JPH10101921A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin compsn. excellent in antistatic properties by incorporating a polycarbonate resin having a specified viscosity average mol.wt., a certain copolymer contg. a rubbery polymer, a polyetheresteramide block copolymer, and a metal salt into the same. SOLUTION: A polycarbonate resin (A) having a viscosity average mol.wt. of 10,000-100,000, a copolymer (B) (e.g. an ABS resin) formed from an arom, vinyl monomer, a vinyl cyanide monomer, and a rubbery polymer, a polyetheresteramide block copolymer (C), and potassium diphenylsulfone-3- sulfonate (D) are mixed to give a mixture comprising 30-96wt.% ingredient A, 1-50wt.% ingredient B, 1-30wt.% ingredient C, and 0.01-2.0wt.% ingredient D. A polycarbonate resin compsn. of the invention is prepd. by melt mixing, kneading, and extruding the above-obtd. mixture with 1-50wt.% (based on the compsn.: the same applies hereunder) copolymer (e.g. a styrene-acrylonitrile copolymer) having a number average mol.wt. of 15,000-200,000, 1-50wt.% inorg. or org. filler, and 1-30wt.% phosphoric ester compd. with a twin-screw extruder, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a polycarbonate (hereinafter sometimes referred to as PC) resin.

[0002]

SUMMARY OF THE INVENTION Polycarbonate (P
C) Resins and polymer alloys blended with ABS (acrylonitrile-butadiene-styrene) resins are widely used in electric and electronic products, OA equipment and the like.
However, since PC and PC / ABS alloy resin have high electric insulating properties, they are easily stained by adhesion of dust to the surface of a molded product due to generation of static electricity, and improvement thereof is desired. Further, in media-related applications, there is also a demand for using a resin that is unlikely to adhere to dust. Conventionally, as a prescription for imparting antistatic performance, there have been a method of adding a conductive filler and a method of adding an antistatic agent such as a surfactant. However, when a conductive filler is added, moldability and impact resistance are poor. Further, the addition of an antistatic agent such as a surfactant does not provide permanent charging performance, and has a disadvantage that the antistatic performance is easily lost by treatment such as washing of a molded article with water.

As a method for imparting permanent antistatic properties to PC resin and PC / ABS alloy resin, a method in which a polyetheresteramide resin is added is disclosed in JP-A-5-4.
No. 3787, JP-A-1-198656, JP-A-7-23
3364. However, satisfactory performance was not obtained by any of the methods.

Accordingly, an object of the present invention is to provide a PC resin composition having a permanent antistatic property and excellent mechanical properties.

Another object of the present invention is to provide a PC resin composition which is excellent in the above-mentioned properties and exhibits excellent flame retardancy.

[0006]

Means for Solving the Problems The present inventors have proposed PC / A.
As a result of intensive studies on the BS resin composition to solve the above problems, excellent permanent antistatic properties were obtained by adding a polyetheresteramide copolymer and a metal salt in combination to a PC / ABS resin composition. It has been found that a resin composition having performance can be obtained. Furthermore, it has been found that a permanent antistatic resin composition imparted with excellent flame retardancy can be obtained by using a phosphate ester-based flame retardant for the requirement of flame retardancy.

That is, the present invention provides: (A) 30 to 96% by weight of a polycarbonate resin having a viscosity average molecular weight of 10,000 to 100,000; (B) (a) an aromatic vinyl monomer component; (b) 1 to 50% by weight of a copolymer containing a vinyl cyanide monomer component and (c) a rubbery polymer as a component of copolymerization, and (C) a polyetheresteramide block copolymer 1
(D) 0.01 to 2.0% by weight of a metal salt.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate resin used in the present invention is an aromatic polycarbonate prepared by a known phosgene method or a melting method, and such a polycarbonate resin is used. Is described, for example, in JP-A-63-2
No. 15763 and JP-A-2-124934. Examples of diphenol used as a raw material include 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A);
5-dibromo-4-hydroxyphenyl) propane;
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane ; 1,1-
Bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) decane; 1,4-bis (4-hydroxyphenyl)
Propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-
(Hydroxyphenyl) cyclododecane; 4,4-dihydroxydiphenyl ether; 4,4-thiodipheno-
4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether. In addition, examples of the precursor for introducing the carbonate include phosgene and diphenyl carbonate.

In the present invention, it is necessary that the polycarbonate resin has a viscosity average molecular weight (Mv) of 10,000 or more. The viscosity average molecular weight is preferably 21,
2,000 or more, more preferably 22,000 or more.
The viscosity average molecular weight needs to be 100,000 or less, and practically 40,000 or less. If the viscosity average molecular weight is less than the above lower limit, physical properties are reduced, and if it exceeds the upper limit, fluidity is impaired. In the present invention, the viscosity average molecular weight (Mv) in methylene chloride is
The intrinsic viscosity (intrinsic viscosity) was measured at 20 ° C., and the viscosity formula of Mark-Houwink was calculated as follows:

[0010]

## EQU1 ## It was determined by calculation using intrinsic viscosity [η] = K (Mv) ^a (where K = 1.23 × 10 ⁻⁴ and a = 0.83 in the above formula).

The component (B) is a copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer. (a) As the aromatic vinyl monomer component, for example, styrene, α-methylstyrene, o
-, m- or p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-ter-butylstyrene, ethylstyrene, vinylnaphthalene and the like. Use one or more. Preferred are styrene and α-methylstyrene.

(B) As the vinyl cyanide monomer component,
For example, acrylonitrile, methacrylonitrile and the like can be mentioned, and one or more of these are used.

(C) The rubbery polymer includes polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene Diene rubbers such as isoprene copolymers, random copolymers and block copolymers of ethylene-propylene, copolymers of ethylene and α-olefins, and ethylene such as ethylene-methacrylate and ethylene-butyl acrylate A copolymer with an unsaturated carboxylic acid ester, an acrylic ester-butadiene copolymer, for example, an acryl-based elastic polymer such as butyl acrylate-butadiene copolymer, an ethylene-fatty acid such as ethylene-vinyl acetate, or the like; Copolymer, ethylene-propylene-hexadiene copolymer Ethylene, such as - propylene nonconjugated Jienta - polymer -, butylene - Isoburen copolymers, chlorinated polyethylene and the like, used in these one or two or more. Preferred rubbery polymers are ethylene-propylene non-conjugated dienter polymers, diene rubbers and acrylic elastic polymers, and particularly preferred are polybutadiene and styrene-butadiene copolymer.

The ratio of the above components in the component (B) copolymer is not particularly limited and is selected according to the use.

The component (B) copolymer includes the above-mentioned component (a)
In addition to (b) and (c), (d) monomers copolymerizable with these components can be used as long as the objects of the present invention are not impaired. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β such as meth) acrylate, 2-ethyl (meth) acrylate and 2-ethylhexyl methacrylate
-Unsaturated carboxylic esters; α, β-unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride;
Imide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, No-chlorophenylmaleimide; and the like. Are used alone or in combination of two or more.

The component (B) copolymer is preferably a graft copolymer obtained by graft copolymerizing other components in the presence of a rubbery polymer (c), and more preferably an ABS resin (acrylonitrile-butadiene-styrene). AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer), A
AS resin (acrylonitrile-acrylic elastic body-styrene copolymer).

The method for producing the component (B) copolymer is not particularly limited, and any of the known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used.
Further, it can be obtained by blending separately copolymerized resins.

In the present invention, regarding the resin composition to which the component (G) flame retardant described below has been added, when the component (B) is produced by bulk polymerization or bulk suspension polymerization, physical properties and the like are considered. And preferred results were obtained.

The component (C) polyetheresteramide copolymer is known per se, and is a polyetheresteramide derived from a polyamide having carboxyl groups at both ends and an ethylene oxide adduct of polyetherdiol or bisphenols. It is a copolymer.
The polymerization method is not particularly limited.

The metal salt of component (D) includes metal salts of organic acids, for example, sulfonic acids, carboxylic acids and the like, and metal sulfonic acid salts are preferred. Examples of the metal include an alkali metal (eg, Li, Na, K, etc.) and an alkaline earth metal (eg, Be, Mg, Ca, etc.). An alkali metal is preferable, and K is particularly preferable. Particularly preferably, potadium diphenyl sulfone-
3-sulfonate.

Component (A) in the resin composition of the present invention,
The amounts of (B), (C) and (D) are from (A) 30 to
96% by weight, (B) 1 to 50% by weight, (C) 1 to 30% by weight and (D) 0.01 to 2.0% by weight. Preferably (A) 50 to 90% by weight, (B) 5 to 20% by weight, (C) 3 to 10% by weight and (D) 0.1 to 0.5%.
% By weight. If the proportion of the component (C) is too small, the antistatic effect is not recognized, and if it is too large, physical properties decrease, delamination and poor appearance may occur. If the proportion of the component (D) is too small, no antistatic effect is observed, while if it is too large, physical properties are reduced.

Next, the optional components will be described. The resin composition of the present invention comprises, as components that contribute to improvement in moldability (flowability), component (E) (a) an aromatic vinyl monomer component and (b)
It may include a copolymer containing a vinyl cyanide monomer component. Examples of (a) the aromatic vinyl monomer component and (b) the vinyl cyanide monomer component include those described above for the component (B). The composition ratio of (a) / (b) is
Although it is not particularly limited, it is preferably in component (E).
(a) is 95 to 50% by weight, (b) is 5 to 50% by weight, more preferably (a) is 92 to 65% by weight, and (b) is 8%.
~ 35% by weight. Preferred examples of the component (E) copolymer include, for example, SAN resin (styrene-acrylonitrile copolymer).

The method for producing the component (E) copolymer is not particularly limited, and a method similar to the above-mentioned component (B) copolymer can be used.

In the present invention, the weight average molecular weight (Mw) of the component (E) copolymer is preferably from 15,000 to 15,000.
200,000, more preferably 30,000-11
It is 0000.

The resin composition of the present invention contains the component (E) in an amount of not more than 50% by weight, preferably 1 to 50% by weight of the whole composition.
At a rate of

The resin composition of the present invention may further contain a component (F) an inorganic or organic filler for the purpose of improving dimensional accuracy and mechanical strength. Examples of the inorganic filler include talc, mica, barium sulfate, glass (glass fiber, milled glass, glass flake, glass beads, etc.), carbon fiber, metal powder (eg, copper powder, aluminum powder, etc.), clay, titanium oxide, Examples include carbon black and potassium titanate. Examples of the organic filler include, for example, wholly aromatic polyamides such as nylon and aramid, heterocyclic compounds such as polyamideimide, polyimide, polyester, polybenzimidazole and polyimidazophenanthroline, and polytetrafluoroethylene. . These fillers may be treated with a silane coupling agent, a titanium coupling agent, or the like.
Component (F) is preferably an inorganic filler selected from talc, mica, barium sulfate, glass fiber, glass flake, carbon fiber and metal powder. When high appearance and high dimensional accuracy are required, a flaky filler such as talc or mica is preferable. When a high specific gravity is required, barium sulfate is effective.

The component (F) can be contained in a proportion of 50% by weight or less of the whole composition, preferably in a proportion of 1 to 50% by weight.

The resin composition of the present invention can also contain a component (G) a phosphate compound, for example, the following formula (I):

[0029]

Embedded image (Where R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but R ¹ = R ² =
Except when R ³ = R ⁴ = H. X represents a divalent or higher valent organic group, p represents 0 or 1, q represents an integer of 1 or more, for example, 30 or less, and r represents an integer of 0 or more. )). However, it is not limited to these.

In the above formula (I), examples of the organic group include an alkyl group which may or may not be substituted, a cycloalkyl group and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group,
Examples thereof include an aryloxy group, an arylthio group, and a halogenated aryl group. A group obtained by combining these substituents (eg, an arylalkoxyalkyl group) or such a substituent is replaced with an oxygen atom, a sulfur atom, a nitrogen atom, or the like. (For example, an arylsulfonylaryl group and the like) may be used as a substituent. The divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-described organic group. Examples include alkylene groups, and preferably (substituted) phenylene groups, those derived from polynuclear phenols such as bisphenols, and the relative positions of the two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, bisphenol A, bisphenol S, dihydroxynaphthalene and the like.

Specific examples of the phosphoric ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl. Phosphate,
Diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate,
Bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate and bis (chloropropyl) monooctyl phosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetraxylyldi Phosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetracresyl diphosphate, hydroquinone tetraxylyl diphosphate, wherein R ¹ -R ⁴ are alkoxy, such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy Bisphenol A in a certain place
Examples include polyphosphates such as bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, and trioxybenzene triphosphate, and are preferably selected from triphenyl phosphate and various bisphosphates.

The component (G) can be contained in a proportion of not more than 30% by weight of the whole composition, preferably 1 to 30% by weight, more preferably 3 to 20% by weight, particularly preferably 5 to 15% by weight. %.

The composition of the present invention may further contain a dripping inhibitor. The fluorinated polyolefin that can be used as such an anti-dripping agent is commercially available or can be produced by a known method. It can be used, for example, in aqueous media using a free radical catalyst (e.g., sodium, potassium or ammonium peroxydisulfate).
1000 psi pressure and 0-200 ° C. preferably 2
It is a white solid obtained by polymerizing tetrafluoroethylene at a temperature of 0 to 100C. For more information, see Brubaker US Patent No. 23939.
No. 67 can be referred to.

Although not essential, relatively large particles, for example an average particle size of 0.3 to 0.7 mm (mainly 0.5 m
It is preferable to use the resin in the state of particles of m). This is better than regular polytetrafluoroethylene powders having a particle size of 0.05-0.5 mm. The reason that such relatively large particle size materials are particularly preferred is that they disperse readily in the polymer and tend to combine the polymers to form a fibrous material. Such a suitable polytetrafluoroethylene is what is referred to as type 3 according to ASTM and is in fact DuPont (EI D
upont de Nemoursand Company), Teflon 6 (Te
It is commercially available as flon 6). Alternatively, it can be obtained commercially as Teflon 30J of Mitsui DuPont Fluorochemicals. The fluorinated polyolefin is preferably used in an amount of 0.1 to 100 parts by weight of the component (A).
It is used in an amount of from 01 to 2 parts by weight, more preferably from 0.05 to 1.0 part by weight.

The resin composition of the present invention may further contain, in addition to the above-mentioned components, other additives commonly used for mixing or molding the resin according to the purpose, as long as the physical properties are not impaired. For example, well-known additives such as pigments, dyes, heat-resistant agents, antioxidant agents, weathering agents, lubricants, release agents, crystal nucleating agents, plasticizers, flow improvers, and antistatic agents can be blended. .

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, generally the melt mixing method is preferred. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, and the like. These devices can be operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0037]

The present invention will be further disclosed below with reference to examples. The substances used in the following examples were as follows. Essential components: Component (A) PC: polycarbonate of bisphenol A, LEXA
N (trade name; manufactured by Japan GE Plastics Co., Ltd.)
0.50 d intrinsic viscosity measured at 20 ° C. in methylene chloride
1 / g, Mv = about 22,000 (calculated value) Component (B) ABS-1: ABS resin, Santac AT-05
ABS-2: ABS resin, UX050 (trademark; manufactured by Ube Sycon Co., Ltd.) Component (C) Polyetheresteramide block copolymer resin: Pe
lestat 6321 (trademark; manufactured by Sanyo Kasei Co., Ltd.) Component (D) Metal salt: Potadium diphenylsulfon-3-sulfonate Component (E) SAN: SAN resin, SR30B (trademark; manufactured by Ube Sykon Co., Ltd.) Component (F Inorganic filler: barium sulfate Component (G) Resorcinol diphosphate: CR733S (trademark);
Daihachi Chemical Co., Ltd.).

Examples 1 to 7 and Comparative Examples 1 to 2 The components shown in Tables 1 to 3 were obtained by using a twin screw extruder manufactured by Toshiba Machine Co., Ltd. at a screw rotation speed of 200 rpm and a barrel temperature of 270 to 280 ° C. Under the extrusion conditions described above, extrusion was carried out and cut into a predetermined length to produce pellets.

Using the pellets thus produced, test pieces for a flame retardancy test were molded using an 80t injection molding machine manufactured by Toyo Kikai Metal Co., Ltd. Molding conditions are barrel temperature 24
The temperature was set to 0 ° C. and the mold temperature to 50 ° C. This test piece was also used for other physical property measurements.

Each physical property evaluation test was performed as follows.
The results are shown in Tables 1 to 3. (1) Izod impact strength 1/8 "notched Izod impact strength was measured according to ASTM D256. (2) Tensile strength was measured according to ASTM D638. (3) Flexural strength and flexural modulus Measured according to ASTM D790. (4) Deflection temperature under load A 1/4 inch thick test piece was measured at a load of 18.6 kg / cm ^{2 in} accordance with ASTM D648. (5) Surface resistivity 50 mm square, wall thickness obtained by injection molding. A test piece having a thickness of 3 mm was left in an atmosphere of 23 ° C. and 50% RH for 24 hours after molding, and then the surface resistivity was measured in accordance with JIS K6911.
ADVANTEST R8340 using chamber R12702
A resistance value measuring machine was used.

The half-life of the test piece left in the above atmosphere was measured using a STATIC HONESTMETER Type manufactured by SHISHIDO.
It evaluated using S-5109. After charging a 9 Kv charge for 20 seconds, the charge was stopped and the decay of the charge was observed, and the time required for the amount of the initially charged charge to be reduced by half was measured and defined as the half life. (6) Flame retardancy test A test was conducted in accordance with UL94 / V0, VI, and VII. Five specimens were tested with Underwriters Laboratories, Inc., Bulletin 94 "Burning Test for Material Classification"
(Hereinafter referred to as UL-94). According to this test method, the test material was UL-9 based on the results of five samples.
4 Evaluated to any of V-0, VI and V-II. The criteria for each V rating for UL-94 are outlined below.

V-0: The average flame holding time after removing the ignition flame is 10 seconds or less, and all the samples do not drop the fine flame igniting the absorbent cotton.

VI: The average flame holding time after removing the ignition flame is 30 seconds or less, and all the samples do not drop the fine flame igniting the absorbent cotton.

V-II: The average flame holding time after removing the ignition flame is 30 seconds or less, and these samples drop fine flames igniting absorbent cotton.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

The physical properties of the molded article obtained from the resin composition of the present invention exhibit excellent permanent antistatic properties as compared with conventional articles. Furthermore, it shows excellent flame retardancy by blending a specific flame retardant. As described above, since the resin composition of the present invention has excellent permanent antistatic properties, the resin composition of the present invention can be applied to a wide range of industrial applications including electric and electronic fields.

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Claims (9)

[Claims] (A) a viscosity average molecular weight of 10,000 to 1
Polycarbonate-based resin having a molecular weight of 0.00000
6% by weight, (B) Copolymers 1 to 50 containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer as constituent components of the copolymer. % By weight, and (C) polyetheresteramide block copolymer 1
(D) 0.01 to 2.0% by weight of a metal salt. 2. The component (B) is selected from ABS resin, AES resin, ACS resin and AAS resin.
The resin composition as described in the above. 3. The resin composition according to claim 1, wherein the component (D) is a metal sulfonic acid salt. 4. A copolymer comprising (E) (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component as constituent components of the copolymer, wherein the weight average A copolymer having a molecular weight of 15,000 to 200,000 is
2. The composition according to claim 1, which is contained in a proportion of 1 to 50% by weight of the whole composition.
The resin composition according to any one of claims 1 to 3. 5. The method according to claim 1, wherein (F) an inorganic or organic filler is
2. The composition according to claim 1, which is contained in a proportion of 1 to 50% by weight of the whole composition.
5. The resin composition according to any one of items 4 to 4. 6. The resin composition according to claim 5, wherein the component (F) is an inorganic filler selected from talc, mica, barium sulfate, glass fiber, glass flake, carbon fiber and metal powder. 7. The resin composition according to claim 1, further comprising (G) a phosphate compound at a ratio of 1 to 30% by weight of the whole composition. 8. The resin composition according to claim 7, wherein the component (B) is a copolymer produced by bulk polymerization. 9. The resin composition according to claim 1, which has a specific gravity of 1.3 or more.