -phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide, and glycidyl group-containing compounds such as glycidyl methacrylate, but aromatic vinyl compounds and alkyl (meth) acrylates are preferable. ,cyan Vinyl compounds, a maleimide compound, more preferably, styrene, acrylonitrile, N- phenylmaleimide, butyl acrylate. These vinyl compounds may be used alone or in combination of two or more.

Vinyl polymers that can be contained in the rubber-reinforced thermoplastic resin (B) include aromatic vinyl compounds such as styrene, α-methylstyrene, paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate. (Meth) acrylic acid such as acrylic acid and methacrylic acid, vinyl cyanide compound such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acid such as maleic anhydride, N-phenyl Maleimide,
Examples thereof include maleimide compounds such as N-methylmaleimide and N-cyclohexylmaleimide, and glycidyl group-containing compounds such as glycidyl methacrylate, but preferably aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide compounds, Maleimide compounds, more preferably styrene, acrylonitrile,
It is a polymer composed of N-phenylmaleimide and butyl acrylate. These vinyl compounds may be used alone or in 2
It is possible to use a combination of two or more species or a copolymer.

The method for producing the rubber-reinforced thermoplastic resin in the present invention is not particularly limited, but an emulsion graft polymerization method in which a vinyl compound is graft-polymerized to a rubber-like polymer latex produced by emulsion polymerization, and an emulsion graft method. A two-stage polymerization method in which polymerization and solution polymerization or suspension polymerization are combined is exemplified. These can be any of a continuous type, a batch type, and a semi-batch type. Also, a graft polymer having a high rubber content is prepared in advance by the above method,
Later, a method of blending a thermoplastic resin containing a vinyl compound as a main component used at the time of graft polymerization produced by bulk polymerization, emulsion polymerization or suspension polymerization to obtain a desired rubber content is also used.

In the present invention, an emulsion graft system in which a vinyl compound is continuously added to a rubber-like polymer produced by emulsion polymerization together with an initiator, a molecular weight modifier and the like is preferable. The pH at the time of polymerization is not particularly limited, but is preferably around neutral (pH 7 to 9) from the viewpoint of the graft reaction.

The emulsifier having a double bond capable of radical polymerization in the molecule (hereinafter abbreviated as a polymerizable emulsifier) used in the present invention has a hydrophilic group and a hydrophobic group in the compound, and a gas-liquid, Of the compounds capable of lowering the liquid-liquid and solid-liquid interfacial tension, the compound has one or more double bonds, and in particular, a conjugated diene rubber, an aromatic vinyl compound, a vinyl cyanide compound and / or Alternatively, it means one capable of radical polymerization with a (meth) acrylic acid ester 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 emulsion graft polymerization, but the total amount of non-polymerizable emulsifiers derived from rubber is 4.0 parts by weight or less based on 100 parts by weight of conjugated diene rubber. Should be. If it exceeds 4.0 parts by weight, the impact resistance of the rubber-reinforced thermoplastic resin composition is lowered, the rigidity is lowered, the gloss is lowered during high temperature molding, the mold is contaminated during molding, and the resin is colored, which is not preferable. . The non-polymerizable emulsifier referred to here may be an emulsifier generally used for emulsion polymerization, a rosin acid salt, a higher fatty acid salt,
Alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate,
Polyoxyethylene alkyl phenyl ether sulfate,
Examples thereof include anionic emulsifiers such as dialkylsulfosuccinates and nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers.

Examples of the polymerizable emulsifier used in the present invention include, but are not limited to, the following. A polymerizable emulsifier represented by the following formula (1),

[0043]

Embedded image In the formula, R ₁ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aralkyl group, and R ₂ is hydrogen or 1 to 12 carbon atoms.
18 alkyl group, alkenyl group or aralkyl group, R ₃ is hydrogen or propenyl group, A is C 2-4
Alkylene group or substituted alkylene group, n is 1 to 20
Indicates an integer of 0. X represents a (meth) allyl group, a (meth) acryloyl group or a (1-propenyl) vinyl group.
Y is hydrogen, or -SO ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or carbon atoms 1
4 hydroxyalkylammonium) or a carboxylic acid represented by —CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) A salt or a phosphoric acid monoester salt represented by the following formula (1 ′) is shown.

[0044]

Embedded image

Specific examples of the polymerizable emulsifier represented by the formula (1) include the following formulas (5) to (8).

[0046]

Embedded image

[0047]

Embedded image

A (meth) allyl glycidyl ether derivative and a (meth) acryl glycidyl ester derivative represented by the following formula (2):

[0049]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. Y is hydrogen, or -SO ₃ M (M is hydrogen,
Alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) or a sulfate ester salt represented by -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal) A carboxylic acid salt, a phosphoric acid monoester represented by the formula (1 ′), or a compound represented by the formula (1 ″) is shown.
Z is an alkyl group having 8 to 30 carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkylaryl group,
It represents a substituted alkylaryl group, an aralkylaryl group, a substituted aralkylaryl group, an acyl group or a substituted acyl group. A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, m is 0 to 100, and n is an integer of 0 to 50.

[0050]

Embedded image

The following equations (9) to (15) are given as examples of equation (2).
An expression can be given.

[0052]

Embedded image (Y1 represents the following formula (11 ').)

[0053]

Embedded image

A succinic acid derivative represented by the following formula (3),

[0055]

Embedded image 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 from each other. Y is M or −
SO ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) is shown. Z represents an alkyl group or an alkenyl group having 8 to 30 carbon atoms. A has 2 to 4 carbon atoms
An alkylene group, which is an alkylene group having a substituent,
m and n are integers of 0 to 50.

As a specific example of the expression (3), the following expression (1
6) to (19).

[0057]

Embedded image

A compound represented by the following formula (4):

[0059]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. Y is hydrogen, or -SO ₃ M (M is hydrogen,
Sulfuric acid ester salt represented by alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms, or -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or carbon number) 1 to 4 hydroxyalkyl ammonium). R ₁ and R ₃ are hydrogen or an alkyl group having 1 to 25 carbon atoms and may be the same or different, and R ₂ and R ₄ are 1 to 2 carbon atoms.
5 represents an alkyl group, a benzyl group, or a styryl group, which may be the same or different, and p is 0 to
Indicates an integer of 2. A is an alkylene group having 2 to 4 carbon atoms and an alkylene group having a substituent, and m and n are integers of 0 to 50.

As a specific example of the equation (4), the following equation (2
0) and (21).

[0061]

Embedded image

A (meth) allyl ether derivative and a (meth) acrylic ester derivative represented by the following formula (22):

[0063]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. Y is hydrogen, a methyl group, or -SO
Sulfate ester salt represented by ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or -CH
₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or a phosphoric acid monoester salt represented by the formula (1 ′) Indicates. Z
Represents an alkyl group having 8 to 30 carbon atoms. A has 2 carbon atoms
~ 4 alkylene group or substituted alkylene group, m is 0
20 and n show the integer of 0-50.

As a concrete example of the equation (22), the following equation (2)
3) and (24).

[0065]

Embedded image

A diol compound represented by the following formula (25),

[0067]

Embedded image In the formula, A is an alkylene group having 2 to 4 carbon atoms, R ₁ is a hydrocarbon group having 8 to 24 carbon atoms, R ₂ is hydrogen or a methyl group, and m and n have m + n of 0 to 100. And M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms.

As a specific example of the equation (25), the following equation (2
6) can be given.

[0069]

Embedded image

A compound represented by the following formula (27),

[0071]

Embedded image In the formula, X represents a (meth) allyl group, a (meth) allyloxy group, a (meth) acryloyl group, a (meth) acryloyloxy group or the following formula (27 ′). Y is hydrogen, or (M hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkyl ammonium having from 1 to 4 carbon atoms) -SO ₃ M sulfuric acid ester salt represented by, or -CH ₂ COOM (M is A carboxylic acid salt represented by hydrogen, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms,
Alternatively, the phosphoric acid monoester represented by the formula (1 ′) or the sulfosuccinic acid monoester salt represented by the formula (1 ″) is shown. Z may have a substituent having 6 to 30 carbon atoms. Represents an alkylene group, A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n and m represent an integer of 0 to 50.

As a specific example of the equation (27), the following equation (2
8) to (30).

[0073]

Embedded image

Of these polymerizable emulsifiers, the polymerizable emulsifiers represented by the formulas (1), (2), (3) and (4) are preferable, and the formula (1) is particularly preferable. It is a polymerizable emulsifier represented. Among the polymerizable emulsifiers represented by the formula (2), preferred structures are the polymerizable emulsifiers represented by the formulas (9) and (11), and a more preferable specific example of the formula (9) is (31) Formulas (34) and (11) are more preferably specific examples of Formulas (35) and (36).

[0075]

Embedded image

The polymerizable emulsifier represented by the formula (1) is
Particularly preferred, and specific examples thereof include the following (37) to (41)
Formulas are particularly preferred.

[0077]

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The polymer latex obtained by the present invention is usually coagulated with an inorganic salting-out agent and 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 (B) polyether amide, polyether ester, polyether ester amide and polyamide imide elastomer in the present invention will be explained.
Examples of the polyether amide, polyether ester, and polyether ester amide include a block or graft copolymer obtained by the reaction of a polyamide component with a polyester component and a compound having an alkylene oxide group.

Examples of the polyamide component include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Or a lactam such as ε-caprolactam and enanthlactam, and a salt of diamine-dicarboxylic acid such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate. And mixtures thereof, preferably caprolactam, 12
-Aminododecanoic acid, hexamethylenediamine-adipate.

Examples of the polyester component include, as dicarboxylic acid, isophthalic acid, terephthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid and naphthalene-
Aromatic dicarboxylic acids such as 2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,
Alicyclic carboxylic acids such as 3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-dicarboxymethylcyclohexane,

Further, one or a mixture of two or more aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and decanedicarboxylic acid and an aliphatic diol such as ethylene glycol, 1,2-propylene glycol, One or a mixture of two or more of 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, neopentyl glycol, hexanediol and the like. The dicarboxylic acid is preferably
Terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sepacic acid, and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3 as decanedicarboxylic acid diol.
4-butanediol.

Examples of the compound having an alkylene oxide group include poly (ethylene oxide) glycol,
Poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, block or random copolymer of ethylene oxide and tetramethylene oxide, and block of ethylene oxide and tetrahydrofuran Alternatively, a random copolymer and a diamine or dicarboxylic acid thereof may be used, and one kind or two or more kinds may be used. Among these, poly (ethylene oxide) glycol is preferable.

Examples of the reaction of the polyether amide, polyether ester, and polyether ester amide elastomers include the reaction of a polyamide component or a polyester component with an alkylene oxide group-containing compound. Depending on the groups, ester or amide reactions are possible. Further, a third component such as dicarboxylic acid or diamine may be used depending on the reaction.

As the dicarboxylic acid component, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid,
Aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and decanedicarboxylic acid. Two or more types are used. Preferred are terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid and decanedicarboxylic acid.

As the polyamide-imide elastomer,
(A) caprolactam, (b) trivalent or tetravalent polycarboxylic acid, and (c) a mixture of polyoxyethylene glycol or polyoxyalkylene glycol mainly containing polyoxyethylene glycol, and
Polyamideimide that serves as a hard segment is obtained from the components (a) and (b), and these are linked with the glycol of the component (c) that is a soft segment by an ester bond to form a multi-block type copolymer.

As the component (b), a trivalent or tetravalent aromatic polycarboxylic acid which can react with an amino group to form at least one imide ring, or an acid anhydride thereof is used. Specific examples of the trivalent tricarboxylic acid used as the component (b) include 1,2,4-trimetic acid, 1,2,5-naphthalene tricarboxylic acid, 2,
6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′,
4-tricarboxylic acid, diphenyl sulfone-3,3 ',
4-tricarboxylic acid, diphenyl ether-3,3 ',
4-tricarboxylic acid etc. are mentioned.

As the tetravalent tetracarboxylic acid,
Specifically, pyromellitic acid, diphenyl-2,2 ',
3,3′-tetracarboxylic acid, benzophenone-2,
2 ', 3,3'-tetracarboxylic acid, diphenyl sulfone-2,2', 3,3'-tetracarboxylic acid, diphenyl ether-2,2 ', 3,3'-tetracarboxylic acid and the like can be mentioned. These polycarboxylic acids are substantially equimolar to the glycol component (c), ie 0.9
It is used in the range of up to 1.1 times mol.

The polyamide-imide which is the hard segment contributes to the heat resistance, strength and hardness of the elastomer and the compatibility with the thermoplastic resin for kneading the polyamide-imide elastomer, and the content of polyamide-imide in this elastomer is It is necessary to be 15 to 70% by weight. If this content is less than 15% by weight, the strength of the elastomer will be low, and when the polyamideimide elastomer is kneaded with the thermoplastic resin, the impact strength will be low, which is not preferable, and if it exceeds 70% by weight, the compatibility will be poor, It is not preferable because the antistatic effect may be lowered.

The number average molecular weight of the polyamide-imide is preferably 500 or more and 3000 or less,
It is more preferably 500 or more and 2000 or less. If the number average molecular weight of the polyamide-imide is less than 500, the melting point will be low and the heat resistance will be lowered, and if it exceeds 3000, the compatibility with the thermoplastic resin to be kneaded will be low, such being undesirable.

In order to improve the heat resistance, when (d) diamine is used together to introduce an imide ring into polyamideimide, the polycarboxylic acid is the total of the glycol component (c) and the diamine component (d). 0 to the number of moles.
It is used in 9 to 1.1 times the molar amount. Examples of the diamine of the component (d) include ethylene diamine, tetramethylene diamine, hexamethylene diamine, and phenylenediamine. This amount is 1 of glycol component (c)
It is preferable that the amount is not more than twice the molar amount, and if it is used in excess of this amount, it becomes difficult to obtain a homogeneous elastomer, and the compatibility with the thermoplastic resin to be kneaded decreases, which is not preferable.

(C) in the polyamide-imide elastomer
As the component, polyoxyethylene glycol or a mixture of polyoxyethylene glycol and polyoxyalkylene glycol other than polyoxyethylene glycol is used. The number average molecular weight of the polyoxyethylene glycol used is not particularly limited, but is 500 to 5
It is preferably in the range of 000. When it is less than 500, the melting point may be lowered and the heat resistance may be insufficient although it depends on the component of the elastomer, which is not preferable. On the other hand, when it exceeds 5,000, it becomes difficult to form a tough elastomer, and when kneaded with a thermoplastic resin, impact strength and rigidity may decrease, which is not preferable.

As the polyoxyalkylene glycol which can be used in combination with the polyoxyethylene glycol, polyoxytetramethylene glycol having a number average molecular weight of 500 to 5000, which is less than 50% by weight of the glycol component, modified polyoxytetramethylene glycol, Polyoxypropylene glycol or the like can be used.

Examples of the modified polyoxytetramethylene glycol include those obtained by substituting a part of — (CH ₂ ) ₄ —O— of ordinary polyoxytetramethylene glycol with —R—O—. Here, R is a C2-C10 alkylene group, for example, ethylene group, 1,2-propylene group, 1,3-propylene group, 2-methyl-1,3.
-Propylene group, 2,2-dimethyl-1,3-propylene group, pentamethylene group, hexamethylene group and the like. The amount of modification is not particularly limited, but usually 3 to
It is selected in the range of 50% by weight. Further, the amount of modification and the kind of the alkylene group are appropriately selected depending on the required properties of the one kneaded with the thermoplastic resin, such as low temperature impact resistance, antistatic property and heat resistance.

The modified polyoxytetramethylene glycol is produced, for example, by copolymerization of tetrahydrofuran and a diol using a heteropoly acid as a catalyst, copolymerization of a diol or a cyclic ether which is a condensate of the diol, and butanediol. be able to.

Regarding the method for producing the polyamide-imide elastomer, any method can be used as long as it can produce a homogeneous amide-imide elastomer, and for example, the following method is used. In a polymer produced by mixing the caprolactam component (a), the aromatic polycarboxylic acid component (b) and the glycol component (c) in a ratio such that the component (b) and the component (c) are substantially equimolar. While maintaining the water content of 0.1 to 1% by weight, the polymerization is carried out at 150 to 300 ° C, more preferably 180 to 280 ° C.
In the present method, the reaction temperature can be raised stepwise during the dehydration condensation.

At this time, some caprolactam remains unreacted, but this is distilled off under reduced pressure and removed from the reaction mixture.
The reaction mixture after removing the unreacted caprolactam can be further polymerized, if necessary, by post-polymerizing under reduced pressure at 200 to 300 ° C, more preferably at 230 to 280 ° C. In this reaction method, coarse phase separation is prevented by simultaneously performing esterification and amidation in the course of dehydration condensation, thereby producing a homogeneous and transparent elastomer. It is considered that this is one of the factors that exert excellent compatibility when the polyamide-imide elastomer is kneaded with the thermoplastic resin and bring about good antistatic properties, mechanical properties, surface gloss and the like.

In order to obtain an elastomer having transparency and homogeneity by simultaneously causing the esterification reaction and the polymerization of caprolactam and controlling the respective reaction rates, the produced water is removed from the system. Then, it is preferable to carry out the polymerization while maintaining the water content of the reaction system in the range of 0.1 to 1% by weight. If this water content exceeds 1% by weight, the polymerization of caprolactam takes precedence and coarse phase separation occurs,
On the other hand, if it is less than 0.1% by weight, the esterification has priority and the caprolactam does not react, and an elastomer having a desired composition cannot be obtained. The water content is appropriately selected within the above range according to the physical properties desired for the elastomer.

In this reaction, the water content in the reaction system may be gradually reduced as the reaction progresses, if desired. The water content can be controlled by, for example, controlling reaction conditions such as a reaction temperature, an inert gas introduction flow rate, and a degree of pressure reduction, or changing a reactor structure.

The degree of polymerization of the polyamide-imide elastomer can be arbitrarily changed as required, but the relative viscosity measured at 30% at 0.5% (weight / volume) in meta-cresol is 1.5 or more. Preferably.
If it is lower than 1.5, the mechanical properties cannot be sufficiently expressed, and the mechanical properties may be insufficient when kneaded with a thermoplastic resin. A preferable relative viscosity is 1.6 or more.

When the diamine (d) is used in combination, it can be carried out by either a one-step reaction method or a two-step reaction method. The former is a method in which caprolactam (a), polycarboxylic acid component (b), glycol component (c), and diamine component (d) are simultaneously charged and reacted. The latter is a method in which the polycarboxylic acid component (b) and the diamine component (d) are first reacted, and then the caprolactam (a) and the glycol component (c) are combined and reacted.

An esterification catalyst can be used as a polymerization accelerator when producing a polyamide-imide elastomer. Examples of this polymerization accelerator include phosphorus compounds such as phosphoric acid, polyphosphoric acid, and metaphosphoric acid; tetraalkyl orthotitanates such as tetrabutyl orthotitanate; tin-based catalysts such as dibutyltin laurate; manganese-based catalysts such as manganese acetate; Preferable are antimony-based catalysts such as antimony oxide; lead-based catalysts such as lead acetate. The catalyst may be added at the beginning of the polymerization or at the middle of the polymerization.

Further, in order to enhance the thermal stability of the obtained polyamide-imide elastomer, various kinds of stabilizers such as a heat resistant anti-aging agent and an antioxidant can be used, and these can be used in the early, middle and final stages of the polymerization. It may be added at any stage. Examples of the heat resistance stabilizer include N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxycinnamic acid amide) and 4,4'-bis (2,6-di-amide).
t-butylphenol), 2,2′-methylenebis (4
-Ethyl-6-t-butylphenol) and various hindered phenols; N, N'-bis (β-naphthyl)
-P-phenylenediamine, N, N'-diphenyl-p
-Aromatic amines such as phenylenediamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline);
Copper salts such as copper chloride and copper iodide; sulfur compounds such as dilauryl thiodipropionate and phosphorus compounds.

In the present invention, the antistatic performance is remarkably improved by using (C) the organic electrolyte or the inorganic electrolyte in combination with the resin of the present invention. As the organic electrolyte,
Examples thereof include organic compounds having an acidic group and metal salts thereof, organic ammonium salts, organic phosphonium salts and the like. Examples of the organic compound having an acidic group and the metal salt thereof include dodecylbenzenesulfonic acid, p-toluenesulfonic acid, dodecylphenyletherdisulfonic acid, naphthalenesulfonic acid, a condensation product of naphthalenesulfonic acid and formalin, polystyrenesulfonic acid and the like. Aromatic sulfonic acids, alkyl sulfonic acids such as lauryl sulfonic acid, organic carboxylic acids such as stearic acid, lauric acid, polyacrylic acid, etc., organic phosphoric acids such as diphenyl phosphite, diphenyl phosphate and their alkali metal salts, Examples thereof include alkaline earth metal salts.

Although the effect is exhibited even in the form of free acid, it is preferably used in the form of a salt of an alkali metal or an alkaline earth metal, for example, sodium, lithium, potassium, magnesium, calcium salt and the like are preferable. Examples of the organic ammonium salt include quaternary ammonium salts such as trimethyloctylammonium bromide, trimethyloctylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and trioctylmethylammonium bromide, and examples of the organic phosphonium salt include , Quaternary phosphonium salts such as amyltriphenylphosphonium bromide and tetrabutylphosphonium bromide.

The inorganic electrolyte is, for example, Ag.
NO ₃ , BeSO ₄ , CaCl ₂ , Ca (NO ₃ ) ₂ ,
CdCl ₂ , Cd (NO ₃ ) ₂ , CoCl ₂ , CrCl
₂ , CsCl, CuCl ₂ , Cu (NO ₃ ) ₂ , CuS
O ₄ , FeCl ₂ , KBr, KH ₂ PO ₄ , KSCN,
KNO ₃ , LiCl, LiOH, LiNO ₃ , MgCl
₂ , Mg (NO ₃ ) ₂ , MgSO ₄ , MnCl ₂ , Mn
SO ₄ , NH ₄ Cl, NH ₄ NO ₃ , (NH ₄ ) ₂ SO
₄ , NaBr, Na ₂ CO ₃ , NaH ₂ PO ₄ , NaN
O ₃ , NiSO ₄ , Pb (NO ₃ ) ₂ , PrCl ₃ , R
Examples thereof include bCl, RbNO ₃ , Zn (NO ₃ ) ₂ and ZnSO ₄ .

The ratio of the polycarbonate (A) to the rubber-reinforced thermoplastic resin (B) depends on the required mechanical strength, rigidity,
Determined according to moldability and heat resistance, (A) is 5-9
8 parts by weight and (B) must be in the range of 2 to 95 parts by weight. The component (A) is preferably 20 to 80 parts by weight, the component (B) is 20 to 80 parts by weight, and more preferably the component (A) is 25 to 75 parts by weight and the component (B) is 75 to 25. Parts by weight.

The blending amount of (C) polyether amide, polyether ester, polyether ester amide and polyamide imide elastomer is 0 based on 100 parts by weight of the total of (A) polycarbonate and (B) rubber reinforced thermoplastic resin. 0.5 to 30 parts by weight, preferably 3 to 2
0 parts by weight. If it is less than 0.5 part by weight, the antistatic property is insufficient, and if it exceeds 30 parts by weight, the resin becomes soft and the mechanical properties are poor.

The compounding amount of (D) organic electrolyte or inorganic electrolyte is 0.01 to 10 parts by weight, preferably 100 parts by weight of the total of (A) polycarbonate and (B) rubber-reinforced thermoplastic resin. It is 0.1 to 5 parts by weight. 0.
If the amount is less than 01 parts by weight, the antistatic effect is not sufficiently exhibited, and
If it exceeds the weight part, mechanical properties are deteriorated, die corrosion, mold deposit, etc. occur.

Further, with respect to the resin composition of the present invention, known antioxidants, ultraviolet absorbers, lubricants, release agents, flame retardants, colorants or glass fibers, glass flakes, carbon fibers, talc, mica, etc. It is optional to add the inorganic filler. Furthermore, the molding method of a molded article made of these thermoplastic resin compositions includes extrusion molding, compression molding, injection molding, gas assist molding, and the like, and is not particularly limited. Examples of molded products include housings for personal computers,
A keyboard etc. are mentioned.

[0111]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail based on the following examples. The present invention is not limited by the embodiments. The parts used below are parts by weight.

(Process for Producing Polycarbonate Resin) (PC-1) Bisphenol A which does not substantially contain a chlorine atom as an aromatic dihydroxy compound, and diphenyl carbonate which does not substantially contain a chlorine atom as a carbonic acid diester (to a molar ratio of bisphenol A). 1.10)
Polycarbonate was produced by a melt transesterification method using a disodium salt of bisphenol A (molar ratio to bisphenol A of 2.8 × 10 -8) as a catalyst. Manufacturing is
The reaction 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 polycarbonate contained substantially no chlorine atom, the hydroxy group terminal ratio was 72%, and the weight average molecular weight was 22,300. The polycarbonate resin produced by the (PC-2) phosgene method had a weight average molecular weight of 22,500.

(Manufacturing Method of Conjugated Diene Rubber): (Rubber Latex (S-1)) A substance (based on solid content) having the following composition was placed in a 50 liter autoclave whose inside was evacuated to a vacuum, and the temperature was raised to 65 ° C. Polymerization was carried out. 1,3-Butadiene 97.0 parts Acrylonitrile 3.0 parts t-dodecyl mercaptan 0.2 parts Potassium rosinate 0.7 parts Beef tallow saponified 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 part

During the 10th to 20th hours after the initiation of the polymerization, the polymerization was continued while continuously adding a solution having the following composition to the autoclave. Potassium rosinate 0.3 part Beef tallow fossil soap 0.1 part Sodium persulfate 0.1 part Sodium hydroxide 0.05 part Sodium hydrogen carbonate 0.15 part Deionized water 50.0 parts Polymerization system after continuous addition Was heated to 80 ° C. and cooled 26 hours after the start of polymerization to complete 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. The results are shown in Table 1.

The rubber-reinforced resins R-1 to R-3 were obtained by the following method. (R-1) 40 parts of rubber latex S-1 (solid content), 100 parts of deionized water, and 10 parts of 0.3 part of potassium rosinate
After being placed in a liter reactor and replacing the gas phase with nitrogen, the initial solution was heated to 70 ° C. Next, an aqueous solution (C) having the composition shown below and a monomer mixed solution (E), and further the formula (3)
The aqueous solution (D) containing the polymerizable emulsifier represented by 7) was continuously added to the reactor over 5 hours. After the addition is complete
The temperature was kept 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 Ethylenediaminetetraacetic acid disodium (EDTA) 0.04 part Ion-exchanged water 50 parts

The composition of the aqueous solution (D) is as follows. Polymerizable emulsifier Formula (37) 1.0 part Ion-exchanged water 20 parts The composition of the monomer mixture liquid (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, after adding an antioxidant to the graft polymer latex prepared, sulfuric acid was added. Aluminum was added to coagulate, washed with water, dehydrated, and dried by heating to obtain a graft copolymer powder (referred to as GRC).

(R-2) R-1 except that the polymerizable emulsifier contained in the aqueous solution (D) was changed to that shown in Table 2 for R-1.
-1 was polymerized in the same manner.

(R-3) 40 parts of rubber latex S-1 (solid content), 100 parts of ion-exchanged water, and 0.3 parts of potassium rosinate were placed in a 10-liter reactor, and the gas phase was replaced with nitrogen. The initial solution was heated to 70 ° C. Next, an aqueous solution (C) having the composition shown below, a monomer mixture solution (E), and an aqueous solution (D) 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 Ethylenediaminetetraacetic acid disodium (EDTA) 0.04 part Ion-exchanged water 50 parts

The composition of the aqueous solution (D) is as follows. Potassium rosinate 2.0 parts Ion-exchanged 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

(Vinyl Polymer (T-1)) Copolymer T-
The composition in 1 was 40% by weight acrylonitrile, 60% by weight styrene from the IR spectrum, and the intrinsic viscosity measured in methyl ethyl ketone (copolymer T-1, 0.61).
30% in 7% by weight) was 0.41. (Polyamideimide elastomer) Nissei Chemical Industry Co., Ltd.
Polyamideimide elastomer (sodium alkylbenzene sulfonate) manufactured by Tokyo Kasei Kogyo Co., Ltd. sodium dodecylbenzene sulfonate (hard type) (other additives) EBS is ethylenebisstearylamide.

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

【Example】

Examples 1 to 9 and Comparative Examples 1 to 6 The resins prepared as described above were blended with the compositions (units are parts by weight) listed in Tables 3 to 5 and the cylinder temperature was 240 ° C.
Twin screw extruder set to (ZSK-25, W & P)
Were kneaded and granulated in order to obtain pellets, and the following evaluations were performed.
The measuring method in the examples of the present invention is as follows. (Characteristics of Polycarbonate Resin) (1) Weight average molecular weight Gel permeation chromatography (GPC)
Was measured. Column: polystyrene gel, solvent: THF.

(Physical Property Evaluation Method) (2) IZOD Impact Strength Pellets were molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C. to obtain test pieces. The test was performed on a test piece with a notch of ½ inch × 1/4 inch × 5/2 inch based on ASTM-D256. (Unit is Kg · cm / c
m) (3) Retention IZOD impact strength The pellets were 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, a test piece having a notch of ½ inch × 1/4 inch × 5/2 inch was used.
(Unit is Kg · cm / cm)

(4) Residence Coloring Degree Pellets were molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C. to obtain reference test pieces. Subsequently, the test piece was obtained by allowing it to stay in the molding machine at 260 ° C. for 30 minutes and molding in the same manner. Test piece: length 216 mm x width 12.6 mm x thickness 3.2 m
m test was performed using Suga Test Instruments Co., Ltd. SM color computer, model SM-5, and the yellow index (YI of the sample before retention)-(YI of the sample after retention) of the test sample with respect to the reference test sample. (ΔYI) was measured. The sample was measured at the center. (5) Surface resistivity Using a flat plate with a thickness of 1/8 inch, room temperature 23 ° C, humidity 50%
It was measured in an RH atmosphere. For the measurement, a polar insulation meter SM-10E type manufactured by Toa Denpa Kogyo Co., Ltd. was used. (Unit: Ω / □) These results are summarized in Tables 3-4.

[0126]

[Table 3]

[0127]

[Table 4]

The following is clear from the examples and comparative examples. The antistatic resin compositions (Examples 1 to 9) of the rubber-reinforced thermoplastic resin using the graft copolymer and the polycarbonate resin synthesized by the transesterification method all have impact resistance (IZOD impact strength). ), Coloration during impact, impact strength, and decrease in molecular weight are suppressed, and mechanical strength and recyclability are excellent.

[0129]

INDUSTRIAL APPLICABILITY According to the present invention, the free residual emulsifier of the rubber-reinforced thermoplastic resin is extremely unlikely to diffuse into the polycarbonate resin blended, and the thermoplastic resin composition is unlikely to undergo thermal decomposition, and the polycarbonate is also thermally stable. It is highly likely. As a result, heat deterioration of the resin during kneading and molding is suppressed, and an antistatic resin composition having excellent mechanical strength and recyclability can be obtained.

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Claims (4)

[Claims] 1. To (A) 5 to 98 parts by weight of a substantially chlorine-free polycarbonate produced by an ester exchange method from an aromatic dihydroxy compound and a carbonic acid diester, and (B) a rubber-like polymer, A graft polymer obtained by graft-polymerizing one or more vinyl compounds copolymerizable with the rubber-like polymer, 95 to 2 parts by weight of a rubber-reinforced thermoplastic resin containing a vinyl polymer, and (A) ( One or two selected from (C) polyether amide, polyether ester, polyether ester amide and polyamide imide elastomer based on 100 parts by weight of B) in total.
An antistatic resin composition comprising at least 0.5 to 30 parts by weight. 2. At least one electrolyte selected from (D) an organic electrolyte or an inorganic electrolyte with respect to 100 parts by weight of a total of (A) polycarbonate and (B) rubber-reinforced thermoplastic resin. The antistatic resin composition according to claim 1, which comprises 10 parts by weight. 3. A process for producing a graft polymer, wherein the rubber-reinforced resin (B) is obtained by graft-polymerizing a rubber-like polymer with one or more vinyl compounds copolymerizable with the rubber-like polymer. A rubber-reinforced thermoplastic resin composed of a vinyl polymer and a graft polymer in which at least one of the vinyl compounds graft-polymerized to the rubber-like polymer is an emulsifier having a radical-polymerizable double bond in the molecule. The antistatic resin composition according to claim 1 or 2, which is a resin. 4. The antistatic resin composition according to claim 1, wherein (B) is a polyamideimide elastomer.