JPH0925335A - Polyether ester and polycarbonate resin composition containing the same - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a polycarbonate resin composition having a permanent antistatic effect, which does not deteriorate the antistatic performance even when washed with water, without impairing the inherent transparency of the polycarbonate resin. [Structure] (1) Aromatic dicarboxylic acid component containing a specific aromatic dicarboxylic acid component substituted with a sulfonate group,
(2) A poly (alkylene oxide) glycol component having a number average molecular weight of 200 to 50,000, (3) For example, the following formula A halogen atom-containing diol component represented by, and (4)
An antistatic polyether ester (A) consisting of an aliphatic glycol component having 2 to 8 carbon atoms, and a polycarbonate resin composition containing 5 to 40 parts by weight of (A).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyether and a polycarbonate resin composition containing the same,
More specifically, an antistatic polyether ester,
Also, the present invention relates to a polycarbonate resin composition having an excellent antistatic effect and containing it, and having a permanent antistatic property in which such an effect is not deteriorated even by washing with water.

[0002]

2. Description of the Prior Art Aromatic polycarbonates such as bisulfite
Polycarbonate obtained by the reaction of Enol A with phosgene
Carbonate has excellent mechanical properties, high heat distortion temperature, excellent
It has electrical characteristics and high transparency.
It is an excellent resin that has a wide variety of uses such as molded products.
You. However, this resin has a high electric insulating property, and
^FifteenAs it has a high surface resistivity of Ω or more,
Static electricity is easily generated and easily accumulated. Therefore,
Adsorbs dust, for example, during shaping or after shaping
However, the product value may be impaired or an electric shock phenomenon may occur
Disadvantages such as hindering or causing danger
have.

In order to eliminate such drawbacks, the method of kneading an ionic antistatic agent (surfactant) such as an alkyl sulfonate or an alkylbenzene sulfonate into a polycarbonate resin as an additive is only an antistatic effect. It has been generally adopted because it is economical.

In Japanese Patent Publication No. 55-4141, a method using an aliphatic monoglyceride as an additive is disclosed in JP-A-6-
In JP-A-22842, a method using a sulfonic acid amine salt is shown respectively.

However, in the method utilizing only such a low-molecular-weight surfactant, since the surfactant oozes out on the resin surface, the electrostatic effect is high, but the effect decreases when wiped or washed with water. There is a problem of doing.

Therefore, the effect does not disappear even if washed with water,
As a method for imparting a permanent electrostatic effect, a method of mixing an antistatic polymer with a resin is described. For example, Japanese Patent Application Laid-Open No. 62-273252 discloses that a polyether ester amide is mixed with a polycarbonate resin as an antistatic polymer and used.

However, when an antistatic polymer such as a thermoplastic resin having transparency such as polycarbonate is used, turbidity occurs and the transparency is remarkably impaired, and its use as a transparent member is restricted.

At present, it is very difficult to obtain a polycarbonate resin composition having a permanent antistatic effect, good physical properties, heat resistance and transparency.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to industrially provide a polycarbonate resin composition having a permanent antistatic effect which does not deteriorate the electrostatic effect even by washing with water and transparency. To provide the advantage.

[0010]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific aromatic dicarboxylic acid component and a halogen atom-containing glycol component which are nuclear-substituted with a sulfonate group are contained. By mixing a specific amount of a specific polyether ester formed into a polycarbonate resin, it has been found that a large antistatic property can be permanently imparted without impairing various physical properties of the polycarbonate resin, particularly transparency. Arrived

That is, the present invention is (A1) having 6 to 2 carbon atoms.
0 aromatic dicarboxylic acid and / or ester thereof, (A
2) poly (alkylene oxide) glycol having a number average molecular weight of 200 to 50,000, (A3) the following formula (1)

[0012]

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[In the formula (1), X is --C (R ³ ) (R ⁴ ).
-[Wherein R ³ and R ⁴ are each independently a hydrogen atom,
It is an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, and R ³ and R ⁴ may be bonded to each other. ] A divalent alkylene group represented by the formula, —SO ₂ — or —O—. k and 1 are each independently 1-2.
It is an integer of 0. Y is C1, Br or I, R
¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms. m and n are each independently an integer of 0 to 4, and they are never 0 at the same time. ] The halogen atom-containing glycol represented by, and (A4) C2-C2
8 is a polyether ester (A) obtained by polycondensation of an aliphatic glycol of 8, and the above (A1) is represented by the following formula (2):

[0014]

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[In the formula (2), Ar is 3 having 6 to 12 carbon atoms.
Represents a valent aromatic group, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms.
Represents an aryl group, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. ] The aromatic dicarboxylic acid and / or ester thereof substituted with a sulfonate group represented by
Including 0 mol%, the content of (A2) is (A1),
5 to 80% by weight of the total amount of (A2), (A3) and (A4), and the content of (A3) is (A1),
The polyether ester is characterized by being 5 to 40% by weight of the total amount of (A2), (A3) and (A4).

Hereinafter, the present invention will be described in detail.

The polyether ester (A) of the present invention is
(A1) C6-C20 aromatic dicarboxylic acid and / or ester thereof, (A2) number-average molecular weight 200-500
00 poly (alkylene oxide) glycol, (A
3) The following formula (1)

[0018]

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[In the formula (1), X is --C (R ³ ) (R ⁴ ).
-[Wherein R ³ and R ⁴ are each independently a hydrogen atom,
It is an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, and R ³ and R ⁴ may be bonded to each other. ] A divalent alkylene group represented by the formula, —SO ₂ — or —O—. k and 1 are each independently 1-2.
It is an integer of 0. Y is C1, Br or I, R
¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms. m and n are each independently an integer of 0 to 4, and they are never 0 at the same time. ] The halogen atom-containing glycol represented by, and (A4) C2-C2
The aliphatic glycol of 8 can be obtained by polycondensation.

Here, examples of the aromatic dicarboxylic acid having 6 to 20 carbon atoms include terephthalic acid, isophthalic acid, and 2,6-
Examples thereof include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid. Examples of the aromatic dicarboxylic acid ester having 6 to 20 carbon atoms include dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate, 2,6-
Examples thereof include dimethyl naphthalenedicarboxylate, diethyl 2,6-naphthalenedicarboxylate, dimethyl 2,7-naphthalenedicarboxylate, and diethyl 2,7-naphthalenedicarboxylate. These may have a substituent such as an alkyl group or halogen on the aromatic ring. Of these, terephthalic acid, 2,6
-Naphthalenedicarboxylic acid, dimethyl terephthalate,
Dimethyl 2,6-naphthalenedicarboxylate is preferred.

In the present invention, the aromatic dicarboxylic acid and / or its ester (A1) is represented by the following formula (2):

[0022]

[Chemical 6]

The sulfonic acid base represented by (-SO ₃ ^- M ⁺⁾ it is necessary to have been containing 2 to 50 mol% aromatic dicarboxylic acids and / or esters thereof substituted with.

In the above formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom or a methyl group. Is an alkyl group having 1 to 3 carbon atoms of an ethyl group.

Here, M ⁺ represents an ion selected from metal ions, tetraalkylphosphonium ions and tetraalkylammonium ions. M ⁺ is an alkali metal ion such as sodium ion, potassium ion or lithium ion, an alkaline earth metal ion such as calcium ion, magnesium ion or barium ion, zinc ion, tetrabutylphosphonium ion, tetramethylphosphonium ion, tetrabutylammonium Ion, tetramethylammonium ion and the like. Of these ions, metal ions are preferable, and alkali metal ions, zinc ions and barium ions are more preferable. However, in the case of a divalent metal ion, 1 mol of the metal ion corresponds to 2 mol of the sulfonate group.

Ar in the above formula (2) is a trivalent aromatic group having 6 to 12 carbon atoms such as a benzene ring and a naphthalene ring, and these are also an alkyl group, a phenyl group, a halogen, an alkoxy group and the like. May have a substituent.

As such an aromatic dicarboxylic acid, 4-
Sodium sulfo-isophthalic acid, 5-natourim sulfo-isophthalic acid, 4-potassium sulfo-isophthalic acid, 5-potassium sulfo-isophthalic acid, 2-sodium sulfo-terephthalic acid, 2-potassium sulfo-terephthalic acid, 4-sulfo-isophthalic acid Zinc acid salt, 5-sulfo-
Zinc isophthalate, 2-sulfo-zinc terephthalate, 4
-Sulfo-barium isophthalate, 5-sulfo-barium isophthalate, 2-sulfo-barium terephthalate,
4-sulfo-isophthalic acid tetraalkylphosphonium salt, 5-sulfo-isophthalic acid tetraalkylphosphonium salt, 4-sulfo-isophthalic acid tetraalkylammonium salt, 5-sulfo-isophthalic acid tetraalkylammonium salt, 2-sulfo-terephthalic acid Tetraalkylphosphonium salt, 2-sulfo-terephthalic acid tetraalkylammonium salt, 4-sodium sulfo-2,
6-naphthalenedicarboxylic acid, 4-sodium sulfo-
2,7-naphthalenedicarboxylic acid, 4-potassium sulfo-2,6-naphthalenedicarboxylic acid, 4-sulfo-2
6-naphthalenedicarboxylic acid zinc salt, 4-sulfo-2,
Examples thereof include 6-naphthalenedicarboxylic acid barium salt. Further, as the aromatic dicarboxylic acid ester,
Specific examples include the dimethyl ester and diethyl ester of the aromatic dicarboxylic acids listed above.

Of these, R ⁵ and R ⁶ are both a methyl group or an ethyl group, Ar is a benzene ring, and M is
It is more preferable that ⁺ is an alkali metal ion such as sodium or potassium in terms of antistatic property, polymerizability, mechanical property, color tone and the like.

The compound represented by the above formula (2) is more preferably 4-sodium sulfo-isophthalate dimethyl, 5-sodium sulfo-isophthalate dimethyl, 4
-Potassium sulfo-isophthalate dimethyl, 5-potassium sulfo-isophthalate dimethyl, 2-sodium sulfo-terephthalate dimethyl, 2-potassium sulfo-terephthalate dimethyl and the like.

According to the present invention, an aromatic dicarboxylic acid substituted with a sulfonate group represented by the above formula (2) and /
Alternatively, the amount of the ester is 2 to 50 mol% of the entire aromatic dicarboxylic acid and / or the ester (A1) used.
Is copolymerized so that the compound represented by the above formula (2) occupies 2 to 50 mol% of the entire aromatic dicarboxylic acid and / or its ester. If the proportion of such a compound is less than 2 mol%, the antistatic effect of the polycarbonate resin composition when it is contained in the polycarbonate resin is not sufficient. On the other hand, if it exceeds 50 mol%, the polymerization reaction becomes difficult, and it becomes difficult to obtain the polyether ester (A) having a sufficient degree of polymerization, or the handleability deteriorates. The preferred usage ratio of the aromatic dicarboxylic acid represented by the above formula (2) and / or its ester is 3 to the aromatic dicarboxylic acid and / or its ester (A1).
It is 40 mol%, and more preferably 4 to 30 mol%.

As the poly (alkylene oxide) glycol (A2) which is one of the constituents of the polyether ester (A) in the present invention, an alkylene oxide such as polyethylene glycol, polypropylene glycol, ethylene oxide or propylene oxide is copolymerized. And a poly (alkylene oxide) glycol obtained by the method. As such poly (alkylene oxide) glycol, polyethylene glycol is preferable.

The poly (alkylene oxide) glycol (A2) having a number average molecular weight of 200 to 50,000 is used. If the molecular weight is less than 200, a sufficient antistatic effect cannot be obtained. Further, from the viewpoint of practicality, the upper limit of the molecular weight is about 50,000.
The number average molecular weight of the poly (alkylene oxide) glycol is preferably 500 to 40,000, more preferably 1,000 to 30,000.

The amount of poly (alkylene oxide) glycol (A2) used is such that the content of (A2) constituting the polyether ester (A) is (A1), (A2), (A3) described later, and later described. The total amount of (A4) charged should be 5 to 80% by weight. If it is less than 5% by weight, the antistatic effect is not sufficient, and if it is more than 80% by weight, the handling properties and heat resistance tend to be poor. The preferred amounts of use are (A1), (A2), (A3) and (A
It is 10 to 60% by weight, and more preferably 12 to 50% by weight of the total amount of 4).

Further, poly (alkylene oxide) glycol may be added to the poly (alkylene oxide) glycol within the range not impairing the effects of the present invention.
A diol compound represented by the following formula (3) may be contained.

[0035]

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[In the formula (3), Ar 'is a divalent aromatic group, R ⁷ and R ⁸ are each independently an ethylene group or a propylene group, and p and q are each independently 1-2.
It is an integer of 0. ] The diol compound represented by the above formula (3) is represented by the following formula (3-
The compounds represented by 1) and (3-2) can be preferably used.

[0037]

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[In the formulas (3-1) and (3-2), R ⁷ and R ⁸ , p and q are the same as those in the above formula (3). The above diol compound is more preferably an ethylene oxide adduct of bisphenol A in which R ⁷ and R ⁸ in the above (3-1) are both ethylene groups.

The halogen atom-containing glycol (A3), which is one of the constituent components of the polyether ester (A) in the present invention, has the following formula (1).

[0040]

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Is represented by

In the above formula (1), X is the following formula

[0043]

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[In the formula, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or 5 to 6 carbon atoms.
R ³ and R ⁴ may be bonded to each other. Divalent (cyclo) alkylene groups represented by], -SO ₂ - is a group or -O- group. Preferred examples of X include an isopropylidene group, a cyclohexylidene group and a —SO ₂ — group.

In the above formula (1), R ¹ and R ² are
Each is independently an alkylene group having 2 to 4 carbon atoms, and an ethylene group and a propylene group are preferable.

K and l are each independently an integer of 1 to 20. When it exceeds 20, the effect of improving the transparency of the polycarbonate resin composition becomes small. Preferably 1 to 1
It is an integer of 0, more preferably 1 to 5, and still more preferably 1 to 3.

Y is a Cl, Br or I atom. Of these, the obtained polyether ester (A) has a heat stability of B and a polycarbonate resin composition having a transparency of B.
The r atom is preferred.

Further, m and n are each independently an integer of 0 to 4, but they are never 0 at the same time. Preferably both m and n are 1 or 2, and more preferably,
Both m and n are 2.

Examples of such a halogen atom-containing glycol include compounds represented by the following formula.

[0050]

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Of these, expressions (1-1) and (1-
The compounds represented by 4) and (1-6) can be preferably used, and the compound of the formula (1-1) can be particularly preferably used.

The amount of the halogen atom-containing glycol (A3) used constitutes the polyether ester (A) (A
The content of 3) is 5 to 40% by weight based on the total amount of (A1), (A2), (A3) and (A4) described later, in other words, substantially obtained polyether ester (A).
The total amount is 5 to 40% by weight. If it is less than 5% by weight, the transparency of the obtained polycarbonate resin composition is not sufficient, and if it is more than 40% by weight, the handleability and heat resistance may be insufficient. The preferred amount used is 7 to 30% by weight of the total amount of (A1), (A2), (A3) and (A4), and more preferably 10 to 2%.
0% by weight.

In the polyether ester of the present invention, by using the halogen atom-containing glycol (A3) as a constituent component, the refractive index of the polyether ester approaches the value of the polycarbonate resin, so that the transparency is maintained. It is estimated to be.

Specific examples of the aliphatic glycol (A4) having 2 to 8 carbon atoms in the present invention include ethylene glycol, 1,4-butanediol, propylene glycol,
Examples thereof include 1,6-hexanediol. Of these, 1,4-butanediol and 1,6-hexanediol are preferable in terms of antistatic performance and handleability.

The polyether ester (A) of the present invention is
Phenol / tetrachloroethane (weight ratio 60/40)
Reduced viscosity (concentration 1.2 g
/ Dl) is preferably 0.3 or more. If the reduced viscosity is less than 0.3, the antistatic effect is not sufficient, which may cause deterioration in heat resistance and mechanical properties. If the polymer is a substantially linear polymer, the upper limit to the reduced viscosity is preferably high in terms of antistatic effect and mechanical properties, but the upper limit of practical polymerization is about 4.0. . The reduced viscosity is more preferably 0.4 or more, and further preferably 0.5 or more.

The polyether ester (A) of the present invention is
It can be obtained by heating and melting the above components (A1) to (A4) at 150 to 300 ° C in the presence of a transesterification catalyst to cause a polycondensation reaction.

The transesterification catalyst is not particularly limited as long as it can be used in a usual transesterification reaction. Such transesterification catalysts include antimony compounds such as antimony trioxide, tin compounds such as stannous acetate, dibutyltin oxide and dibutyltin diacetate, titanium compounds such as tetrabutyl titanate, zinc compounds such as zinc acetate and calcium acetate. Calcium compounds such as sodium carbonate,
Examples thereof include alkali metal salts such as potassium carbonate. Of these, tetrabutyl titanate is preferably used.

The amount of the catalyst used may be the amount used in a normal transesterification reaction, and is generally 0.01 to 0.5 mol with respect to 1 mol of the aromatic dicarboxylic acid and / or its ester used. % Is preferable, and 0.03 to
0.3 mol% is more preferable.

It is also preferable to use various stabilizers such as antioxidants together during the reaction.

The temperature at which these compounds (A1) to (A4) are heated and melted and polycondensed is 15 at the initial reaction.
After the esterification reaction and / or transesterification reaction is carried out at 0 ° C. to 200 ° C. for several tens of minutes to dozens of hours while distilling the distillate, a polymerization reaction for polymerizing the reaction product is performed at 180 ° C. to 300 ° C. Done in. This is because if the temperature is lower than 180 ° C, the reaction does not proceed, and if the temperature is higher than 300 ° C, side reactions such as decomposition easily occur. Polymerization reaction temperature is 200 ℃
To 280 ° C is more preferable, and 220 ° C to 250 ° C is even more preferable. Although the reaction time of this polymerization reaction depends on the reaction temperature and the amount of catalyst, it is usually several tens of minutes to several tens of hours.

The polycarbonate resin composition of the present invention mainly comprises 5 to 40 parts by weight of the polyether ester (A) and 95 to 60 parts by weight of the polycarbonate resin (B). When the amount of the polyether ester (A) is less than 5 parts by weight, the antistatic effect of the resin composition may be insufficient. If it exceeds 40 parts by weight, the transparency of the polycarbonate resin itself may be significantly reduced. A preferable ratio is 7 to 30 parts by weight of the polyether ester (A) and 93 to 70 parts by weight of the polycarbonate resin (B).

As the polycarbonate resin (B), those known in the art which are produced from bisphenols and carbonate precursors such as phosgene and diaryl carbonate can be used. Of these, a polycarbonate resin using 2,2-bis (4-hydroxyphenyl) propane as the bisphenol is preferable.

The viscosity average molecular weight of the polycarbonate resin is preferably about 10,000 to 30,000.

The method for producing the polycarbonate resin composition of the present invention is not particularly limited, but the above-mentioned polyether ester (A), polycarbonate resin (B) and, if necessary, the ionic interface described below. Activator, and various additives, in a commonly used method,
It can be easily manufactured by melt-kneading.
Of these, melt-kneading using a twin-screw extruder is preferable.
The mixing temperature depends on the polycarbonate (B) used, but is generally about 200 ° C to 300 ° C, preferably 220 ° C to 280 ° C.

The polycarbonate resin composition containing the polyether ester of the present invention shows an excellent permanent antistatic property by itself, but when it further contains an ionic surfactant, it exhibits an excellent antistatic property. preferable.

As such a surfactant, an ionic surfactant such as an alkyl sulfonate or an alkylbenzene sulfonate is preferable. Examples of the alkyl sulfonate include sodium dodecyl sulfonate, potassium dodecyl sulfonate, sodium decyl sulfonate, potassium decyl sulfonate, sodium cetyl sulfonate, and potassium cetyl sulfonate. Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium decylbenzenesulfonate, potassium decylbenzenesulfonate, sodium cetylbenzenesulfonate, and potassium cetylbenzenesulfonate. These ionic surfactants can be used alone or in combination of two or more.

Such an ionic surfactant is used in an amount of 0.1 to 1 with respect to 100 parts by weight of the polycarbonate resin composition.
The ratio is 0 part by weight. This is because if it is less than 0.1 part by weight, the effect of containing the antistatic property is not sufficient, and if it exceeds 10 parts by weight, it may cause deterioration of physical properties and deterioration of handleability. As such an ionic surfactant, 0.
Preferably 5 to 5 parts by weight, more preferably 1 to 3 parts by weight.

If desired, various additives may be added to the polycarbonate resin composition of the present invention to the extent that transparency is not impaired. Such various additives include glass fiber, metal fiber, aramid fiber, ceramic fiber,
Fibrous reinforcement such as potassium whisker titanate, carbon fiber, asbestos, talc, calcium carbonate, mica, clay, titanium oxide, aluminum oxide, glass flake,
Various fillers such as milled fiber, metal flakes, and metal powder, heat stabilizers or oxidation stabilizers represented by phosphoric acid esters and phosphorous acid esters, light stabilizers, lubricants, pigments,
Additives such as flame retardants, flame retardant aids, and plasticizers may be added as appropriate.

Molded articles made of the polycarbonate resin composition obtained by the present invention are characterized by excellent antistatic property and good transparency. For example, the surface resistivity is about 10 ¹³ Ω or less for antistatic property, and the lightness index value L in the Hunter's color difference formula is 2 for transparency.
It is preferably about 0 or more.

[0070]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a polycarbonate resin composition having a permanent antistatic effect that does not deteriorate the antistatic performance even when washed with water, without impairing the inherent transparency of the polycarbonate resin. . Therefore, it is useful for OA equipment, electronic members, automobile housings, medical members, various containers, covers, films, sheets and the like.

[0071]

EXAMPLES The preferred embodiments of the present invention will be described below with reference to examples, but the present invention is not limited to the examples. In the examples, "part" means "part by weight".

The reduced viscosity is a value measured at 35 ° C. at a concentration of 1.2 (g / dl) in a mixed solvent of phenol / tetrachloroethane (weight ratio 60/40) unless otherwise specified.

Glass transition temperature (Tg) and melting point (Tm)
Was measured by DSC at a heating rate of 10 ° C./min.

Impact strength is 1 / in accordance with ASTM D256
8 inches, heat distortion temperature (HDT) ASTM D64
8 was measured at 1/8 inch and a load of 18.6 kg / cm ² .

The surface specific resistance was measured by leaving a molded product of the polycarbonate resin composition in an atmosphere of 20 ° C. and a humidity of 65% for 24 hours, and then measuring it with a super insulation meter (SM manufactured by Toa Denpa Kogyo Co., Ltd.).
-8210) at an applied voltage of 1000 V before and after washing with water. The molded product was washed with running water at 30 ° C. for 2 hours, and the water was wiped off with clean paper.

Regarding the transparency of the molded product, JIS Z
According to 8730, the lightness index L in the Hunter color difference formula was used for evaluation. The measurement is Z-manufactured by Nippon Denshoku Industries Co., Ltd.
The measurement was carried out by a transmission method at a sample thickness of 2 mm with 300A.

Example 1 30 parts of dimethyl 5-sodium sulfoisophthalate, 78 parts of dimethyl terephthalate, 89 parts of 1,6-hexanediol, 70 parts of polyethylene glycol (number average molecular weight 2000), 35
2 parts of 2,2-bis (3,5-dibromo-4-hydroxyethoxyphenyl) propane and 0.1 part of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the vessel was filled with nitrogen. After the replacement, the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 1.2 mmHg to obtain a polymer. The obtained polyether ester polymer had a reduced viscosity of 1.24, a Tm of 111 ° C. and a Tg of
Could not be detected.

Example 2 24 parts of dimethyl 5-sodium sulfoisophthalate, 78 parts of 2,6-dimethylnaphthalate, 70 parts of 1,6-hexanediol, 10 parts
2 parts of polyethylene glycol (number average molecular weight 200
0), 51 parts of 2,2-bis (3,5-dibromo-4-
(Hydroxyethoxyphenyl) propane and 0.1 part of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the atmosphere in the vessel was replaced with nitrogen.
The temperature was raised to 200 ° C. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that point, the pressure in the reaction system was gradually reduced, and after 30 minutes, 30
mmHg to obtain a high-viscosity polymer. The infrared absorption spectrum of such a polyether ester is shown in FIG. The reduced viscosity of the obtained polyether ester is 0.47, Tm
Was 121 ° C., and Tg could not be detected.

[Example 3] 24 parts of dimethyl 5-sodium sulfoisophthalate, 78 parts of 2,6-dimethylnaphthalate, 71 parts of 1,6-hexanediol, 11
1 part polyethylene glycol (number average molecular weight 200
0), 111 parts of 2,2-bis (3,5-dibromo-4)
-Hydroxyethoxyphenyl) propane, and 0.1
Part of the tetrabutyl titanate was charged into a reactor equipped with a rectification column and a stirring device, and after the inside of the vessel was replaced with nitrogen, under normal pressure,
The temperature was raised to 200 ° C. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that point, the pressure in the reaction system was gradually reduced, and after 30 minutes, 30
mmHg to obtain a high-viscosity polymer. The obtained polyether ester has a reduced viscosity of 0.41 and a Tm of 168 ° C.
And Tg could not be detected.

Example 4 24 parts of 5-sodium sulphate
Dimethyl foisophthalate, 78 parts of 2,6-dimethylna
Phthalate, 70 parts of 1,6-hexanediol, 47
Parts of polyethylene glycol (number average molecular weight 200
0), 47 parts of 2,2-bis (3,5-dibromo-4-
Hydroxyethoxyphenyl) propane, 47 parts bis
Phenol A-ethylene oxide 10mol addition product
(Molecular weight 670, R in the above formula (3-1) ⁷And R⁸But
Both are ethylene groups, and p + q = 10. )as well as
0.1 part of tetrabutyl titanate is used as a rectification column and a stirrer.
After placing the reactor equipped with a reactor and replacing the inside of the vessel with nitrogen,
The pressure was raised to 200 ° C. Distill off methanol at 200 ° C
After reacting for 180 minutes while leaving, the reaction product was stirred.
Placed in a reactor having a vacuum distillation system equipped with a device, under normal pressure,
Distilling the reaction distillate up to 240 ° C over 120 minutes
The temperature was raised. At that point, the pressure inside the reaction system was gradually reduced, and 70 minutes
After that, the pressure was adjusted to 30 mmHg to obtain a high-viscosity polymer. Got
Reduced viscosity of polyether ester is 0.37, Tm is 1
It was 13 ° C, and Tg could not be detected.

Example 5 24 parts of dimethyl 5-sodium sulfoisophthalate, 78 parts of 2,6-dimethylnaphthalate, 70 parts of 1,6-hexanediol, 11
1 part polyethylene glycol (number average molecular weight 200
0), 56 parts of 2,2-bis (3,5-dibromo-4-
Hydroxyethoxyphenyl) propane, 56 parts of bisphenol A-ethylene oxide 10 mol adduct (molecular weight 670, in the formula (3-1), both R ⁷ and R ⁸ are ethylene groups, and p + q = 10) and A reactor equipped with a rectification column and a stirrer was charged with 0.1 part of tetrabutyl titanate, the inside of the container was replaced with nitrogen, and then the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirring device, and under normal pressure,
While distilling off the reaction distillate, the temperature was raised to 240 ° C. over 120 minutes. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 30 mmHg to obtain a high-viscosity polymer. The reduced viscosity of the obtained polyether ester is 0.60 and Tm is 1.
It was 70 ° C., and Tg could not be detected.

[Examples 6 to 10] Polycarbonate resin ("Panlite" L1250 manufactured by Teijin Chemicals Ltd.) manufactured from 2,2-bis (4-hydroxyphenyl) propane and phosgene was used in Examples 1 to 5. The amount of sodium dodecylbenzene sulfonate described above as the polyether ester produced in 1 and the ionic surfactant is 30 mm.
⌀Coaxial rotating 2-axis extruder (Ikegai Iron Works Co., Ltd.)
Manufactured by PCM30) and melt-kneaded under the conditions of a polymer temperature of 280 ° C. and an average residence time of about 10 minutes, and pelletized. Next, an injection molding machine (M-made by Meiki Seisakusho Co., Ltd.)
50B) was used for injection molding at a cylinder temperature of 260 ° C. and a mold temperature of 50 ° C. to produce a molded product having a thickness of 2 mm, and the L value and the surface resistivity were measured. The results are shown in Table 1 together with the mechanical properties.

Comparative Example 1 The polycarbonate resins used in Examples 6 to 10 were molded and evaluated in the same manner as in Examples 6 to 10. The results are shown in Table 1.

Comparative Example 2 Elf Atochem Japa was used instead of the polyether ester used in Examples 6-10.
n, polyether ester amide "PEBAX (MX
1723B) ”was used to obtain a molded product in the same manner as in Examples 6 to 10 and the transparency was evaluated. As a result, the L value was 5.

[0085]

[Table 1]

The polycarbonate resin composition of the present invention comprises
The polycarbonate resin itself did not significantly impair the original transparency, its surface resistivity did not change before and after washing with water, and exhibited a permanent antistatic effect.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum chart of the polyether ester obtained in Example 2.

Claims (3)

[Claims] 1. A1) an aromatic dicarboxylic acid having 6 to 20 carbon atoms and / or its ester, (A2) a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 50,000, and (A3) the following formula (1): Chemical 1] [In the formula (1), X is -C (R ³ ) (R ⁴ )-[where R
³ and R ⁴ are each independently a hydrogen atom or a carbon number of 1 to 5
Represents an alkyl group or a cycloalkyl group having 5 to 6 carbon atoms, and R ³ and R ⁴ may be bonded to each other. ] A divalent alkylene group represented by —SO ₂ — or —O—
It is. k and 1 are each independently an integer of 1 to 20. Y is C1, Br or I, and R ¹ and R ² are each independently an alkylene group having 2 to 4 carbon atoms. m
And n are each independently an integer of 0 to 4, and they are never 0 at the same time. ] A halogen atom-containing glycol represented by: and a polyether ester (A) obtained by polycondensing (A4) an aliphatic glycol having 2 to 8 carbon atoms, wherein (A1) is represented by the following formula (2): [Chemical 2] [In the formula (2), Ar represents a trivalent aromatic group having 6 to 12 carbon atoms, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms. Represents an aryl group, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. ] 2-50 mol% of aromatic dicarboxylic acid and / or its ester substituted by the sulfonate group represented by the above, and the content of the above (A2) is (A1), (A2),
It is 5 to 80% by weight of the total amount of (A3) and (A4), and the content of (A3) is (A1), (A
2), 5 to 40% by weight of the total amount of (A3) and (A4)
Is a polyether ester. 2. The polyether ester (A) according to claim 1 in an amount of 5 to 40% by weight and a polycarbonate resin in an amount of 60 to 60% by weight.
A polycarbonate resin composition consisting essentially of 95% by weight. 3. An ionic surfactant is added to 100 parts by weight of the polycarbonate resin composition according to claim 2 in an amount of 0.
A polycarbonate resin composition containing 1 to 10 parts by weight.