JPH07233364A - Antistatic resin composition - Google Patents

Abstract

PURPOSE:To obtain an antistatic resin composition excellent in antistatic durability, shock resistance and heat resistance and useful in an electric and electronic field, etc., by compounding a polycarbonate resin (and a vinyl thermoplastic resin) with a specific copolymer. CONSTITUTION:This antistatic resin composition is obtained by compounding 100 pts.wt. of a resin mixture consisting of (A) 30-100wt.% of a polycarbonate resin and (B) 0-70wt.% of a vinyl thermoplastic resin) with (C) 3-30 pts.wt. a polyether-ester amide. The polyether-ester amide is obtained by copolymerizing a compound selected from a >=6C aminocarboxylic acid, lactam and dicarboxylic acid diamine salt with a compound of the formula [R1 is a l-6C alkylene or alkylidene, a 5-15C cycloalkylene, etc.; R2 and R3 are each H, a 1-6C alkyl, a halogen, etc.; R4 and R5 are each an ethylene oxide group or a propylene oxide group; m and n are each >=1 and m+n=16-50; X=0-4] and a 4-20C dicarboxylic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition having a permanent antistatic property, excellent mechanical properties and heat resistance.

[0002]

2. Description of the Related Art Generally, a polycarbonate resin or a polycarbonate / ABS blend resin has good mechanical properties and processability and is used in a wide range of fields. However, since they have a high electric insulation property, dust and the like are easily attached to the surface of the resin molded product and easily soiled, and improvement thereof is desired. Conventionally, in order to improve antistatic performance, a method of adding a conductive inorganic filler to make the resin itself conductive, or a method of adding an antistatic agent such as a surfactant to the resin has been carried out. In the former case, the impact resistance and workability are inferior, and in the latter case, the effect is remarkably reduced by washing once, and the durability is inferior.

As a method for imparting a permanent antistatic ability to a polycarbonate resin, for example, JP-A-5-437 is used.
Japanese Patent Publication No. 87 discloses a resin composition in which a polyether ester amide, a phosphite, and a phenol compound are mixed with a polycarbonate resin. Also ABS
As a method for imparting a permanent antistatic ability to a resin or a polycarbonate resin / ABS resin alloy,
For example, JP-A-62-273252 and JP-A-1
JP-A-198656 discloses a resin composition in which a polyether ester amide is added to an addition polymerization type resin or a polyether ester amide in which an aromatic diol compound is partially introduced into a polyether portion is mixed. However, none of the methods has achieved satisfactory thermal stability, heat resistance, and low chargeability.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition which retains its mechanical properties and heat resistance and does not lose its antistatic effect even when washed with water.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that (A) polycarbonate resin 30 to 100% by weight and (B) vinyl-based thermoplastic resin 0 to 70. (C) (a) an aminocarboxylic acid having 6 or more carbon atoms, a lactam having 6 or more carbon atoms or a lactam having 6 or more carbon atoms, or a diamine and a dicarboxylic acid, and having 6 or more carbon atoms, relative to 100 parts by weight of a resin mixture consisting of 1 wt% One or more compounds selected from salts, (b) the following general formula (I)

[0006]

[Chemical 2]

[Wherein R ₁ is an alkylene group having 1 to 6 carbon atoms, an alkylidene group, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group, or>O,>
S,>SO,> SO ₂ ,> CF ₂ groups, R ₂ and R
₃ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, halogen, a sulfonic acid group and a metal base thereof, R ₄ and R ₅ represent an ethylene oxide group or a propylene oxide group, m and n are positive integers, and m + n is m + n. 16-50 and X
Represents 0 or a positive number of 1 to 4] and a polyether ester obtained by copolymerizing a compound obtained by adding an alkylene oxide to an aromatic diol and (c) a dicarboxylic acid having 4 to 20 carbon atoms. The present inventors have found that a composition containing 3 to 30 parts by weight of an amide maintains mechanical properties and heat resistance and has excellent permanent antistatic property, and thus reached the present invention. Hereinafter, the present invention will be specifically described.

The (A) polycarbonate resin of the present invention is
It is produced by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method. Typical examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], bis (4-hydroxyphenyl) methane, and 2,2-bis (4).
-Hydroxy-3,5-dimethylphenyl) propane,
2,2- (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfone,
1,1-bis (4-hydroxyphenyl) ethane, 1,
Examples thereof include 1-bis (4-hydroxyphenyl) cyclohexane. A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane, particularly bisphenol A as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate, and the like. Specifically, phosgene,
Diphenyl carbonate, dihaloformates of dihydric phenols and mixtures thereof. In producing a polycarbonate resin, the dihydric phenols may be used alone or in combination of two or more. Further, an appropriate molecular weight regulator, branching agent, catalyst for accelerating the reaction and the like can also be used. Although the molecular weight of the aromatic polycarbonate resin is not specified, if the molecular weight is less than 10,000, the impact resistance and the like decrease, and if it exceeds 50,000, the molding processability decreases, so it is expressed as a viscosity average molecular weight. 1
50,000 to 50,000 are preferable, and 15.0
Those of 00 to 30,000 are particularly preferable. Also, two or more kinds of aromatic polycarbonate resins may be mixed.

The vinyl-based thermoplastic resin used in the present invention is, for example, acrylonitrile, methacrylonitrile,
Vinyl cyanide compounds such as chloroacrylonitrile, styrene, α-methylstyrene, p-methylstyrene, aromatic vinyl compounds such as halogenated styrene, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate , Copolymers and copolymers of acrylic acid esters such as ethyl methacrylate, butyl methacrylate, octyl methacrylate, etc., or two or more copolymerizable vinyl-based compounds in the presence of diene rubber. The graft copolymer obtained by polymerizing a monomer can be mentioned. Examples of the diene rubber used here include polybutadiene, polyisoprene,
Examples thereof include a butadiene-styrene copolymer and a butadiene-acrylonitrile copolymer. The graft copolymer may be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and the grafting method may be single-stage grafting or multi-stage grafting. Further, it may be a mixture with a copolymer having only a graft component produced as a by-product during production, or two or more kinds of thermoplastic graft copolymers may be mixed. Further, among the vinyl-based thermoplastic resins of the present invention, there is one type of composite rubber having a structure in which the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated. Alternatively, a composite rubber-based graft copolymer (hereinafter abbreviated as IPN-type vinyl-based polymer) obtained by graft-polymerizing two or more kinds of vinyl-based monomers as described above is also included. Among these, preferred are a butadiene-based rubber-reinforced acrylonitrile-styrene copolymer (ABS resin), a butadiene-based rubber-reinforced methyl methacrylate-styrene copolymer (MBS resin), and an IPN-type vinyl-based polymer.

Among the constituent components of the polyether ester amide used in the present invention, the polyamide constituent component is an aminocarboxylic acid having 6 or more carbon atoms, a lactam having 6 or more carbon atoms, or a lactam having 6 or more carbon atoms. There are salts of diamine and dicarboxylic acid, and as aminocarboxylic acid, ω-aminocaproic acid, ω-aminoenanthic acid,
ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, 12
-Aminododecanoic acid and the like, lactams such as caprolactam, enantolactam, capryllactam and laurolactam, and the like, diamines such as tetramethylenediamine and hexamethylenediamine, and dicarboxylic acids such as adipine. Acid, sebacic acid, decanedicarboxylic acid, isophthalic acid and the like can be mentioned, and as the salt of diamine and dicarboxylic acid, salts such as hexamethylediamine-adipate and hexamethylediamine-sebacate can be used. Among these, preferred is caprolactam, 11
-Aminoundecanoic acid, 12-aminododecanoic acid and hexamethylediamine-adipate are preferably used. An aminocarboxylic acid having 6 or more carbon atoms, a lactam having 6 or more carbon atoms, or a salt having 6 or more carbon atoms synthesized from a diamine and a dicarboxylic acid is 10 to 90% by weight as a constitutional unit of polyetheresteramide. Used in a range. If the amount is less than 10% by weight, the antistatic property is poor and 90
If it exceeds 5% by weight, mechanical strength is low, which is not preferable.

A compound obtained by adding an alkylene oxide to an aromatic diol of the following general formula (I)

[0012]

[Chemical 3]

[Wherein R ₁ is an alkylene group having 1 to 6 carbon atoms, an alkylidene group, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group, or>O,>
S,>SO,> SO ₂ ,> CF ₂ groups, R ₂ and R
₃ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, halogen, a sulfonic acid group and a metal base thereof, R ₄ and R ₅ represent an ethylene oxide group or a propylene oxide group, m and n are positive integers, and m + n is m + n. 16-50 and X
Represents 0 or a positive number of 1 to 4], R ₄ and R ₅ are ethylene oxide groups, and m + n is 30 to 4
The case of 0 is preferable. When m + n is less than 16, chargeability is poor, and when it is more than 50, heat resistance and polymerizability are poor, which is not preferable. Specifically, a compound obtained by adding ethylene oxide or propylene oxide to bisphenol A, a compound obtained by adding ethylene oxide or propylene oxide to tetramethylbisphenol A, a compound obtained by adding ethylene oxide or propylene oxide to bisphenol S, etc. Among them, one obtained by adding 30 to 40 mol of ethylene oxide to 1 mol of bisphenol A (that is, m + n = 30 to 40) is particularly preferable from the viewpoint of polymerizability, antistatic property and economical efficiency. Examples of the dicarboxylic acid having 4 to 20 carbon atoms (c) which forms a polyetherester unit together with the compound (b) include aromatic carboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid,
Alternatively, there may be mentioned aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedioic acid, and terephthalic acid, isophthalic acid, sebacic acid, adipic acid and dodecanedioic acid are particularly preferred from the viewpoint of polymerizability and physical properties. .

The polyether ester amide used in the present invention is prepared by reacting the aminocarboxylic acid (a) or its lactam with the dicarboxylic acid (c) to prepare a pre-polyamide having carboxylic acid groups at both ends, and It can also be produced by condensing a compound obtained by adding an alkylene oxide to the aromatic diol of b), but the polymerization method is not particularly limited.

In the resin composition of the present invention, the component (A)
The polycarbonate resin is 30 to 100% by weight, preferably 40 to 80% by weight, particularly preferably 50 to 70% by weight.
% By weight. The content of the vinyl-based thermoplastic resin as the component (B) is 0 to 70% by weight, preferably 20 to 60, and particularly preferably 30 to 50% by weight. The polyether ester amide of the component (C) is 3 to 30 parts by weight based on 100 parts by weight of the resin mixture of (A) and (B),
It is particularly preferably 5 to 15 parts by weight. When the content of the polycarbonate resin as the component (A) is less than 30% by weight, the heat resistance is poor, and when the content of the polyether ester amide as the component (C) is less than 3 parts by weight, the antistatic performance is insufficient and 30 parts by weight is used. If it exceeds, the heat resistance of the resin composition tends to be poor, which is not preferable.

In the present invention, the resin composition comprising the above-mentioned (A) polycarbonate resin, (B) vinyl-based thermoplastic resin and (C) specific polyetheresteramide is prepared, for example, by adding each component to a V-type blender. , Throw it into a ribbon mixer or tumbler, and mix it evenly.
A usual preparation method is used, such as melt-kneading with an ordinary extruder such as a single-screw or twin-screw machine, cooling and cutting into pellets.

In the composition of the present invention, a phosphoric acid ester such as trimethyl phosphate, triphenyl phosphite, tris nonyl phenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,6-di-tert-phosphite) is used. 0.005 to 1% by weight of phosphite such as butyl-4-methylphenyl) pentaerythritol diphosphite, based on the total composition.
Blending is preferable because the thermal stability is further improved. It is preferable to add 0.05 to 2% by weight of an antistatic agent such as sodium alkyl sulfonate or sodium alkylbenzene sulfonate to the entire composition because the antistatic property is further improved.

Further, various additives, inorganic fillers and other thermoplastic resins may be blended within a range not impairing the object of the present invention. As various additives, flame retardants (for example, brominated bisphenol, brominated polystyrene, carbonate oligomer of brominated bisphenol A, etc.), flame retardant aids (for example, antimony trioxide, sodium antimonate, etc.), antioxidants ( For example, hindered phenol compounds, etc.), ultraviolet absorbers, release agents, lubricants, coloring agents and the like. Further, as the inorganic filler, glass fiber, glass beads, calcium carbonate, talc, silica, mica,
Examples include clay and titanium oxide. Examples of other thermoplastic resins include polyethylene terephthalate and polybutylene terephthalate. The composition thus obtained can be easily molded by a known method such as injection molding, extrusion molding, compression molding or rotational molding.

[0019]

EXAMPLES The present invention will now be described in more detail with reference to examples. The polycarbonate resin, the vinyl-based thermoplastic resin, the polyether ester amide, and the additives used in the respective examples and comparative examples were as follows. (1) Polycarbonate resin; Panlite L-1225
[Teijin Kasei Co., Ltd., viscosity average molecular weight 22,500] (2) Vinyl-based thermoplastic resin; ABS resin Santac
UT-61 [manufactured by Mitsui Toatsu Chemicals, Inc.] (3) Polyether ester amide A; a compound (m + n = 33) represented by the following general formula (II) obtained by adding ethylene oxide to polycaprolactam + bisphenol A.
To 35) + a copolymer obtained from terephthalic acid [polyamide part: polyether ester part = 50:50 (weight ratio)] polyether ester amide B; polycaprolactam +
Copolymer obtained from polyethylene glycol having a number average molecular weight of 2000 and adipic acid [polyamide part: polyether ester part = 50: 50 (weight ratio)]

[0020]

[Chemical 4]

(4) Antistatic agent; Anionic antistatic agent Chemistat 3033 [manufactured by Sanyo Kasei Co., Ltd.] (5) Stabilizer; Stabilizer A: Trimethyl phosphate Stabilizer B: Distearyl pentaerythritol diphosphite Example And the evaluation in the comparative examples is based on the following methods. (A) Surface resistivity: flat plate (50
X 100 x 2 mm) at 23 ° C and 50% R. H. After standing for 24 hours in a thermostatic chamber with the above humidity, measurement was performed with a super insulation resistance meter (SM-10E manufactured by Toa Denpa Co., Ltd.). After further measurement, after thoroughly washing with water and removing water from the surface,
50% R.I. H. The sample was left standing in a humidity-controlled room for 24 hours and measured again. (B) Impact strength: measured according to ASTM D256. (Thickness ⅛ inch) (C) Heat distortion temperature: Measured according to ASTM D648.

[Examples 1 to 6, Comparative Examples 1 to 6] Tables 1 and 2
Polycarbonate resin, ABS resin in the weight ratio shown in
30mmφ bent type extruder [V manufactured by Nakatani Co., Ltd. V mixed with polyetheresteramide, antistatic agent and stabilizer
SK-30] and the cylinder temperature is 240-250.
Melt extruded at ℃ and pelletized. The obtained pellets were dried at 110 ° C. for 5 hours with a hot air circulation dryer, and were then evaluated by an injection molding machine [FANUC T-150D] at a cylinder temperature of 250 to 280 ° C. and a mold temperature of 70 ° C. for evaluation. A test piece was obtained. The evaluation results are as shown in Tables 1 and 2.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

INDUSTRIAL APPLICABILITY The antistatic resin composition of the present invention has excellent antistatic properties, impact resistance and heat resistance, and is effectively used in a wide range of industrial fields including electric and electronic fields.

Claims (1)

[Claims] 1. (A) Polycarbonate resin 30 to 10
(C) to 100 parts by weight of a resin mixture consisting of 0% by weight and (B) 0 to 70% by weight of a thermoplastic vinyl resin.
(A) one or more compounds selected from aminocarboxylic acids having 6 or more carbon atoms, lactams having 6 or more carbon atoms or diamines and salts having 6 or more carbon atoms, and (b) The following general formula (I): [Wherein R ₁ is an alkylene group having 1 to 6 carbon atoms, an alkylidene group, a cycloalkylene group having 5 to 15 carbon atoms,
Cycloalkylidene group or>O,>S,>SO,>
SO ₂ and> CF ₂ groups, R ₂ and R ₃ represent hydrogen, an alkyl group having 1 to 6 carbon atoms, halogen, a sulfonic acid group and a metal base thereof, and R ₄ and R ₅ represent an ethylene oxide group or propylene oxide. Represents a group, m and n are positive integers, m + n is 16 to 50, and X is 0 or 1 to
Represents a positive number of 4] and a compound obtained by adding an alkylene oxide to an aromatic diol and (c) having 4 to 4 carbon atoms.
An antistatic resin composition comprising 3 to 30 parts by weight of a polyether ester amide obtained by copolymerizing 3 components of 20 dicarboxylic acids.