JP4541078B2 - Aromatic polycarbonate resin composition, method for producing the resin composition, and molded article of the resin composition - Google Patents

Description

  The present invention relates to a novel aromatic polycarbonate resin composition. More specifically, the present invention relates to a conductive (antistatic) property, solvent resistance, fluidity containing an aromatic polycarbonate resin, a polyolefin-based resin, carbon nanotubes and a compatibilizer as necessary. The present invention relates to an aromatic polycarbonate resin composition having excellent properties, flame retardancy, impact resistance and molded appearance, a method for producing the resin composition, and a molded article of the resin composition.

In recent years, information processing apparatuses and electronic office equipment are rapidly spreading due to the development of electronics technology.
With the widespread use of electronic devices, troubles such as electromagnetic interference and malfunction due to static electricity that noise generated from electronic components affect peripheral devices are increasing, becoming a major problem.
In order to solve these problems, a material excellent in conductivity (antistatic) property and antistatic property is required.
Conventionally, a conductive polymer material in which a conductive filler or the like is blended with a low-conductivity polymer material has been widely used.
As the conductive filler, metal fiber, metal powder, carbon black, carbon fiber and the like are generally used. However, when the metal fiber and metal powder are used as the conductive filler, there is an excellent conductivity imparting effect, but the corrosion resistance. There is a disadvantage that the mechanical strength is difficult to obtain.
When carbon black is used as a conductive filler, conductive carbon black such as ketjen black, Vulcan XC72, and acetylene black, which can obtain high conductivity with a small amount of addition, is used. Is bad.
Since the dispersibility of carbon black affects the conductivity of the resin composition, a unique blending and mixing technique is required to obtain stable conductivity.

In addition, when carbon fiber is used as a conductive filler, desired strength and elastic modulus can be obtained with a general reinforcing carbon fiber. Physical properties are reduced.
Furthermore, when trying to obtain a molded product having a complicated shape, the conductive filler is displaced, which causes variations in conductivity, which is not satisfactory.
In the case of carbon fiber, when the same amount of fiber is added to the thinner fiber diameter, the contact area between the resin and the fiber is increased, so that it is expected to be excellent in providing conductivity.
An ultrafine carbon fibril having excellent conductivity is disclosed (for example, see Patent Document 1).
However, when mixed with a resin, the dispersibility into the resin is poor, the surface appearance of the molded product is impaired, and it is not satisfactory.
In addition, when the resin is colored, when a known carbon black for pigment is used as a colorant, it is necessary to use a large amount in order to develop black, and there are problems in terms of dispersibility in the resin and the surface appearance of the molded product. is there.
Although a method of adding ultrafine carbon fibrils is disclosed (for example, see Patent Document 2), the flame retardancy exerted by ultrafine carbon fibrils is not described at all.
In addition, the disclosed method has low flame retardancy and cannot be used for products that require high flame retardancy.
There is known a resin composition comprising a thermoplastic resin, carbon nanotubes, and one or more compounds selected from a phosphorus compound, a phenol compound, an epoxy compound, and a sulfur compound (see, for example, Patent Document 3). However, the examples are only polycarbonate resin / acrylonitrile-butadiene-styrene resin, and there is no example about the combination of polycarbonate resin / polyolefin resin.
In addition, when a large amount of carbon nanotubes are blended in order to develop conductive performance, appearance defects may be caused or impact strength may be lowered, and there is no description about improvement of solvent resistance.
Conventionally, a polycarbonate resin / polyolefin resin alloy has low compatibility and low impact strength, and the molded product has a poor appearance because it causes delamination, and a compatibilizer or the like is indispensable.

JP-T 62-500094 Japanese Patent Laid-Open No. 3-74465 JP 2004-182842 A

  In the present invention, the phase structure of the aromatic polycarbonate resin / polyolefin resin is stabilized, there is no delamination, and the conductive (antistatic) property, solvent resistance, fluidity, flame resistance, impact resistance, molded appearance, etc. An aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin, a polyolefin resin, a carbon nanotube and, if necessary, a compatibilizer, a method for producing the resin composition, and a molded article of the resin composition Is an issue.

  As a result of intensive studies on the above problems, the present inventors have blended a predetermined amount of carbon nanotubes and, if necessary, a compatibilizer into a mixture composed of a specific proportion of an aromatic polycarbonate resin and a polyolefin resin. The inventors have found that the phase structure of the aromatic polycarbonate resin / polyolefin resin is stabilized and the re-aggregation of the polyolefin resin at the time of melting and the domain orientation at the time of injection molding can be reduced, and the present invention has been completed.

That is, the present invention
1. (A) The content of amorphous carbon particles is 20% by mass or less with respect to 100 parts by mass of the resin component composed of 50 to 99% by mass of the aromatic polycarbonate resin and (B) 50 to 1% by mass of the polyolefin resin , An aromatic polycarbonate resin composition containing 0.1 to 30 parts by mass of carbon nanotubes having an outer diameter of 0.5 to 120 nm and a length of 500 nm or more and having an open end , and containing no compatibilizer ,
2. (A) The aromatic polycarbonate resin composition according to 1 above, wherein the component has a viscosity average molecular weight of 10,000 to 40,000,
3. The fragrance according to 1 or 2 above, wherein the component (B) is one or more compounds selected from polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer, and ethylene- (meth) acrylic acid copolymer ester. Group polycarbonate resin composition,
4. The aromatic polycarbonate resin composition according to any one of the above 1 to 3 , which is a composition for OA equipment, information / communication equipment, automobile parts, or home appliances,
5 . (B) after the component (C) were melt-kneaded, the 1-4 that this kneaded product was added the component (A), or components (A) and component (D), characterized by melt-kneading A method for producing an aromatic polycarbonate resin composition according to any one of
6 . The molded object obtained using the aromatic polycarbonate resin composition in any one of said 1-4 is provided.

In the aromatic polycarbonate resin composition of the present invention, the phase structure of the aromatic polycarbonate resin / polyolefin resin is stabilized, there is no delamination, and the conductive (antistatic) property, solvent resistance, fluidity, flame retardancy, Excellent impact resistance and molding appearance.
Since carbon nanotubes can be blended in a much larger number (about 10 ⁶ times) than carbon fibers, they have an effect of preventing delamination and forming a conductive path.
Moreover, the compounding quantity of a carbon nanotube can be reduced by alloying aromatic polycarbonate resin / polyolefin-type resin.

In the aromatic polycarbonate resin composition of the present invention, as the resin component, a combination comprising (A) 50 to 99% by mass of aromatic polycarbonate resin and (B) 50 to 1% by mass of polyolefin-based resin is used.
In the resin component, if the content of the component (A) and the component (B) is in the above range, the obtained aromatic polycarbonate resin composition exhibits the characteristics of the aromatic polycarbonate resin sufficiently and is resistant to solvents. Property and impact resistance are improved.
Preferable content ratio of the component (A) and the component (B) is that the component (A) is 60 to 95% by mass and the component (B) is 40 to 5% by mass.
In the aromatic polycarbonate resin composition of this invention, (C) 0.1-30 mass parts of carbon nanotubes with respect to 100 mass parts of total amounts of (A) component and (B) component, Preferably 0.5- 10 parts by mass is blended.
When the blending amount of the carbon nanotube is 0.1 part by mass or more, the conductive (antistatic) property and flame retardancy of the aromatic polycarbonate resin composition of the present invention are improved, and when the blending amount is 30 parts by mass or less. The performance is improved according to the amount, and the impact strength and formability are increased.
Moreover, in the aromatic polycarbonate resin composition of the present invention, if necessary, 10 parts by mass or less of (D) compatibilizer is blended with respect to 100 parts by mass of the total amount of component (A) and component (B). Preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass.
If the blending amount of the compatibilizing agent is within the above range, the aromatic polycarbonate resin / polyolefin resin compatibilizing effect is satisfactorily exhibited, the domain of the polyolefin resin agent is miniaturized, and the resulting aromatic polycarbonate resin is obtained. The physical properties of the composition are improved.

The (A) aromatic polycarbonate resin of the present invention is not particularly limited and includes various types.
Usually, an aromatic polycarbonate resin produced by a reaction between a dihydric phenol and a carbonate precursor can be used.
That is, a product prepared by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol and phosgene, a transesterification method of a dihydric phenol and diphenyl carbonate or the like is used. be able to.

  Various divalent phenols can be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy). Phenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, Examples thereof include bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, and halogen substituted products thereof.

In particular, preferred dihydric phenols are bis (hydroxyphenyl) alkanes, particularly bisphenol A.
The carbonate precursor is carbonyl halide, carbonyl ester, haloformate or the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate or the like.
In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol.
These dihydric phenols may be used alone or in combination of two or more.

In addition, the aromatic polycarbonate resin may have a branched structure, and 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4- Hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol) and the like.
Moreover, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, etc. are used for adjustment of molecular weight.

The aromatic polycarbonate resin used in the present invention may be a copolymer having a polycarbonate part and a polyorganosiloxane part, or a polycarbonate resin containing this copolymer.
Further, it may be a polyester-polycarbonate resin obtained by polymerizing a polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof.
A mixture of various polycarbonate resins can also be used.
The viscosity average molecular weight of the aromatic polycarbonate resin of the present invention is usually 10,000 to 40,000, preferably 13,000 to 30,000, more preferably from the viewpoint of mechanical strength and moldability. 14,000-27,000.

Examples of the (B) polyolefin resin of the present invention include various polyolefin resins such as a polyethylene resin, a polypropylene resin, and a poly-1-butene resin.
Examples of the polyethylene resin include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, and copolymers of ethylene and other α-olefins.
Examples of other α-olefins include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene.
Polypropylene resins include crystalline propylene homopolymers, crystalline propylene-ethylene blocks and random copolymers, crystalline propylene-ethylene-α-olefin copolymers, and crystalline propylene polymers and elastomers. And a mixture thereof.
Examples of the α-olefin include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene.
As the elastomer, styrene-based or olefin-based elastomers such as styrene- (1-butene) -styrene triblock copolymer (SBS) and styrene- (ethylene / 1-butene) -styrene triblock copolymer (SEBS), Furthermore, core-shell type elastomers such as methyl methacrylate-butadiene-styrene resin (MBS) and methyl methacrylate-acrylonitrile-styrene resin (MAS) are preferable.
The polyolefin resin of the present invention can be used as the above resin alone or as a mixture of two or more.
The melt flow rate [MFR] (230 ° C., 21.18 N) of the polyolefin resin of the present invention and the mixture thereof is usually 0.5 to 600 g / 10 minutes, preferably 1 to 500 g / 10 minutes.
When the melt flow rate is 0.5 g / 10 min or more, molding is easy, and when it is 600 g / 10 min or less, mechanical properties such as impact resistance are remarkably increased.

Moreover, as (B) polyolefin resin of this invention, an ethylene- (meth) acrylic acid copolymer and / or its ester are mentioned.
The ethylene- (meth) acrylic acid copolymer and / or ester thereof is a binary copolymer composed of ethylene and (meth) acrylic acid (ester), and an ethylene- (meth) acrylic acid copolymer and ester thereof, and An ethylene-carbon monoxide- (meth) acrylic acid copolymer which is a terpolymer containing carbon monoxide as a third monomer and an ester thereof, and one or more of these are appropriately selected. Can be used.

In order to produce an ethylene- (meth) acrylic acid copolymer and / or an ester thereof, for example, each monomer together with a radical initiator such as t-butylperoxyisobutyrate or azobisisobutyronitrile What is necessary is just to supply in a high speed stirring reactor by a ratio, and to mix by high speed stirring (for example, 160-300 degreeC) under high pressure (for example, 160-300 MPa), and to copolymerize.
Here, as the (meth) acrylic acid ester, a linear or branched alkyl ester having 1 to 18 carbon atoms, preferably about 1 to 8 carbon atoms is usually preferable.
More specifically, esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl and the like can be mentioned.

  As the monomer (meth) acrylic acid ester, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl Acrylic esters such as acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, It can be mentioned methacrylic acid esters such as emissions Jill methacrylate.

In the ethylene-carbon monoxide- (meth) acrylic acid copolymer and its ester, 30 to 90% by mass of ethylene units, preferably 40 to 80% by mass, 1 to 40% by mass of carbon monoxide units, preferably 5 to 5%. It is desirable that it is contained in an amount of 30% by mass, 5 to 60% by mass of (meth) acrylic acid (ester) units, preferably 15 to 50% by mass, and further copolymerize other monomers as necessary. Is also possible.
By using this ethylene- (meth) acrylic acid copolymer and / or its ester, impact resistance, fluidity, and solvent resistance can be imparted to the aromatic polycarbonate resin composition of the present invention.

The carbon nanotube (C) of the present invention is a cylindrical hollow fibrous substance composed of carbon, preferably having an outer diameter of 0.5 to 120 nm and a length of preferably 500 nm or more, more preferably The outer diameter is 1 to 100 nm and the length is 800 to 15,000 nm.
When the outer diameter of the carbon nanotube is 0.5 nm or more, the dispersion is easy and the conductivity (antistatic property) is improved. When the outer diameter is 120 nm or less, the appearance of the molded product is good and the conductivity (charging) Prevention) also increases.
When the length of the carbon nanotube is 500 nm or more, particularly 800 nm or more, the conductivity (antistatic) is sufficient, and when the length is 15,000 nm or less, the appearance of the molded product is good and easy to disperse. It becomes.
From the viewpoint of electrical conductivity (antistatic property) and flame retardancy of the aromatic polycarbonate resin composition of the present invention, the amorphous carbon particles contained as impurities in the carbon nanotubes are preferably 20% by mass or less.
By controlling the amorphous carbon particles to 20% by mass or less, the electrical conductivity (antistatic) performance is improved and there is an effect of preventing deterioration during molding.
By blending the carbon nanotube, the phase structure of the aromatic polycarbonate resin / polyolefin resin is stabilized, and the realignment of the polyolefin resin during melting and the domain orientation during injection molding can be reduced.

As the carbon nanotube of the present invention, various known carbon nanotubes and carbon microcoils can be used.
For the carbon nanotube, catalytic chemical vapor deposition method (CCVD method), vapor deposition method (CVD method), laser ablation method, carbon rod / carbon fiber, etc. in which iron or cobalt-based catalyst was introduced into the pores of zeolite were used. It can be manufactured by an arc discharge method or the like.
The terminal shape of the carbon nanotube is not necessarily cylindrical, and may be deformed, for example, conical.
Further, either a structure in which the end of the carbon nanotube is closed or an open structure can be used, but a structure having an open end is preferable.
A carbon nanotube having a closed end can be opened by a chemical treatment such as nitric acid.
Furthermore, the structure of the carbon nanotube may be a multilayer or a single layer.
Moreover, the aromatic polycarbonate resin composition of this invention can also be manufactured using the masterbatch of polyolefin resin and a carbon nanotube.

Examples of the compatibilizer (D) of the present invention include acid-modified polyolefin resins modified with unsaturated carboxylic acids or derivatives thereof.
Examples of the polyolefin resin used for the acid-modified polyolefin resin include polypropylene, polyethylene, ethylene-α-olefin copolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, and ethylene-α-olefin. Examples thereof include copolymer rubber, ethylene-α-olefin-nonconjugated diene compound copolymer (for example, EPDM), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer rubber, and the like.
Examples of the α-olefin include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, and the like. These may be used alone or in combination of two or more. It may be used.
Among these polyolefin resins, a polypropylene resin and a polyethylene resin containing a copolymer are preferable, and among them, a polypropylene resin is most preferable.

Specific examples of the unsaturated carboxylic acid or derivative thereof used for modification include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid and the like. Unsaturated carboxylic acids, maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butyl Examples thereof include acid anhydrides such as maleimide, sodium acrylate, and sodium methacrylate, esters, amides, imides, and metal salts.
Of these, unsaturated dicarboxylic acids and derivatives thereof are preferred, and maleic anhydride is particularly preferred.

These unsaturated carboxylic acids and derivatives thereof may be used singly or in combination of two or more when the polyolefin resin is modified.
Moreover, there is no restriction | limiting in particular about the modification | denaturation method, A conventionally well-known various method can be used.
For example, a method in which the polyolefin resin is dissolved in a suitable organic solvent, an unsaturated carboxylic acid or a derivative thereof, and a radical generator are added and stirred and heated, or the above components are supplied to an extruder and melt-kneaded. The method of performing etc. can be used.
As this acid-modified polyolefin-based resin, those having an addition amount of the unsaturated carboxylic acid or its derivative in the range of 0.01 to 20% by mass, preferably 0.1 to 10% by mass are preferable. 10 mass% of maleic anhydride addition modified polypropylene resin is suitable.

In addition, examples of the (D) compatibilizing agent of the present invention include epoxy-modified or oxazoline-modified polyolefin resins.
The epoxy-modified or oxazoline-modified polyolefin-based resin means a copolymer of an epoxy group- or oxazolinyl group-containing unsaturated monomer and an olefin-based or acrylic-based monomer copolymerizable therewith.
Examples of the epoxy group-containing unsaturated monomer include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, hydroxyalkyl (meth) acrylate glycidyl ether, polyalkylene glycol (meth) acrylate glycidyl ether, glycidyl itaconate, and the like.

（式中、Ｚは重合可能な二重結合を示す。）
で表わされるオキサゾリン化合物が挙げられる。 Moreover, as an oxazolinyl group containing unsaturated monomer, general formula (1)

(In the formula, Z represents a polymerizable double bond.)
The oxazoline compound represented by these is mentioned.

上式中、Ｒ²は、水素原子、炭素原子１〜６のアルキル基又はアルコキシ基を示す。
炭素原子１〜６のアルキル基としては、メチル基、エチル基、イソプロピル基、ｎ−プロピル基、ブチル基、ペンチル基、ヘキシル基が挙げられ、炭素原子１〜６のアルコキシ基としては、メトキシ基、エトキシ基、イソプロポキシ基、ｎ−プロポキシ基、ブトキシ基、ペントキシ基、ヘキソキシ基が挙げられる。 Examples of Z include the following substituents.

In the above formula, R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, butyl group, pentyl group, and hexyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group. Ethoxy group, isopropoxy group, n-propoxy group, butoxy group, pentoxy group, and hexoxy group.

（式中、Ｒ²は、水素原子、炭素原子１〜６のアルキル基又はアルコキシ基を示す。）
で表わされるビニルオキサゾリン化合物が挙げられ、Ｒ²が水素原子又はメチル基の化合物が好ましい。
エポキシ基又はオキサゾリニル基含有不飽和単量体と共重合可能なオレフィン単量体としては、エチレン、プロピレン、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン等のα−オレフィンが挙げられる。
α−オレフィン成分の他に、少量のブタジエン、イソプレン、１，４−ヘキサジエン、５−エチリデン−２−ノルボルネン、５−ビニル−２−ノルボルネン等のジエン成分、酢酸ビニル、アクリル酸（塩）、メタアクリル酸（塩）、アクリル酸エステル、メタアクリル酸エステル、（無水）マレイン酸、マレイン酸エステル、２−ノルボルネン−５，６−ジカルボン酸（無水物）等の不飽和カルボン酸又はその誘導体成分、スチレン等の芳香族ビニルモノマー、又はアクリロニトリル等のシアン化ビニル系単量体が共重合体中に含まれていてもよい。
共重合体がエポキシ基とオキサゾリニル基の両者を有することもできる。
エポキシ基又はオキサゾリニル基含有不飽和単量体と共重合可能なアクリル単量体としては、アクリル酸、メタクリル酸及びこれらの誘導体、例えば、塩、エステル等が挙げられる。
これらの成分の他に、少量のα−オレフィン、ジエン成分、不飽和カルボン酸又はその誘導体成分、芳香族ビニル単量体又はシアン化ビニル系単量体等が共重合体中に含まれていてよい。
上記オレフィン系又はアクリル系共重合体において、エポキシ基及びオキサゾリニル基を有する不飽和単量体由来の単位の量は、共重合体に対して０．０５〜３０質量％が好ましい。
０．０５質量％以上であると、相溶性が良好であり、３０質量％以下であると、耐溶剤性の改良効果が高い。
相溶化剤を配合することにより、芳香族ポリカーボネート樹脂／ポリオレフィン系樹脂を相溶化し、ポリオレフィン系樹脂を微小化することができる。 Preferred compounds include those represented by the general formula (2)

(In the formula, R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group.)
And a compound in which R ² is a hydrogen atom or a methyl group is preferable.
Examples of the olefin monomer copolymerizable with an epoxy group or oxazolinyl group-containing unsaturated monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. , 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and other α-olefins.
In addition to the α-olefin component, a small amount of diene components such as butadiene, isoprene, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, vinyl acetate, acrylic acid (salt), meta Unsaturated carboxylic acid such as acrylic acid (salt), acrylic acid ester, methacrylic acid ester, (anhydrous) maleic acid, maleic acid ester, 2-norbornene-5,6-dicarboxylic acid (anhydride) or a derivative component thereof, An aromatic vinyl monomer such as styrene or a vinyl cyanide monomer such as acrylonitrile may be contained in the copolymer.
The copolymer can also have both an epoxy group and an oxazolinyl group.
Examples of the acrylic monomer copolymerizable with the epoxy group or oxazolinyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, and derivatives thereof such as salts and esters.
In addition to these components, a small amount of α-olefin, diene component, unsaturated carboxylic acid or derivative component thereof, aromatic vinyl monomer or vinyl cyanide monomer is contained in the copolymer. Good.
In the olefin-based or acrylic-based copolymer, the amount of the unit derived from the unsaturated monomer having an epoxy group and an oxazolinyl group is preferably 0.05 to 30% by mass with respect to the copolymer.
When it is 0.05% by mass or more, the compatibility is good, and when it is 30% by mass or less, the effect of improving the solvent resistance is high.
By blending the compatibilizing agent, the aromatic polycarbonate resin / polyolefin resin can be made compatible and the polyolefin resin can be miniaturized.

  Furthermore, the aromatic polycarbonate resin composition of the present invention is not limited to its physical properties, and other resins and additives such as pigments, dyes, reinforcing agents, fillers, heat-resistant agents, oxidative degradation, during mixing and molding. Inhibitors, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, fluidity improvers, antistatic agents, and the like can be added.

As a manufacturing method of the aromatic polycarbonate resin composition of this invention, the method of melt-kneading each component by a conventionally well-known method is mentioned.
For example, a method in which each component is dispersed and mixed with a high-speed mixer represented by a turnbull mixer, a Henschel mixer, a ribbon blender, or a super mixer, and then melt-kneaded with an extruder, a Banbury mixer, a roll, or the like is appropriately selected.
As a manufacturing method, each component may be added all at once and melt-kneaded. However, after melt-kneading a polyolefin resin and carbon nanotubes in advance and then melt-kneading an aromatic polycarbonate resin or the like, the conductivity (antistatic property) is improved. The phase structure of the aromatic polycarbonate resin / polyolefin resin is stabilized.
As a method of melt kneading, other components such as an aromatic polycarbonate resin may be added from the middle of the extruder while the polyolefin resin and carbon nanotubes are melted, or a polyolefin resin and carbon nanotubes produced in advance The master batch may be used.
The amount of carbon nanotubes in the master batch is preferably 5 to 40% by mass.
Since the aromatic polycarbonate resin composition of the present invention has the above-mentioned properties, it is suitably used, for example, for OA equipment, information / communication equipment, automobile parts, home appliances, and the like.
The present invention also provides a molded article obtained using the above-described aromatic polycarbonate resin composition.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
Examples 1-4 , Comparative Examples 1-3 and Reference Example 1
Each component was blended in the proportions shown in Table 1, supplied to a vent type twin screw extruder (model name: TEM35, manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at 280 ° C., and pelletized.
The obtained pellets were dried at 120 ° C. for 10 hours, and then injection-molded at a molding temperature of 280 ° C. (mold temperature of 80 ° C.) to obtain test pieces.
The performance was evaluated by the following various tests using the obtained test pieces, and the results are shown in Table 1.

The blending components and performance evaluation methods used are shown below.
[Composition ingredients]
(A) Aromatic polycarbonate resin PC: A1900 [made by Idemitsu Kosan Co., Ltd.], viscosity average molecular weight = 19,500
(B) Polyolefin resin PO: Homopolypropylene H700 [manufactured by Idemitsu Kosan Co., Ltd.], MFR (230 ° C., 21.18 N) = 8
(C) Carbon nanotube: Multi-wall, diameter 10-30 nm, length 1-10 μm, open at both ends, amorphous carbon particle amount 15% by mass (manufactured by Sun Nanotech)
(B) + (C): PO / carbon nanotubes MB: Master batch of carbon nanotubes and homopolypropylene H700; manufactured using a twin screw extruder (TEM-35) at a set temperature of 220 ° C.
(D) Compatibilizer: Epoxy-modified polyethylene [Bondfast E, manufactured by Sumitomo Chemical Co., Ltd.]

[Performance evaluation method]
(1) IZOD (Izod impact strength): conforming to ASTM D256, 23 ° C. [wall thickness 1/8 inch (0.32 cm)], unit: kJ / m ²
(2) Volume specific resistance value: compliant with JISK6911 (test flat plate: 80 × 80 × 3 mm). Unit: Ω
(3) Flame retardancy: compliant with UL94 combustion test (test piece thickness: 3.0 mm).
(4) Solvent resistance: Evaluation was made based on changes in appearance and the like when the test piece was immersed in gasoline for 10 minutes and then bent by hand.
(5) Molding appearance: Evaluated visually.

Table 1 shows the following.
The examples are excellent in impact resistance, conductivity (antistatic) property, solvent resistance, flame retardancy, and molded appearance, and when a masterbatch is used, the impact resistance and conductivity (antistatic) property are further improved.
On the other hand, it can be seen from Comparative Example 1 that the aromatic polycarbonate resin alone has no conductivity (antistatic property) and low solvent resistance.
From Comparative Example 2, the aromatic polycarbonate resin alone does not improve the conductivity (antistatic property), solvent resistance, and flame retardancy even when the same amount of carbon nanotubes as in Examples 1 and 2 is added. It can be seen that the value also decreases.
In Comparative Example 3, the same amount of aromatic polycarbonate resin and polyolefin resin as those in Examples 3 and 4 are blended. However, if carbon nanotubes are not added, the conductive (antistatic) property and flame retardancy are not exhibited. It is considered that the impact resistance is low, delamination occurs in the molded product, and the orientation of the polypropylene domain is large.

In the aromatic polycarbonate resin composition of the present invention, the phase structure of the aromatic polycarbonate resin / polyolefin resin is stabilized, there is no delamination, and the conductive (antistatic) property, solvent resistance, fluidity, flame retardancy, Excellent impact resistance and molding appearance.
Accordingly, expansion of application fields such as housings or parts of electrical / electronic equipment such as OA equipment, information / communication equipment, automobile parts or home appliances, and automobile parts is expected.

Claims (6)

(A) The content of amorphous carbon particles is 20% by mass or less with respect to 100 parts by mass of the resin component composed of 50 to 99% by mass of the aromatic polycarbonate resin and (B) 50 to 1% by mass of the polyolefin resin , An aromatic polycarbonate resin composition containing 0.1 to 30 parts by mass of carbon nanotubes having an outer diameter of 0.5 to 120 nm and a length of 500 nm or more and having an open end , and containing no compatibilizer .   The aromatic polycarbonate resin composition according to claim 1, wherein the component (A) has a viscosity average molecular weight of 10,000 to 40,000.   The component (B) is at least one compound selected from polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer, and ethylene- (meth) acrylic acid copolymer ester. Aromatic polycarbonate resin composition. The aromatic polycarbonate resin composition according to any one of claims 1 to 3 , which is a composition for OA equipment, information / communication equipment, automobile parts, or household electrical appliances. The aromatic polycarbonate resin according to any one of claims 1 to 4 , wherein the component (B) and the component (C) are melt-kneaded, and then the component (A) is added to the kneaded product and melt-kneaded. A method for producing the composition. The molded object obtained using the aromatic polycarbonate resin composition in any one of Claims 1-4 .