JP2875168B2 - Antistatic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In general, polycarbonate resins or polycarbonate / ABS blend resins have good mechanical properties and workability, and are used in a wide range of fields. However, since they have high electrical insulation properties, dust and the like adhere to the surface of the resin molded product and are easily contaminated, and their improvement is desired. Conventionally, in order to improve the 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 have been performed. In the former case, the impact resistance and workability are poor, and in the latter case, there is a drawback that the effect is remarkably reduced by a single washing with water and the durability is poor.

A method for imparting a permanent antistatic property to a polycarbonate resin is disclosed in, for example, JP-A-5-437.
No. 87 discloses a resin composition in which a polyetheresteramide, a phosphite, and a phenolic compound are mixed with a polycarbonate resin. Also, ABS
As a method for imparting permanent antistatic ability to resin or polycarbonate resin / ABS resin alloy,
For example, Japanese Patent Application Laid-Open Nos. 62-273252 and
JP-A-1986656 discloses a resin composition in which a polyetheresteramide or a polyetheresteramide in which an aromatic diol compound is partially introduced into a polyether portion is mixed with an addition polymerization type resin. However, none of these 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 by washing with water.

[0005]

The present inventors have made intensive studies to achieve the above object, and as a result, (A) 30-100% by weight of a polycarbonate resin and (B) 0-70% of a vinyl thermoplastic resin. (C) (a) an aminocarboxylic acid having 6 or more carbon atoms, a lactam or diamine having 6 or more carbon atoms and 6 or more carbon atoms synthesized from a dicarboxylic acid with respect to 100 parts by weight of the resin mixture consisting of 100% by weight. One or more compounds selected from salts, (b) the following general formula (I)

[0006]

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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 , and> CF ₂ groups, and R ₂ and R
₃ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a 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 16 to 50, and X
Represents a positive number of 0 or 1 to 4] and a polyether ester obtained by copolymerizing a compound obtained by adding an alkylene oxide to an aromatic diol represented by the following formula: 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 amide maintains mechanical properties and heat resistance and has excellent permanent antistatic properties, and has reached the present invention. Hereinafter, the present invention will be described specifically.

The (A) polycarbonate resin of the present invention comprises:
It is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Representative examples of dihydric phenols 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,
1-bis (4-hydroxyphenyl) cyclohexane and the like. Preferred dihydric phenols are those based on bis (4-hydroxyphenyl) alkane, especially bisphenol A. Examples of the carbonate precursor include carbonyl halide, carbonate ester and haloformate, and specifically, phosgene,
Diphenyl carbonate, dihaloformate of dihydric phenol and mixtures thereof. In producing the polycarbonate resin, the dihydric phenol may be used alone or in combination of two or more. In addition, a suitable molecular weight regulator, a branching agent, a catalyst for accelerating the reaction, and the like can be used. Although the molecular weight of the aromatic polycarbonate resin is not specified, if the molecular weight is less than 10,000, impact resistance and the like will be reduced, and if it is more than 50,000, the moldability will be reduced. 1
It is preferably from 0000 to 50,000,
Those having a size of from 00 to 30,000 are particularly preferred. Further, two or more aromatic polycarbonate resins may be mixed.

The vinyl thermoplastic resin used in the present invention is, for example, acrylonitrile, methacrylonitrile,
Vinyl cyanide compounds such as chloroacrylonitrile, aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, halogenated styrene, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate , Ethyl methacrylate, butyl methacrylate, polymers and copolymers such as acrylates such as octyl methacrylate, or copolymers of two or more in the presence of diene rubber, such as vinyl-based as shown above Examples include a graft copolymer obtained by polymerizing a monomer. As the diene rubber used here, polybutadiene, polyisoprene,
Butadiene-styrene copolymer, butadiene-acrylonitrile copolymer and the like. 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 a single-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer of only a graft component produced as a by-product at the time of production, or two or more thermoplastic graft copolymers may be mixed. One of the vinyl thermoplastic resins of the present invention is a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled 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 the above-mentioned vinyl-based monomers is also used. Among these, butadiene rubber-reinforced acrylonitrile-styrene copolymer (ABS resin), butadiene rubber-reinforced methyl methacrylate-styrene copolymer (MBS resin), and IPN type vinyl polymer are preferable.

Among the constituent components of the polyetheresteramide used in the present invention, the constituent components of the polyamide include 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 diamines and dicarboxylic acids, and as aminocarboxylic acids, 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 include caprolactam, enantholactam, caprylactam and laurolactam, and diamines include tetramethylene diamine, hexamethylenediamine, and the like; dicarboxylic acids include adipine Acids, sebacic acid, decanedicarboxylic acid, isophthalic acid and the like can be mentioned, and as salts of diamine and dicarboxylic acid, salts such as hexamethylenediamine-adipate and hexamethylediamine-sebacate are used. Preferred among these are caprolactam, 11
-Aminoundecanoic acid, 12-aminododecanoic acid, and hexamethylenediamine-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 constituent unit of polyetheresteramide. Used in range. If it is less than 10% by weight, the antistatic property is poor, and
Exceeding the weight% is not preferred because the mechanical strength is low.

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

[0012]

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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 , and> CF ₂ groups, and R ₂ and R
₃ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a 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 16 to 50, and X
Represents 0 or a positive number of 1 to 4], wherein R ₄ and R ₅ are ethylene oxide groups, and m + n is 30 to 4
0 is preferred. If m + n is less than 16, the chargeability is poor, and if it exceeds 50, heat resistance and polymerizability are poor, which is not preferable. Specifically, compounds obtained by adding ethylene oxide or propylene oxide to bisphenol A, compounds obtained by adding ethylene oxide or propylene oxide to tetramethylbisphenol A, compounds obtained by adding ethylene oxide or propylene oxide to bisphenol S, etc. Among them, those obtained by adding 30 to 40 mol of ethylene oxide to 1 mol of bisphenol A (that is, m + n = 30 to 40) are particularly preferable from the viewpoint of polymerizability, antistatic properties, and economy. 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, succinic acid, oxalic acid, adipic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanediic acid, and the like, in particular, terephthalic acid, isophthalic acid, sebacic acid, adipic acid, and dodecanediic acid are preferable in terms of polymerizability and physical properties. .

The polyetheresteramide used in the present invention is prepared by reacting the aminocarboxylic acid (a) or the lactam thereof with the dicarboxylic acid (c) to form a prepolyamide having carboxylic acid groups at both ends. 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)
Is 30 to 100% by weight, preferably 40 to 80% by weight, particularly preferably 50 to 70% by weight.
% By weight. The amount of the vinyl thermoplastic resin as the component (B) is 0 to 70% by weight, preferably 20 to 60, particularly preferably 30 to 50% by weight. The polyetheresteramide 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).
Particularly preferably, it is 5 to 15 parts by weight. When the content of the polycarbonate resin of the component (A) is less than 30% by weight, the heat resistance is inferior. When the content of the polyetheresteramide of the component (C) is less than 3 parts by weight, the antistatic performance is insufficient. If it exceeds, the heat resistance of the resin composition becomes 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 by, for example, adding each component to a V-type blender. , Into a ribbon mixer or tumbler, etc.
An ordinary preparation method is used, such as melting and kneading with a single-screw or twin-screw ordinary extruder, cooling, and cutting into pellets.

The composition of the present invention contains a phosphate such as trimethyl phosphate, or triphenyl phosphite, trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, bis (2,6-di-tert-phosphate). A phosphite, such as (butyl-4-methylphenyl) pentaerythritol diphosphite, in an amount of 0.005 to 1% by weight based on the total composition;
Blending is preferable because thermal stability is further improved. It is preferable to add an antistatic agent such as sodium alkyl sulfonate or sodium alkylbenzene sulfonate in an amount of 0.05 to 2% by weight based on the total composition, since the antistatic property is further improved.

Further, various additives, inorganic fillers, and other thermoplastic resins may be blended as long as the object of the present invention is not impaired. Examples of the various additives include a flame retardant (for example, brominated bisphenol, brominated polystyrene, carbonate oligomer of brominated bisphenol A, etc.), a flame retardant auxiliary (for example, antimony trioxide, sodium antimonate, etc.), an antioxidant ( For example, a hindered phenol compound), an ultraviolet absorber, a release agent, a lubricant, a colorant, and the like. In addition, as the inorganic filler, glass fiber, glass beads, calcium carbonate, talc, silica, mica,
Clay, titanium oxide and the like. 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]

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

[0020]

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(4) Antistatic agent; anionic antistatic agent Chemistat 3033 [manufactured by Sanyo Chemical Co., Ltd.] (5) Stabilizer; stabilizer A: trimethyl phosphate stabilizer B: distearyl pentaerythritol diphosphite Evaluations in Comparative Examples and Comparative Examples are based on the following methods. (A) Surface resistivity: flat plate obtained by injection molding (50
× 100 × 2 mm) at 23 ° C., 50% R.C. H. After standing for 24 hours in a constant temperature chamber with a humidity of, the 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 the water on the surface, 23 ° C,
50% R. H. The measurement was carried out again after being left for 24 hours in a humidity constant temperature room. (B) Impact strength: measured according to ASTM D256. (1/8 inch thickness) (C) Heat deformation temperature: Measured according to ASTM D648.

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

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

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 the electric and electronic fields.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 77/12 C08L 77/12

Claims (1)

(57) [Claims] (A) polycarbonate resin 30 to 10
(C) based on 100 parts by weight of a resin mixture comprising 0% by weight and (B) 0 to 70% by weight of a vinyl thermoplastic resin.
(A) one or two or more compounds selected from salts having 6 or more carbon atoms synthesized from aminocarboxylic acids having 6 or more carbon atoms, lactams or diamines having 6 or more carbon atoms and dicarboxylic acids, (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,> represents CF ₂ group, R ₂ and R ₃ are hydrogen, an alkyl group having 1 to 6 carbon atoms, halogen, sulfonic acid group and represents the metal base, R ₄ and R ₅ ethylene oxide groups or propylene oxide M and n are positive integers, m + n is 16 to 50, and X is 0 or 1
And a compound obtained by adding an alkylene oxide to an aromatic diol represented by the formula (C):
An antistatic resin composition comprising 3 to 30 parts by weight of a polyetheresteramide obtained by copolymerizing three components of 20 dicarboxylic acids.