JPH0940855A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition which has permanent antistatic properties and is excellent in mechanical properties, thermal stability and moldability. SOLUTION: This resin composition comprises (A) 98-50wt.% of an aromatic polycarbonate resin, (B) 2-50wt.% of a polyester-ether containing the hard segment formed from a dicarboxylic acid component including an ester-forming alkali metal sulfonate salt and the glycol component and the soft segment formed from an alkylene glycol component and/or an alkylene oxide adduct to a bisphenol and (C) 0-10wt.% of an organic sulfonate salt type antistatic agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having a permanent antistatic property.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent mechanical properties and are widely used in various fields such as electric and electronic equipment fields, automobile fields, machine fields, medical fields and the like. However, the polycarbonate resin has a high electric resistivity,
Since it is easily charged, various troubles due to static electricity can occur. For example, if a resin molded product is electrostatically charged, dust or dirt may adhere to the surface, impairing its appearance and reducing its commercial value.
It has a drawback that it causes an electric shock phenomenon and hinders its handling. Further, in the electric / electronic parts, there is a case where an erroneous operation is caused, which may cause a serious problem in function. Therefore, it has been desired to develop a so-called permanent antistatic material having an antistatic function and capable of maintaining the function permanently.

Conventionally, in order to impart antistatic properties to polymer materials, a method of applying an antistatic agent on the surface and a method of kneading various low molecular weight antistatic agents into a resin have been generally performed. . However, the antistatic performance is not sufficient with these methods, and when washing with water or wiping the surface, the antistatic property disappears, and the kneading component bleeds out on the surface to deteriorate the quality of the material. In addition, there is a problem in that the antistatic property changes with time and the performance changes.

On the other hand, as a method of imparting a continuous antistatic function to a resin, that is, a permanent antistatic property, it is known to use a polyetheresteramide.
However, when a polyether ester amide is mixed with a polycarbonate resin and kneaded and molded, the temperature at the time of kneading or molding is high, so that there is a problem that a molded product is colored or a defective appearance is likely to occur due to generation of silver or the like. It was
Further, since the polyether ester amide has poor compatibility with other thermoplastic resins, delamination occurs or impact strength is deteriorated, and it is difficult to obtain a resin composition having desirable mechanical properties. There was a problem.

Therefore, JP-A-60-23435 discloses a method of using a modified vinyl polymer having a carboxyl group in a polyether ester amide as a compatibilizing agent, and JP-A-2-70739. The publication proposes a method in which a rubber-modified styrene-based thermoplastic resin containing a vinyl monomer having a hydroxyl group as a copolymerization component is used as a compatibilizer. However, although the compatibility problem is improved by these methods, it is necessary to add a large amount of a compatibilizing agent, and the antistatic property is deteriorated as compared with the case where only two other thermoplastic resins are kneaded. was there.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition having a permanent antistatic property and excellent mechanical properties, thermal stability and moldability.

[0007]

The present invention has been made to solve the above-mentioned problems, and the gist thereof is [A] aromatic polycarbonate resin 98 to 50% by weight [B] ester-forming sulfone. 2 to 50% by weight of a polyester ether comprising a hard segment formed from a dicarboxylic acid containing an acid alkali metal salt compound and a glycol and a soft segment formed from an alkylene glycol and / or an alkyleneoside adduct of bisphenol And [C] an organic sulfonate-type antistatic agent in an amount of 0 to 10% by weight.

The present invention will be described in detail below. The aromatic polycarbonate resin [A] in the present invention is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate. Another example is copolymerization, and a typical example thereof is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compound include bisphenol A, bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, and 2,2 '-(4-hydroxyphenyl).
Butane, 2,2 '-(4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 1,1'-bis ( 4-hydroxy-3
-Tert-butylphenyl) propane, 2,2'-bis (4
-Hydroxy-3-bromophenyl) propane, 2,
2'-bis (4-hydroxy-3,5 dibromophenyl) propane, 2,2'-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5 dichlorophenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclopentane, 1,1′-bis (4-
Bis (hydroxyaryl) cycloalkanes such as hydroxyphenyl) cyclohexane, 4,4′-
Dihydroxy diphenyl ethers, dihydroxy diaryl ethers such as 4,4'dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-
Dihydroxydiaryl sulfides such as 3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4, Examples thereof include dihydroxydiarylsulfones such as 4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

These may be used alone or in admixture of two or more, but in addition to these, piperazine, dipiperidyl, hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like may be mixed and used. The molecular weight of the polycarbonate resin is preferably 14,000 to 50,000 from the viewpoint of the balance between fluidity and strength,
More preferably, it is 18,000 to 30,000. The ratio of the polycarbonate resin to the composition of the present invention is 5
It is 0 to 98% by weight, preferably 60 to 95% by weight.

The polyester ether [B] in the present invention comprises a hard segment and a soft segment. The hard segment is composed of polyester formed from a dicarboxylic acid component containing an ester-forming alkali metal sulfonate compound and a glycol component. The ester-forming alkali metal sulfonate compound is one component of the dicarboxylic acid component, and forms a polyester with a dicarboxylic acid and a glycol component other than the ester-forming alkali metal sulfonate compound.
Specific examples of the ester-forming alkali metal sulfonate compound include 5-sodium sulfoisophthalic acid and 5-sodium sulfoisophthalic acid.
Examples thereof include potassium sulfoisophthalic acid, and ester-forming derivatives thereof, such as dimethyl ester, diethyl ester, diphenyl ester and the like. Among these, 5-sodium sulfoisophthalic acid and its ester-forming derivative are preferable.

The ester-forming alkali metal sulfonate compound is 1 to 50 mol% based on the entire dicarboxylic acid component. When it is less than 1 mol%, the antistatic property of the polycarbonate resin composition becomes insufficient, and when it is more than 50 mol%, the polymerization when forming the polyester segment becomes extremely difficult. From the viewpoint of the balance between antistatic property and polymerizability, it is preferably 2 to 40 mol%, more preferably 3 to 35 mol%.

Ester-forming sulfonic acid dicarboxylic acid components other than alkali metal include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, trimesic acid. , Trimellitic acid, and ester-forming derivatives thereof.
These dicarboxylic acid components may be used alone or in admixture of two or more.

As the glycol component in the present invention,
Examples thereof include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, diethylene glycol and the like. These may be used alone or in combination of two or more. Other diols or polyhydric alcohols together with these aliphatic glycols,
For example, cyclohexanedimethanol, xylylene glycol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2'-bis (4-hydroxyethoxy) Phenyl) propane, 2,2′-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, glycerin, pentaerythritol and the like may be mixed and used.

The soft segment in the present invention is formed from an alkylene glycol component and / or an alkyleneoside adduct component of bisphenol. Examples of the alkylene glycol component include aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol and thiodiethylene glycol. Particularly preferred is ethylene glycol. These can be used as a mixture of two or more kinds.

In addition to these aliphatic glycols, other diols or polyhydric alcohols such as cyclohexanedimethanol, xylylene glycol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-) Mix 3,5-dibromophenyl) propane, 2,2'-bis (4-hydroxyethoxyphenyl) propane, 2,2'-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, glycerin, pentaerythritol, etc. Can be used.

The alkylene oxide adduct component of bisphenol is a component obtained by addition reaction of alkylene oxide with bisphenol. As bisphenols, bisphenol A, bisphenol S, brominated bisphenol A, 4,4'-bis (hydroxyphenyl)
Examples thereof include sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether and bis (4-hydroxyphenyl) amine. Bisphenol A is preferred.

Examples of the alkylene oxide include ethylene oxide (EO) and / or propylene oxide (PO). When EO and PO are used in combination, they may be random addition or block addition. Preferably EO
It is. The number of moles of alkylene oxide added is 2 to 80 mol, preferably 10 to 1 mol of bisphenol.
50 moles.

The proportion of the alkylene glycol and the alkylene oxide adduct of the bisphenol in the soft segment formed from the alkylene oxide adduct of the alkylene glycol and the bisphenol can be arbitrarily selected. When the proportion of the alkylene oxide adduct of bisphenol is increased, the heat resistance is improved, and when the proportion of the alkylene glycol is increased, the antistatic property is improved.

The number average molecular weight of the soft segment, which is a polymer formed from an alkylene oxide adduct of alkylene glycol and / or bisphenol, is 400.
If it is less than 400, the antistatic property becomes insufficient, and if it exceeds 40,000, the reactivity decreases.
The antistatic property of the resulting composition also decreases. From the viewpoint of the balance between antistatic property and reactivity, the number average molecular weight of the soft segment is preferably 1,000 to 30,000, more preferably 2,000 to 25,000.

The ratio of the soft segment to the polyester ether is 10 to 90% by weight. 10% by weight
If it is less than 90% by weight, the antistatic property is insufficient, and if it exceeds 90% by weight, the heat resistance and mechanical properties of the polycarbonate resin composition are deteriorated. From the viewpoint of the balance between antistatic property, heat resistance and mechanical properties, it is preferably 20 to 90% by weight.

In the present invention, the ratio of [B] polyester ether to the polycarbonate resin composition is 2 to
50% by weight. If it is more than 50% by weight, heat resistance and mechanical properties are deteriorated, and if it is less than 2% by weight, the antistatic property is not sufficient. From the viewpoint of the balance between heat resistance, mechanical properties and antistatic properties, it is preferably 3 to 30% by weight.

The production of the polyester ether [B] in the present invention is carried out by a conventionally known production method of polyester ether. For example, the alkyl ester of the dicarboxylic acid component and the glycol component are transesterified in the presence of a suitable catalyst (such as a titanium compound) to produce the hard segment portion. Then, a method of adding a polymer comprising an alkylene glycol and / or an alkylene oxide adduct of bisphenol, which is a soft segment component, and carrying out a polycondensation reaction under reduced pressure can be mentioned. Alternatively, a method of reacting a polyester segment previously produced with a soft segment component,
Examples thereof include a method of reacting a relatively high molecular weight polyester in the presence of a soft segment while depolymerizing. In such a reaction, it is preferable to add a small amount of antioxidant to the polymerization system from the viewpoint of thermal stability of the obtained polymer.

The solution viscosity ηrel of the polyester ether is 1.2 to 8.0, preferably 1.0 to 5.0. The solution viscosity of polyester ether is 1, 1, 2,
Using a mixed solvent of 2-tetrachloroethane / phenol = 1/1 (weight ratio), the temperature is 30 ° C. and the solution concentration is 0.5.
Measured in g / 100 cc, the solution viscosity ηrel is determined by the number of seconds of dropping the solution / second of dropping the mixed solvent.

In the polycarbonate resin composition of the present invention, by adding the organic sulfonate type antistatic agent [C], even if a relatively small amount of polyester ether is added, the permanent antistatic property can be obtained. A composition having excellent heat resistance and mechanical properties is obtained.

The organic sulfonate type antistatic agent in the present invention is a compound represented by the general formula (1). R-SO ₃ M (1) formula (1), R is 1 to 32 carbon atoms, a linear or branched aliphatic hydrocarbon group or an aromatic hydrocarbon radical, preferably having a carbon number of 8-28 Is a linear or branched aliphatic hydrocarbon group or aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group, which may have a substituent such as an alkyl group. M is
Examples thereof include alkali metal, alkaline earth metal, phosphonium ion, ammonium ion and carbonium ion. M is preferably an alkali metal, and most preferably sodium ion.

Specific examples of the organic sulfonate-type antistatic agent represented by the general formula (1) include sodium n-hexylsulfonate, sodium n-dodecylsulfonate, and n.
-Alkyl sulfonate type antistatic agents such as sodium octadecyl sulfonate and potassium dodecyl sulfonate,
Alkylbenzene sulfonic acid metal salt type antistatic agents such as sodium decylbenzene sulfonate, sodium dodecylbenzene sulfonate, sodium stearyl benzene sulfonate, sodium octyl benzene sulfonate, potassium dodecyl benzene sulfonate, sodium octyl naphthalene sulfonate, dodecyl naphthalene sulfone Examples thereof include alkyl naphthalene sulfonic acid metal salt type antistatic agents such as sodium acid salt and potassium dodecyl naphthalene sulfonate.

The organic sulfonate type antistatic agents may be used either individually or in combination of two or more. The ratio of the organic sulfonate type antistatic agent to the polycarbonate resin composition is 0 to 10% by weight. If it exceeds 10% by weight, the mechanical properties of the polycarbonate resin will be significantly reduced. From the viewpoint of the balance between antistatic properties and mechanical properties, it is preferably 0.1 to 10% by weight, more preferably 0.5 to 5%.
% By weight. As described above, a composition obtained by blending a specific amount of a specific polyether ester with a polycarbonate resin, or a composition obtained by blending a predetermined amount of an organic sulfonate-type antistatic agent with such a composition has an antistatic property,
Excellent in mechanical properties and heat resistance.

The resin composition of the present invention comprises the above component [A].
In addition to [B] and [C], various known additives such as glass fibers, glass flakes, glass beads, carbon fibers, mineral fibers, metal fibers, and ceramics may be added, if necessary, within a range that does not impair the characteristics of the composition. Reinforcing agents such as whiskers, fillers such as titanium oxide, silica, alumina, carbon black, calcium carbonate, mold release agents such as paraffin wax, polyethylene wax, bees wax, silicone oil, various plasticizers, and hindered phenols , Antioxidants such as phosphorous acid ester type, sulfur-containing ester compound type,
It may contain a flame retardant such as a halogen compound or a phosphoric acid compound, an ultraviolet absorber or a weather resistance-imparting agent, a dye, a pigment or a foaming agent, and a polyester resin such as PET or PBT, nylon 6, nylon 66, Various nylons such as nylon 12, nylon MXD6, various nylon elastomers, polystyrene, ABS, AS, MS and other styrene resins, various acrylic resins, polyethylene, polypropylene, ethylene-propylene copolymers and other olefin resins, and elastomers. As the material, isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, ionomer resin, phenoxy resin, polycaprolactam, etc. may be contained.

The resin composition of the present invention can be produced by mixing the above-mentioned components [A], [B] and [C], and various additive components used as necessary, and kneading. it can. The compounding is a commonly used method, for example,
It is carried out with a ribbon blender, a Hensell mixer, a drum blender, or the like. Various extruders, Brabender Plastograph, Labo Plastomill, kneader, Banbury mixer, etc. are used for melt-kneading. The heating temperature at the time of melt-kneading is usually about 220 to 300 ° C. In order to suppress decomposition during kneading, it is preferable to use the above-mentioned antioxidant.

The polycarbonate resin composition of the present invention comprises
Various known molding methods, such as injection molding, blow molding,
By extrusion molding, compression molding, calender molding, rotational molding and the like, molded products in the fields of electric and electronic devices, automobiles, machines, medical fields and the like can be obtained. Upon molding to obtain the final molded product, it is preferable to control the resin temperature to about 220 to 300 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.

EXAMPLES "Parts" in the examples means "parts by weight". still,
The resin compositions of Examples and Comparative Examples were molded into molded pieces by injection molding, and then the performance was evaluated by the following test methods.

1) Antistatic Property The antistatic property was evaluated by measuring the surface specific resistance value. Using an Ultra High Resistance Meter (Advantest), according to ASTM D-257,
A test piece (a disk with a diameter of 10 cm and a thickness of 3 mm) is heated at a temperature of 2
After standing for 3 days or more at 3 ° C and 50% humidity,
The surface specific resistance value was measured. The smaller the value, the better the antistatic property.

2) Permanent antistatic property After the test piece evaluated for antistatic property was washed with water, it was allowed to stand for 3 days or more under the conditions of temperature 23 ° C. and humidity 50%.
After adjusting the condition, the surface resistivity of the water-washed product was measured. It can be said that the material is excellent in permanent antistatic property if the surface resistivity without washing treatment is low and the surface resistivity of the rinsed product is kept low. In addition, the washing process is 8m inside diameter
While flowing tap water at a flow rate of 5 L / min from the hose of m, on a molded test piece placed 15 cm directly under the hose,
The tap water was moved at a vertical angle for 40 seconds so as to be uniformly applied. After that, the test piece was sprinkled with demineralized water, and was easily replaced and washed.

3) Mechanical Properties Bending strength and flexural modulus were measured by ASTM D790. 4) Thermal Properties The deflection temperature under load (HDT) was measured according to ASTM D-648 on a prismatic test piece having a cross section of 6.4 mm × 12.7 mm under a high load of 18.5 kgf / cm ² . The higher this value, the better the heat resistance. 5) Appearance (defect phenomenon, change in color tone) The appearance was evaluated by visually observing a continuously molded forming test piece and observing whether there was a change in color tone or a defect phenomenon. The evaluation was based on the following criteria. ◯ indicates good (no defective phenomenon), Δ indicates slightly defective, and x indicates defective (mostly defective phenomenon).

Details of the raw materials used in Examples and Comparative Examples are as follows. a) Polycarbonate resin PC (manufactured by Mitsubishi Engineering Plastics Co., Ltd., Iupilon S-3000, viscosity average molecular weight 21,000) b) Organic sulfonate type antistatic agent R-SO ₃ Na (Nikko Petrochemical Industry Co., Ltd.) Atrai 1030) c) Heat stabilizer (trade name ADEKA STAB P manufactured by Asahi Denka Co., Ltd.)
EP-36)

[Example-1] 125 parts of dimethyl terephthalate (DMT) and dimethyl isophthalate (DMI) were placed in a reactor equipped with a stirrer, a thermometer, and a methanol distilling tube.
125 parts, 50 parts of dimethyl 5-sodium sulfoisophthalate (SDM), ethylene glycol (EG) 185
Parts, sodium acetate 3.8 parts, zinc acetate 0.24 parts (2.5% EG solution), and antimony trioxide 0.24.
(1.0% EG solution) was charged, and the temperature was gradually raised with stirring. After distilling a predetermined amount of methanol (internal temperature 22
(0 ° C.) 0.24 parts of phenylphosphonic acid was added and stirred. 700 parts of polyethylene glycol (PEG) having a molecular weight of 4000 and 1,3,5-
1.5 parts of trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene was charged. Then, while stirring the autoclave having an internal temperature of about 220 ° C, the temperature was raised to 250 ° C in about 30 minutes, and the pressure was reduced to 1 mmHg or less. After reacting at that temperature for 2 hours, the pressure was restored to normal pressure with nitrogen gas. Then, the polymer was taken out from the pores in the lower part of the autoclave and pelletized. The solution viscosity ηrel of the obtained polymer was 2.
It was 700. The obtained polymer is referred to as polyether ester A.

10 parts by weight of the above polyether ester A, 88 parts by weight of a polycarbonate resin, 2 parts by weight of an organic sulfonate type antistatic agent R-SO ₃ Na and 0.3 parts by weight of a heat stabilizer were tumbled. Blended for 10 minutes.
Using a twin-screw extruder, blend the mixture at a cylinder temperature of 27.
The mixture was melt-kneaded at 0 ° C. and pelletized. After drying the obtained pellets, injection molding was performed at 270 ° C. to obtain test pieces for evaluating physical properties. Surface resistivity after humidity control is 8.9 x
It was 109 Ω / cm ² . The surface specific resistance value of the water-washed product was 7.5 × 10 10 Ω / cm 2. As a result of measuring the mechanical properties, the flexural modulus was 22800 Kgf / cm ² ,
The bending strength was 880 Kgf / cm ² . HDT (18.
The load (5 Kgf / cm ² load) was 125 ° C. In addition, when the appearance of the molded product was observed, it was good without any defective phenomenon (such as occurrence of silver streak) and color tone change.

[Example-2] 15 parts by weight of the above polyether ester A, 85 parts by weight of a polycarbonate resin,
0.3 part by weight of the heat stabilizer was blended in the same manner as in Example 1, melt-kneaded using a twin-screw extruder, and pelletized. The surface specific resistance value of this injection-molded test piece after humidity control was 5.0 × 10 10 Ω / cm ² , and the surface specific resistance value of the water-washed product was 8.1 × 10 10 Ω / cm ² .
As a result of measuring the mechanical properties, the bending elastic modulus is 21000 Kg.
The bending strength was f / cm ² and the bending strength was 780 kgf / cm ² . HD
T (18.5 Kgf / cm ² load) was 119 ° C. Defects in the appearance of molded products (such as the occurrence of silver streaks)
No change in color tone was observed and it was good.

Examples-3 to 8 and Comparative Examples-1 to 3 In the same manner as in Example 1, various polyester ethers shown in Table 1 were produced. In Table 1, TPA is terephthalic acid unit, IPA is isophthalic acid unit, SD
M represents a sodium sulfoisophthalic acid unit, and EG represents an ethylene glycol unit. The composition and solution viscosity of the obtained polyester ether are shown in Table 1. Each of these polyester ethers was blended in the same manner as in Example 1, melt-kneaded using a twin-screw extruder, and pelletized. Using the obtained pellets, test pieces were obtained by injection molding, and various physical properties were evaluated. The results are shown in Table 2.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

EFFECT OF THE INVENTION The polycarbonate resin composition of the present invention has good and permanent antistatic properties, less deterioration of mechanical properties inherent to the base polymer, excellent thermal properties, and stable heat of fusion. The property is also good. Molded articles comprising the polycarbonate resin composition of the present invention are less likely to have dust or dirt attached to the surface due to electrostatic charging, have an excellent appearance and enhance the commercial value, and also have functional problems such as causing erroneous operation and charging troubles due to electric shock phenomenon. Is less likely to occur, and can be widely used in many fields such as electric and electronic equipment fields, automobile fields, machine fields, medical fields, and the like.

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[Procedure amendment]

[Submission date] February 14, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction contents]

The solution viscosity ηrel of the polyester ether is 1. 0 to 8.0, preferably 1. 2 to 5.0. The solution viscosity of polyester ether is 1, 1, 2,
Using a mixed solvent of 2-tetrachloroethane / phenol = 1/1 (weight ratio), the temperature is 30 ° C. and the solution concentration is 0.5.
Measured in g / 100 cc, the solution viscosity ηrel is determined by the number of seconds of dropping the solution / second of dropping the mixed solvent.

[Procedure amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction contents]

The resin composition of the present invention comprises the above component [A].
In addition to [B] and [C], various known additives such as glass fibers, glass flakes, glass beads, carbon fibers, mineral fibers, metal fibers, and ceramics may be added, if necessary, within a range that does not impair the characteristics of the composition. Reinforcing agents such as whiskers, fillers such as titanium oxide, silica, alumina, carbon black, calcium carbonate, mold release agents such as paraffin wax, polyethylene wax, bees wax, silicone oil, various plasticizers, and hindered phenols phosphite et <br/> ester-based antioxidants such as sulfur-containing ester compound-based,
It may contain a flame retardant such as a halogen compound or a phosphoric acid compound, an ultraviolet absorber or a weather resistance-imparting agent, a dye, a pigment or a foaming agent, and a polyester resin such as PET or PBT, nylon 6, nylon 66, Various nylons such as nylon 12, nylon MXD6, various nylon elastomers, polystyrene, ABS, AS, MS and other styrene resins, various acrylic resins, polyethylene, polypropylene, ethylene-propylene copolymers and other olefin resins, and elastomers. As the material, isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, ionomer resin, phenoxy resin, polycaprolactam, etc. may be contained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0037

[Correction method] Change

[Correction contents]

Example 1 125 parts of dimethyl terephthalate (DMT) and dimethyl isophthalate (DMI) were placed in a reactor equipped with a stirrer, a thermometer, and a methanol distilling tube.
125 parts, 50 parts of dimethyl 5-sodium sulfoisophthalate (SDM), ethylene glycol (EG) 185
Parts, sodium acetate 3.8 parts, zinc acetate 0.24 parts (2.5% EG solution), and antimony trioxide 0.24.
(1.0% EG solution) was charged, and the temperature was gradually raised with stirring. After distilling a predetermined amount of methanol (internal temperature 22
(0 ° C.) 0.24 parts of phenylphosphonic acid was added and stirred. 700 parts of polyethylene glycol (PEG) having a molecular weight of 4000 and 1,3,5-
1.5 parts of trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene was charged. Then, while stirring the autoclave having an internal temperature of about 220 ° C, the temperature was raised to 250 ° C in about 30 minutes, and the pressure was reduced to 1 mmHg or less. After reacting at that temperature for 2 hours, the pressure was restored to normal pressure with nitrogen gas. Then, the polymer was taken out from the pores in the lower part of the autoclave and pelletized. The solution viscosity ηrel of the obtained polymer was 2.
It was 700. The obtained polymer is referred to as polyether ester A.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction contents]

10 parts by weight of the above polyether ester A, 88 parts by weight of a polycarbonate resin, 2 parts by weight of an organic sulfonate type antistatic agent R-SO ₃ Na and 0.3 parts by weight of a heat stabilizer were tumbled. Blended for 10 minutes.
Using a twin-screw extruder, blend the mixture at a cylinder temperature of 27.
The mixture was melt-kneaded at 0 ° C. and pelletized. After drying the obtained pellets, injection molding was performed at 270 ° C. to obtain test pieces for evaluating physical properties. Surface resistivity after humidity control is 8.9 x
It was 10 ⁹ Ω / cm ² . The surface resistivity of the water-washed product was 7.5 × 10 ¹⁰ Ω / cm ² . As a result of measuring the mechanical properties, the flexural modulus was 22800 Kgf / cm ² and the flexural strength was 880 Kgf / cm ² . HDT (18.5Kg
The f / cm ² load) was 125 ° C. In addition, when the appearance of the molded product was observed, it was good without any defective phenomenon (such as occurrence of silver streak) and color tone change.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

Example 2 15 parts by weight of the above polyether ester A, 85 parts by weight of a polycarbonate resin,
0.3 part by weight of the heat stabilizer was blended in the same manner as in Example 1, melt-kneaded using a twin-screw extruder, and pelletized. The surface resistivity of the injection-molded test piece after conditioning was 5.0 × 10 ¹⁰ Ω / cm ² , and the surface resistivity of the water-washed product was 8.1 × 10 ¹⁰ Ω / cm ^2. It was As a result of measuring the mechanical properties, the flexural modulus is 21000 Kgf /
cm ² , and bending strength was 780 Kgf / cm ² . HDT
(18.5 Kgf / cm ² load) was 119 ° C. The appearance of the molded product was good without any defective phenomenon (such as occurrence of silver streak) and color change.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction contents]

[ Examples 3 to 8 and Comparative Examples 1 to 3] Example 1
Various polyester ethers shown in Table 1 were produced in the same manner as in. In Table 1, TPA is a terephthalic acid unit, IPA is an isophthalic acid unit, SDM is a sodium sulfoisophthalic acid unit, and EG is an ethylene glycol unit. The composition and solution viscosity of the obtained polyester ether are shown in Table 1. Each of these polyester ethers was blended in the same manner as in Example 1, melt-kneaded using a twin-screw extruder, and pelletized. Using the obtained pellets,
Test pieces were obtained by injection molding, and various physical properties were evaluated.
The results are shown in Table 2.

Claims (6)

[Claims] 1. [A] Aromatic polycarbonate resin 98 to 50 wt% [B] A hard segment formed from a dicarboxylic acid component containing an ester-forming alkali metal sulfonate compound and a glycol component, an alkylene glycol component, and Polycarbonate resin composition consisting of 2 to 50% by weight of a polyester ether composed of a soft segment formed of an alkyleneoside adduct component of bisphenol and / or 0 to 10% by weight of [C] an organic sulfonate type antistatic agent Stuff 2. The polycarbonate resin composition according to claim 1, wherein the ester-forming alkali metal sulfonate compound is 1 to 50 mol% based on the entire dicarboxylic acid component. 3. The ratio of the soft segment consisting of an alkylene glycol and / or an alkyleneoside adduct of bisphenol to the polyester ether is 10 to 9.
It is 0 weight%, The polycarbonate resin composition of Claim 1 or 2 characterized by the above-mentioned. 4. The number average molecular weight of a soft segment formed from an alkyleneglycoside and / or an alkyleneoside adduct of bisphenol has a number average molecular weight of 400 to 40,000. Polycarbonate resin composition. 5. The organic sulfonate-type antistatic agent comprises
It is 1 to 10 weight%, The polycarbonate resin composition in any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. The polycarbonate according to claim 1, wherein the organic sulfonate type antistatic agent is an organic sulfonate type antistatic agent represented by the general formula (1). Resin composition. _{R-SO 3 M (1)} ( wherein, R 1 to 32 carbon atoms, a linear or branched aliphatic hydrocarbon group or an aromatic hydrocarbon group, M is an alkali metal, alkaline earth metal, It is a phosphonium ion or an ammonium ion.)