JP3357741B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition comprising a polyester having an aromatic residue whose nucleus is substituted with a sulfonate group, a polyalkylene glycol, and a polycarbonate, and having a permanent antistatic ability.

[0002]

2. Description of the Related Art Polycarbonate has excellent properties such as heat resistance, mechanical properties, moldability, and dimensional stability.
It is used as medical parts, optical parts, and other various molded products. Like other plastics, polycarbonate also has the characteristic of high electrical insulation, but it does not easily dissipate the charged static electricity, causing dust to adhere to products, electric shock to workers, malfunction of instruments and IC chips, etc. The problem has arisen. For this reason, studies on antistatic grades have been made for various plastics including polycarbonate.

[0003] As a method for preventing static charge of plastics, there are an internal addition type and a coating type. The coating type requires a separate process, and the internal addition type is more advantageous in the manufacturing process.

[0004] An internal addition type antistatic method for polycarbonate is generally a method in which a low molecular ionic surfactant such as an alkyl sulfonate or an alkylbenzene sulfonate is kneaded into a polymer because of its excellent effect and economy. Widely known. Above all, there have been proposed many ones using an alkyl (aryl) sulfonate, and those having great effects are disclosed in, for example, JP-A-5-22224.
No. 1 describes an alkane in which the secondary position is substituted with a metal salt of sulfonic acid. In addition, JP-A-62-2
No. 230835 describes a sulfonate utilizing a phosphonium salt.

[0005] Furthermore, Japanese Patent Application Laid-Open No. 55-4141 discloses the use of a low molecular weight surfactant other than the sulfonate, such as a fatty acid ester, as to the use of fatty acid monoglyceride.
JP-A-2-99559 describes the use of a diglycerin fatty acid ester, and JP-A-2-99559 describes the combined use of a glycerin fatty acid maleate and a phosphorus-based antioxidant for improving heat resistance. However, in the method using such a low molecular weight surfactant, although the antistatic effect is high, there is a problem that the effect is weakened by wiping or washing with water since the surfactant seeps out onto the surface.

[0006] Therefore, as a method of solving the above-mentioned drawbacks and imparting a permanent antistatic effect to polycarbonate, i) a method of using a modified polymer by polymer modification, and ii) a method of mixing the antistatic polymer with the polycarbonate. Has been proposed.

I) As a result of the modification of the polymer,
JP-A-63-264627, JP-A-64-14268
In JP-A No. 195, a method is described in which a phosphonium salt of phenolsulfonic acid is chemically bonded to the terminal of a polycarbonate to exert a permanent antistatic effect. Although this method has a permanent antistatic effect, it is less effective if the degree of polymerization of the polymer is increased to utilize molecular terminals, and if the antistatic effect is increased by increasing the antistatic end, mechanical properties are improved. And the heat resistance is reduced.

[0008] On the other hand, ii) a method for preventing electrification by mixing an antistatic polymer with polycarbonate is described in, for example, JP-A-62-273252, in which polyetheresteramide is used as the antistatic polymer. Techniques are disclosed. JP-A-5-9798
In No. 4, it is stated that a graft polymer composed of a polyamide as a trunk polymer and a block polymer of a polyalkylene ether and a polyester as a branch polymer has an effect of reducing the surface resistivity as the antistatic polymer. In JP-A-3-255161, caprolactam, a polycarboxylic acid component capable of forming an imide ring,
An antistatic polymer comprising a polymer of an organic diisocyanate and polyethylene glycol is disclosed in
-222289, polyethylene ether;
There are disclosures of antistatic polymers consisting of isocyanates and glycols. However, in any of the methods of mixing such an antistatic polymer, the expected antistatic effect cannot be obtained unless a relatively large amount is mixed with polycarbonate. Is done. In addition, the heat resistance of the antistatic polymer itself is insufficient, so that it is decomposed when melt-mixed with polycarbonate, and the antistatic polymer becomes special and expensive and costly. are doing.
Furthermore, in this polymer mixed system, there is also a problem that the application is largely limited because only a molded product that hardly transmits light can be obtained.

As an antistatic polymer, polyalkylene glycol has been known for a long time. For example, a method of increasing the antistatic effect by mixing with a synthetic fiber or the like is well known. However, even if polyalkylene glycol is added as an antistatic polymer to a general polymer including polycarbonate, the polyalkylene glycol component is uniformly dispersed because the compatibility between the two is too good, and the antistatic effect is usually reduced. It is known that it cannot be obtained. Therefore, as a solution, EP 0555197 discloses a modified polyalkylene glycol having a reactive group such as a hydroxy group, an epoxy group or an amino group, and an alkali metal salt or an alkaline earth salt capable of forming a complex therewith. A technical content is disclosed in which a polyalkylene glycol is applied to a resin product by using a metal salt in combination. However, such a method is preferable for a polyamide resin or an ABS resin, but it is presumed that the functional group of the polyalkylene glycol reacts with the polycarbonate with respect to the polycarbonate, thereby deteriorating the heat resistance and physical properties of the polycarbonate. Is done.

Further, in US Pat. No. 4,600,123 and US Pat. No. 4,035,346, polymers having an aromatic ring substituted with a sulfonate, specifically, a glass transition temperature having a phosphonium sulfonate salt in the molecule are used as antistatic polymers. Describes polyamides and N-alkylated polyetheresters having a temperature of 25 ° C. or lower. But,
When these polymers are mixed with polycarbonate,
It is easily expected that the heat resistance of the obtained polycarbonate resin composition will be insufficient, and it is considered that it is difficult to obtain a good molded product. Further, JP-A-5-222190 discloses a polyamide having a sulfoisophthalic acid structure as an antistatic polymer. However, polyamide and polycarbonate have poor compatibility, and polyamide has an amine terminal and a carboxylic acid terminal as molecular terminals, and such a reactive molecular terminal is likely to react with polycarbonate and cause foaming. There is a concern, and it is insufficient as an antistatic polymer for a polycarbonate resin.

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

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polycarbonate resin having a permanent antistatic effect without lowering the antistatic effect even by washing with water, good physical properties, heat resistance and transparency. It is to provide a composition industrially advantageously.

[0013]

Means for Solving the Problems The present inventors have conducted intensive studies to obtain a polycarbonate resin having a permanent antistatic property. As a result, a specific polyester containing a core sulfonated aromatic group and a polyester having a core sulfonated aromatic group were obtained. The present inventors have found that a composition containing a polyalkylene glycol exhibits a stable antistatic effect even after washing with water, without impairing the transparency and various physical properties of polycarbonate, and has reached the present invention.

That is, the present invention provides a compound represented by the following formula (I):

[0015]

Embedded image

[In the formula (I), M ⁺ represents an ion selected from the group consisting of a metal ion, a tetraalkylphosphonium ion, and a tetraalkylammonium ion.
Ar is an optionally substituted aromatic group having 6 to 12 carbon atoms. An aromatic residue substituted by sulfonate group represented by] as essential components, the proportion of the polyester repeat unit comprises the components and (A ¹⁾ with other polycarbonate or polyester repeating units (A ²⁾ (A ¹ / a ²⁾ is a polyester (a) 5 to 40% by weight is 10 / 90-50 / 50 in molar ratio, number average molecular weight of 5000 or more polyalkylene glycol (B) 2 to 15% by weight and polycarbonate (C). 45 to It is a polycarbonate resin composition characterized by comprising 93% by weight.

The polyester (A) constituting the resin composition of the present invention must contain the aromatic residue represented by the above formula (I) as an essential component. In Formula (I), Ar is a sulfonate ^- is (-SO ₃ M ⁺⁾ that is substituted with an aromatic group having from 6 to 12 carbon atoms, an alkyl group,
It may have a substituent such as a phenyl group, a halogen or an alkoxy group. As such an aromatic residue, the following formula (VI
I)

[0018]

Embedded image

[In the formula (VII), M ⁺ represents M in the above formula (I)
Same as ⁺ . ] Can be preferably exemplified.

In the above formulas (I) and (VII), M ⁺ represents an ion selected from a metal ion, a tetraalkylphosphonium ion and a tetraalkylammonium ion. Specific examples of M ⁺ include a sodium ion, a potassium ion, a lithium ion, a calcium ion, a magnesium ion, a zinc ion, a tetrabutylphosphonium ion, a tetramethylphosphonium ion, a tetrabutylammonium ion, and a tetramethylammonium ion. Among these ions, metal ions are preferred, and alkali metal ions are more preferred. Here, in the case of divalent ions, 1 mol of M ⁺ ion corresponds to 2 mol of the sulfonic acid group (—SO ₃ ⁻ ) in the sulfonic acid salt group.

The polyester used in the present invention (A) consists of polyester repeat unit A ¹ and the other polycarbonate or polyester repeat unit A ² Metropolitan containing the above essential components. Here, A ¹ is an aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid having a structure represented by the above formula (I) in the molecule or an ester derivative thereof, and 2,2-bis (4-hydroxy (A) a compound obtained by melt polymerization of an aromatic diol such as phenyl) propane, an alkylene glycol such as ethylene glycol, or a polyalkylene glycol such as polyethylene glycol, or a compound having a structure represented by the above formula (I) in the molecule. -It is obtained by melt polymerization or the like from an aromatic diol such as sodium sulfohydroquinone and an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid.

A^TwoIs like unsubstituted terephthalic acid
An aromatic dicarboxylic acid or an ester derivative thereof;
Such as 2,2-bis (4-hydroxyphenyl) propane
Aromatic diols, alkylenes such as ethylene glycol
Glycol or polyethylene glycol
Polyester obtained from polyalkylene glycol,
Aromatic diols such as hydroquinone and terephthal
Acids, aromatic dicarboxylic acids such as isophthalic acid
Corresponding repeating units A, such as polyester ¹During ~
Polyesters without sulfonate group substitution
Return unit or polycarbonate repeat unit
Modified polyethylene with some amide bonds
And terephthalate repeating units.

The above polyester (A) has a reduced viscosity (concentration: 1.2 g / dl) measured at 35 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio: 60/40), depending on the type of sulfonate. Are preferably in the range of 0.05 to 1.2, and 0.07 to 1.0
Are more preferable.

The above-mentioned polyester (A) has the above-mentioned formula (I)
(A ¹ ) comprising a polyester repeating unit (A ¹ ) containing an aromatic residue substituted with a sulfonic acid group as an essential component and another polycarbonate or polyester repeating unit (A ² ), and the ratio (A ¹ / A ² ) Is in a molar ratio of 10/90 to 50/50. A ¹ / A ² is 10/9
If the value is smaller than 0, the effect of adding the polyester is small, and the polyester is uniformly dispersed in the polycarbonate resin composition of the present invention, and the antistatic effect is not sufficient. Also 50/5
When it is larger than 0, the viscosity at the time of melting becomes too high, so that it is difficult to obtain a polyester having a high degree of polymerization. A ¹
/ A ² is preferably 15 / 85-40 / 60.

The polyester (A) may be used alone or in combination of two or more.

The polyester (A) comprising the above two repeating units A ¹ and A ² is represented by the following formula (II)

[0027]

Embedded image

[In the formula (II), M ⁺ represents an ion selected from the group consisting of a metal ion, a tetraalkylphosphonium ion, and a tetraalkylammonium ion. A
r is an optionally substituted aromatic group having 6 to 12 carbon atoms. R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 6 carbon atoms, and R ¹ and R ² may be bonded to each other.
R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and m and n are each independently 0, 1 or 2. And a repeating unit A ¹ represented by the following formula (III):

[0029]

Embedded image

[In the formula (III), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
And R ¹ and R ² may be bonded to each other. R ³ and R ⁴ are each independently
They are an alkyl group having 1 to 5 carbon atoms, a halogen atom and a phenyl group, and m and n are each independently 0, 1 or 2. Polyester consisting essentially of polycarbonate repeat units A ² Metropolitan represented by, i.e. it can be preferably exemplified a polyester carbonate.

The above-mentioned formula (II), in the repeating units A ^1, A ² represented by (III), M ⁺ is a metal ion, especially sodium ions, alkali metal ions such as potassium ions preferably, R ^1, R ² Is preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group and an ethyl group, and both m and n are preferably 0.

In the polyester, the above-mentioned formula (II) and the above-mentioned formula (II) can be used within a range in which the properties are not substantially changed (for example, 20 mol% or less, preferably 10 mol% or less of the whole).
It may contain a repeating unit other than (III). An example of such a case is a repeating unit represented by the following formula (VIII) that does not contain a sulfonate.

[0033]

Embedded image

[In the formula (VIII), R ¹ , R ² , R ³ , R ⁴ ,
m and n are R ¹ , R ² , R ³ , R ⁴ , m,
Same as n. Ar ″ is an aromatic group having 6 to 12 carbon atoms which may be substituted by other than a sulfonate group. ] The above formula
In (VIII), R ¹ and R ² are preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group and an ethyl group, and both m and n are preferably 0. Ar ″ is preferably a phenylene group or a naphthylene group.

The polyester carbonate is produced by heating and melting a diaryl ester of an aromatic dicarboxylic acid, a diaryl carbonate and a bisphenol substituted with a sulfonate group at 250 to 320 ° C. in the presence of a transesterification catalyst. They have a molar ratio of a diaryl carbonate aromatic dicarboxylate and a diaryl carbonate substituted by a sulfonic acid salt group of 10/9.
Used in the range of 0 to 50/50.

The degree of polymerization of the obtained polyester carbonate depends on the kind of the sulfonate, but it is determined that the degree of polymerization in a phenol / tetrachloroethane (60/40 by weight) mixed solvent is 3%.
The reduced viscosity (concentration: 1.2 g / dl) measured at 5 ° C. is 0.
It is preferably in the range of 05 to 1.0. When the reduced viscosity is less than 0.05, the physical properties of the polycarbonate resin composition of the present invention may be significantly reduced during use as compared with the original polycarbonate. In addition, the permanent antistatic effect is not sufficient, and the handling property may be further deteriorated, which is not preferable. On the other hand, if it exceeds 1.0, the viscosity at the time of melting becomes too high, and it becomes difficult to handle, which is not preferable. A more preferred reduced viscosity is 0.06
-0.9, particularly preferably 0.07-0.8.

Examples of the aromatic aryl dicarboxylic acid diaryl ester substituted with a sulfonic acid group include diphenyl 4-sodium sulfoisophthalate, diphenyl 5-sodium sulfoisophthalate, diphenyl 4-potassium sulfoisophthalate, and 5-potassium sulfoisophthalate. Diphenyl phosphoisophthalate, diphenyl 2-sodium sulfoterephthalate, diphenyl 2-potassium sulfoterephthalate, phenyl zinc 4-sulfoisophthalate, diphenyl zinc 5-sulfoisophthalate, diphenyl zinc sulfoterephthalate Zinc salt, diphenyltetraalkylphosphonium 4-sulfoisophthalate, 5-diphenyltetraalkylphosphonium 5-sulfoisophthalate, diphenyltetraalkylammonium 4-sulfoisophthalate , 5 over sulfo over isophthalate diphenyl tetraalkylammonium salts, 2-sulfo over diphenyl terephthalate tetraalkylphosphonium salt, 2
-Diphenyltetraalkylammonium sulfoterephthalate, 4-sodium sulfo 2,6-diphenyl naphthalenedicarboxylate, 4-sodium sulfo 2,7-diphenyl naphthalenedicarboxylate, 4-potassium sulfo 2,6-naphthalenedicarboxylic acid A diaryl ester sulfonate such as diphenyl acid, 4-sulfo 2,6-naphthalenedicarboxylic acid diphenyl zinc salt can be used. Among these, diphenyl 4-sodium sulfoisophthalate, diphenyl 5-sodium sulfoisophthalate, diphenyl 4-potassium sulfoisophthalate, and diphenyl 5-potassium sulfoisophthalate are preferred. These may be used alone or in combination of two or more.

Examples of the diaryl carbonate include diphenyl carbonate, bis (2-methylphenyl) carbonate, bis (4-methylphenyl) carbonate, bis (2-methoxyphenyl) carbonate and bis (4-methoxyphenyl) carbonate. Of these, diphenyl carbonate is particularly preferred.

Examples of bisphenols include 2,2-bis- (4-hydroxyphenyl) -propane and bis-
(4-hydroxyphenyl) -methane, 1,1-bis-
(4-hydroxyphenyl) -ethane, 2,2-bis-
Bis such as (4-hydroxyphenyl) -butane
(Hydroxyphenyl) -alkanes, 1,1-bis-
Bis- (hydroxyphenyl) -cycloalkanes, such as (4-hydroxyphenyl) -cyclohexane, and those compounds that are nuclear alkylated and nuclear halogenated. Of these, the most commonly used representative is 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A). Further, a mixture of the above bisphenols may be used.

The temperature at which these compounds are heated and melted is as follows: an initial reaction is carried out at a temperature of from 200 ° C. to 250 ° C. for several tens of minutes to several tens of hours; Perform at 320 ° C. Reaction temperature is 27
0 ° C to 300 ° C is more preferred. If the temperature is lower than 250 ° C., the reaction does not proceed, and if the temperature is higher than 320 ° C., side reactions such as decomposition tend to occur. The reaction time of this polymerization reaction depends on the reaction temperature and the amount of catalyst, but is usually about several tens to several tens of hours.

The transesterification catalyst used in the above reaction is not particularly limited as long as it can be used in a usual transesterification reaction. For example, antimony compounds such as antimony trioxide, stannous acetate, dibutyltin oxide, tin compounds such as dibutyltin diacetate, titanium compounds such as tetrabutyl titanate, zinc compounds such as zinc acetate, calcium compounds such as calcium acetate, sodium carbonate, Examples thereof include alkali metal salts such as potassium carbonate, and tertiary amines.

The amount of the catalyst used may be the amount used in a normal transesterification reaction, and is generally preferably from 0.01 mol% to 0.5 mol%, and more preferably from 0.03 mol% to 1 mol of a bisphenol. To 0.3 mol% is more preferred.

It is also preferable to use various additives such as an antioxidant at the time of the reaction.

As the polyester (A) constituting the polycarbonate resin composition of the present invention, the following copolymerized polyesters can also be preferably used. That is, the following formula (IV)

[0045]

Embedded image

[In the formula (IV), M ⁺ represents an ion selected from the group consisting of a metal ion, a tetraalkylphosphonium ion, and a tetraalkylammonium ion. A
r is an optionally substituted aromatic group having 6 to 12 carbon atoms. X is an alkylene group having 2 to 12 carbon atoms which may be branched. And a polyester repeating unit A ¹ represented by the following formula (V):

[0047]

Embedded image

[In the formula (V), Ar ′ is an aromatic group having 6 to 12 carbon atoms which may be substituted with a group other than a sulfonate group. X is an alkylene group having 2 to 12 carbon atoms which may be branched. Mention may be made of other polyester repeat consisting essentially of units A ² copolyesters represented by.

In the repeating units A ¹ and A ² represented by the above formulas (IV) and (V), M ⁺ is preferably a metal ion, particularly an alkali metal ion such as a sodium ion or a potassium ion. Ar ′ is an alkyl group other than a sulfonate group, such as a methyl group or an ethyl group, or an aromatic group having 6 to 12 carbon atoms which may be substituted with a halogen atom, and is preferably a phenylene group. X is preferably an alkylene group having 2 to 8 carbon atoms such as an ethylene group and a tetramethylene group. Further, the alkylene group may contain an ether bond or a thioether bond.

The degree of polymerization of the above copolymerized polyester is as follows:
Although it depends on the type of the sulfonate, the reduced viscosity (concentration 1.2 g / dl) measured at 35 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio 60/40) is 0.05 to
It is preferably in the range of 1.2. If it is less than 0.05, the material properties during use, permanent antistatic effect is reduced, and handleability is deteriorated. If it exceeds 1.2, the viscosity at the time of melting becomes high. It is not preferable because it becomes too difficult to handle. A more preferred reduced viscosity is 0.06
0.9, more preferably 0.07 to 0.8.

The above-mentioned copolymerized polyester can be produced by a conventionally known transesterification reaction or a polymerization reaction by direct esterification. That is, a method of heating and melting an aromatic dicarboxylic acid or an ester derivative thereof substituted with a sulfonic acid salt group and an unsubstituted aromatic dicarboxylic acid or an ester derivative thereof at 220 ° C. to 300 ° C. together with an alkylene glycol in the presence of a catalyst. Can be obtained by They are used in a molar ratio of 10/90 to 50/50 of the aromatic dicarboxylic acid or its ester derivative substituted with a sulfonic acid group and the unsubstituted aromatic dicarboxylic acid or its ester derivative.

Examples of the aromatic dicarboxylic acid substituted with a sulfonic acid group or its ester derivative include dimethyl 4-sodium sulfoisophthalate, dimethyl 5-sodium sulfoisophthalate, and dimethyl 4-potassium sulfoisophthalate. Dimethyl potassium sulfoisophthalate, dimethyl 2-sodium sulfoisophthalate, 4-sodium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid, 4-potassium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 2- Sodium sulfoterephthalic acid and the like can be mentioned. Among them, 5-sodium sulfoisophthalic acid,
A preferred example is 5-potassium sulfoisophthalic acid. These may be used alone or in combination of two or more.

Further, unsubstituted aromatic dicarboxylic acids or ester derivatives thereof include dimethyl terephthalate, dimethyl isophthalate, dimethyl 2,6-naphthalenedicarboxylate, terephthalic acid, isophthalic acid, 2,
Examples thereof include 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, phenylindanedicarboxylic acid, and those dicarboxylic acids in which the aromatic ring is alkyl-substituted or halogen-substituted. Of these, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferred. These may be used alone or in combination of two or more.

The alkylene glycol has 2 to 2 carbon atoms.
It is preferable to use those having 12 carbon atoms, and more preferably those having 2 to 8 carbon atoms. Specifically, ethylene glycol, tetramethylene glycol and the like can be exemplified. Such an alkylene glycol may contain an ether bond or a thioether bond. These compounds may be used alone or in combination of two or more.

As the conditions for heating and melting the above compound, the heating temperature is 200 ° C. to 300 ° C., preferably 22 ° C.
The temperature is 0 ° C to 260 ° C, and the reaction time is about several tens minutes to several hours.

In addition, the kind of a preferable catalyst used at that time,
With regard to the amount used, in the case of transesterification, the same transesterification catalyst as used in the production of the polyester carbonate and the amount used can be applied.

The structure of the polyester (A) which is one component of the polycarbonate resin composition of the present invention is represented by NMR, IR,
It can be confirmed by a general analysis method such as elemental analysis. The content of the sulfur atom derived from the sulfonate group in the polyester (A) can also be known by the Doman method, ICP emission analysis, or the like.

According to the present invention, the polyalkylene glycol (B) constituting the polycarbonate resin composition of the present invention must have a number average molecular weight of 5,000 or more. When the molecular weight is less than 5000, a sufficient antistatic effect cannot be obtained. Preferred number average molecular weight is 10,000 or more. There is no particular upper limit to the number average molecular weight as long as it is a substantially linear polymer, and a larger one is more preferable, but from a practical point of view, the upper limit is about 50,000.

The polyalkylene glycol (B) is preferably a polyalkylene glycol mainly composed of polyethylene glycol. As other components, polypropylene glycol or the like may be added.

The polycarbonate (C) used in the present invention is obtained from bisphenols and carbonic acid or a derivative thereof. Here, bisphenols and carbonic acid or their derivatives refer to their esters, salts, and halides.

The polycarbonate (C) used in the present invention has the following formula (VI)

[0062]

Embedded image

[In the formula (VI), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
And R ⁷ and R ⁸ may be bonded to each other. R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and p and q are each independently 0, 1 or 2. ]
The polycarbonate which consists of a repeating unit represented by these is preferable.

In the formula (VI), R ⁷ and R ⁸ are each independently a hydrogen atom,
An alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, for example, methyl, ethyl, propyl,
Normal butyl, isobutyl, pentyl, cyclohexyl and the like can be exemplified. R ⁷ and R ⁸ may be bonded to each other, in which case they form a cycloalkane ring.

Next, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, for example, methyl, ethyl, propyl, normal butyl, isobutyl, pentyl, phenyl, chloro, bromo Etc. can be exemplified. P and q are each independently 0, 1 or 2.

The polycarbonate (C) represented by the above formula (VI) may be a copolymer or a blend polymer containing two or more kinds of the above-mentioned repeating units. Examples of the polycarbonate having a repeating unit of the above formula (VI) include bisphenol A-type polycarbonates wherein R ⁷ and R ⁸ are methyl groups, R ⁹ and R ¹⁰ are hydrogen atoms, and p and q are both 0. Is particularly preferred.

In addition to carbonic acid or its derivative, a small amount of another aromatic or aliphatic dicarboxylic acid or its derivative may be used as a copolymer component.

The polycarbonate used in the present invention is:
It is synthesized by any method such as an interfacial polymerization method, a melt polymerization method, and a solution polymerization method.

In order to obtain the polycarbonate resin composition of the present invention, a viscosity average molecular weight of 15,000 to 400
It is preferred to use a polycarbonate of 00.

The polycarbonate resin composition of the present invention comprises
Substantially, the above three components are 5 to 40% by weight of the polyester (A), 2 to 15% by weight of the polyalkylene glycol (B), and 45 to 93% by weight of the polycarbonate (C). When the content of the polyester (A) is less than 5% by weight, the antistatic effect of the resin composition cannot be sufficiently obtained. On the other hand, if it exceeds 40% by weight, the physical properties of the polycarbonate itself decrease, which is not preferable. The preferred range depends on the use of the resin composition of the present invention. When transparency is more required, it is preferably in the range of 10 to 40% by weight of polyester (A), 2 to 12% by weight of polyalkylene glycol (B), and 48 to 88% by weight of polycarbonate (C). When the antistatic property is more required, the content is preferably in the range of 15 to 35% by weight of the polyester (A), 5 to 15% by weight of the polyalkylene glycol (B), and 50 to 80% by weight of the polycarbonate (C). is there. When heat resistance is further required, the content is preferably in the range of 5 to 35% by weight of polyester (A), 2 to 12% by weight of polyalkylene glycol (B), and 53 to 93% by weight of polycarbonate (C). .

The method for producing the polycarbonate resin composition of the present invention is not particularly limited, but the above-mentioned polyester (A), polyalkylene glycol (B), polycarbonate (C) and, if necessary, further are used. Various additives can be easily produced by melt-kneading by a commonly used method. Among them, melt kneading using a twin screw extruder can be preferably performed. The order of kneading is not particularly limited, and the polyalkylene glycol component (B) and the polycarbonate component (C) may be kneaded in advance and then kneaded with the polyester component (A), or the component (A) and the component (A). A mixture obtained by kneading (C) and a mixture obtained by kneading component (B) and component (C) may be mixed. The kneading temperature at that time is preferably about 200 ° C to 320 ° C, more preferably 2 ° C to 320 ° C.
20 ° C to 300 ° C.

The polycarbonate resin composition of the present invention may contain, if necessary, a fibrous reinforcing agent such as glass fiber, metal fiber, aramid fiber, ceramic fiber, potassium whisker, carbonate fiber, asbestos, and talc. Various fillers such as calcium carbonate, mica, clay, titanium oxide, aluminum oxide, glass flake, milled fiber, metal flake, and metal powder may be appropriately compounded.

In the polycarbonate resin composition of the present invention, a heat stabilizer, an oxidation stabilizer, a light stabilizer,
One or more additives such as a lubricant, a pigment, a flame retardant, and a plasticizer may be mixed.

[0074]

The polycarbonate resin composition of the present invention has a permanent antistatic effect and has good physical properties and transparency. Therefore, it is useful for OA equipment, electronic components, automobile housings, medical components, various containers, covers, and the like.

The polyester (A), the polyalkylene glycol (B) and the polycarbonate (C) that constitute the polycarbonate resin composition of the present invention are not completely uniformly dispersed, but form an antistatic polymer phase. It is presumed that it has an effect of permanently preventing charging.

[0076]

EXAMPLES 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, “parts” means “parts 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. The glass transition temperature (Tg) was measured at a heating rate of 10 ° C./min by DSC. Further, the transparency of the molded product was evaluated by the lightness index L in the Hunter's color difference equation according to JIS Z 8730. The measurement was performed with a sample thickness of 2 mm using Z-300A manufactured by Nippon Denshoku Industries Co., Ltd.
Was measured by a transmission method. Impact strength is ASTM D25
1/8 inch according to 6, heat distortion temperature (HDT) is AS
According to TM D648, 1/4 inch, load 18.6k
g / cm ² .

[Reference Example 1] (Production of polyester carbonate) 60.48 parts of 5
-Diphenyl sodium sulfoisophthalate, 123.
30 parts of diphenyl carbonate, 164.16 parts of bisphenol A, and 0.076 parts of dibutyltin diacetate were placed in a reactor having a vacuum distillation system equipped with a stirrer, and the atmosphere in the vessel was replaced with nitrogen. 2 over 60 minutes
The temperature was raised to 00 ° C. Thereafter, the temperature was raised to 250 ° C. over 180 minutes. At that time, the temperature of the reaction system was gradually raised while reducing the pressure, and after 70 minutes, the temperature was increased to 130 mmHg and 290 ° C. Further, the mixture was reacted for 80 minutes under reduced pressure to obtain a high-viscosity polyester carbonate. The reduced viscosity of this polyester carbonate was 0.16, the Tg was 127 ° C., and the color was pale yellow.

Reference Example 2 (Production of copolymerized polyester) 59.2 parts of dimethyl 5-sodium sulfoisophthalate, 155.2 parts of dimethyl terephthalate, 180 parts of ethylene glycol,
0.17 parts of dibutyltin diacetate was placed in a reactor having a vacuum distillation system equipped with a stirrer, and after the atmosphere in the vessel was replaced with nitrogen, transesterification was performed at 200 ° C. for 180 minutes under normal pressure to remove methanol. Distilled off. Thereafter, the temperature was raised to 280 ° C. while removing the reaction product over 120 minutes.
From that point, the pressure inside the reaction system was gradually reduced to 40 m after 70 minutes.
The pressure was reduced to mHg to obtain a high-viscosity polyester. The reduced viscosity of the polyester was 0.39, the Tg was 47 ° C., and the color was pale yellow.

REFERENCE EXAMPLE 3 (Production of copolymerized polyester) 74.0 parts of dimethyl 5-sodium sulfoisophthalate, 145.5 parts of dimethyl terephthalate, 250 parts of 1,4 butanediol, 0.10 parts of Tetrabutyl titanate was placed in a reactor having a vacuum distillation system equipped with a stirrer, and the inside of the vessel was replaced with nitrogen. Thereafter, transesterification was carried out at 200 ° C. for 180 minutes under normal pressure to remove methanol. Thereafter, the temperature was raised to 240 ° C. while distilling the reaction product over 80 minutes. From that point, the pressure inside the reaction system was gradually reduced, and after 70 minutes, the pressure was reduced to 1.0 mmHg to obtain a high-viscosity polyester. The reduced viscosity of the polyester was 0.17, the Tg was 49 ° C., and the color was pale yellow.

[Reference Example 4] (Production of polyester carbonate) 90.72 parts of 5
-Diphenyl sodium sulfoisophthalate, 107.
86 parts of diphenyl carbonate, 164.16 parts of bisphenol A, and 0.076 parts of dibutyltin diacetate were placed in a reactor having a vacuum distillation system equipped with a stirrer, and the atmosphere in the vessel was replaced with nitrogen. 2 over 60 minutes
The temperature was raised to 00 ° C. Thereafter, the temperature was raised to 250 ° C. over 180 minutes. At that time, the temperature of the reaction system was gradually raised while reducing the pressure, and after 70 minutes, the temperature was increased to 130 mmHg and 290 ° C. Further, the mixture was reacted for 80 minutes under reduced pressure to obtain a high-viscosity polyester carbonate. The reduced viscosity of this polyester carbonate was 0.97, the Tg was 120 ° C., and the color was yellow.

Example 1 15 parts of the polyester carbonate produced in Reference Example 1, 10 parts of polyethylene glycol (molecular weight: 20,000, manufactured by Sanyo Chemical Co., Ltd.) and polycarbonate (“Panlite L1250, manufactured by Teijin Chemicals Ltd.)
75 parts were melt-kneaded using a 30 mmφ co-rotating biaxial extruder (PCM30, manufactured by Ikegai Iron Works Co., Ltd.) under the conditions of a polymer temperature of 280 ° C. and an average residence time of about 10 minutes, and pelletized. Next, using an injection molding machine (M-50B manufactured by Meiki Seisakusho Co., Ltd.), the cylinder temperature was set to 2
Injection molding was performed at 80 ° C. and a mold temperature of 50 ° C. to obtain a molded product having a thickness of 2 mm. After drying this molded product under the conditions of 20 ° C. and 65% humidity for 24 hours, the surface resistivity was measured using a super insulation meter (SM-8210 manufactured by Toa Denpa Kogyo Co., Ltd.).
It measured at 000V. Further, the molded article was washed with running water of 30 ° C. for 2 hours, and after wiping off the moisture, dried under the above-mentioned conditions, and the measurement of the surface resistivity was performed again. The results are shown in Table 1 together with the mechanical properties.

Example 2 20 parts of the polyester carbonate produced in Reference Example 1, 10 parts of polyethylene glycol (molecular weight: 20,000, manufactured by Sanyo Chemical Co., Ltd.) and polycarbonate ("Panlite L1250", manufactured by Teijin Chemicals Ltd.)
70 parts were melt-kneaded in the same manner as in Example 1, and the molded product was evaluated. The results are also shown in Table 1.

Example 3 20 parts of the polyester produced in Reference Example 2, 10 parts of polyethylene glycol (molecular weight: 20,000, manufactured by Sanyo Chemical Co., Ltd.) and 70 parts of polycarbonate (“PANLITE” L1250, manufactured by Teijin Chemicals Limited) were used. Melt kneading was performed in the same manner as in Example 1, and the molded product was evaluated.
The results are also shown in Table 1.

Example 4 15 parts of the polyester produced in Reference Example 3, 10 parts of polyethylene glycol (molecular weight: 20,000, manufactured by Sanyo Chemical Co., Ltd.) and 70 parts of polycarbonate (“Panlite” L1250, manufactured by Teijin Chemicals Limited) were used. Melt kneading was performed in the same manner as in Example 1, and the molded product was evaluated.
The results are also shown in Table 1.

Example 5 20 parts of the polyester carbonate produced in Reference Example 4, 10 parts of polyethylene glycol (molecular weight: 20,000, manufactured by Sanyo Chemical Co., Ltd.) and polycarbonate (“Panlite L1250, manufactured by Teijin Chemicals Ltd.)
70 parts were melt-kneaded in the same manner as in Example 1, and the molded product was evaluated. The results are also shown in Table 1.

[0087]

[Table 1]

[Comparative Example 1] 2 parts of sodium dodecylbenzenesulfonate, 10 parts of polyethylene glycol and polycarbonate resin (“PANLITE” manufactured by Teijin Chemicals Ltd.)
(L1250) 88 parts were melt-kneaded in the same manner as in Example 1, and the molded product was evaluated. Table 2 shows the results.

Comparative Example 2 10 parts of polyethylene glycol (molecular weight: 20,000, manufactured by Sanyo Chemical Co., Ltd.) and polycarbonate (“Panlite” L1250, manufactured by Teijin Chemicals Limited)
90 parts were melt-kneaded in the same manner as in Example 1, and the molded product was evaluated. The results are also shown in Table 2.

Comparative Example 3 20 parts of the polyester carbonate produced in Reference Example 1 and 80 parts of polycarbonate (“Panlite” L1250 manufactured by Teijin Chemicals Ltd.) were used in Example 1.
The mixture was melt-kneaded in the same manner as described above, and the molded product was evaluated. The results are also shown in Table 2.

[0091]

[Table 2]

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08L 69/00

Claims (5)

(57) [Claims] 1. A compound represented by the following formula (I): [In the formula (I), M ⁺ represents an ion selected from the group consisting of a metal ion, a tetraalkylphosphonium ion, and a tetraalkylammonium ion. Ar is an optionally substituted aromatic group having 6 to 12 carbon atoms. An aromatic residue substituted with a sulfonate group represented by the formula (1), and a polyester repeating unit (A
¹⁾ the molar ratio of the other polycarbonate or polyester repeating units ^{(A 2) (A 1 /} A 2) is 10/90
5 to 40% by weight of a 50/50 polyester (A),
2 to 15% by weight of a polyalkylene glycol (B) having a number average molecular weight of 5,000 or more, and polycarbonate (C) 4
A polycarbonate resin composition comprising 5 to 93% by weight. 2. The polyester (A) has the following formula (II): [In the formula (II), M ⁺ represents an ion selected from the group consisting of a metal ion, a tetraalkylphosphonium ion, and a tetraalkylammonium ion. Ar is an optionally substituted aromatic group having 6 to 12 carbon atoms. R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 6 carbon atoms;
¹ and R ² may be bonded to each other. R ³ and R ⁴
Each independently represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and m and n each independently represent 0, 1 or 2. And a polyester repeating unit (A ¹ ) represented by the following formula (III): [In the formula (III), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms, and R ¹ and R ² are mutually bonded. It may be. R ³ and R ⁴ each independently have 1 to 5 carbon atoms.
An alkyl group, a halogen atom, and a phenyl group;
n is each independently 0, 1 or 2. A polyester carbonate substantially consisting of the polycarbonate repeating unit (A ² ) represented by the formula:
2. The reduced viscosity (concentration 1.2 g / dl) measured at 35 [deg.] C. in a mixed solvent of tetrachloroethane (weight ratio 60/40) is in the range of 0.05 to 1.0. Polycarbonate resin composition. 3. The polyester (A) has the following formula (IV):[In the formula (IV), M⁺Is a metal ion, tetraalkylphospho
Ion and tetraalkylammonium ion
Represents an ion selected from the group consisting of Ar is substituted
And an aromatic group having 6 to 12 carbon atoms. X is minute
It is an alkylene group having 2 to 12 carbon atoms which may be branched. ]
A polyester repeating unit represented by the formula (A ¹), And below
Notation (V)[In the formula (V), Ar ′ is substituted with a group other than a sulfonate group.
And an aromatic group having 6 to 12 carbon atoms. X
Is an alkylene group having 2 to 12 carbon atoms which may be branched.
You. ] Other polyester repeating units represented by
(A^TwoA) a more substantially copolyester,
And phenol / tetrachloroethane (weight ratio 60/4)
0) at 35 ° C. in a mixed solvent (concentration 1.
2g / dl) is in the range of 0.05 to 1.2.
The polycarbonate resin composition according to claim 1, wherein
object. 4. The polycarbonate resin composition according to claim 1, wherein the polyalkylene glycol (B) is mainly composed of polyethylene glycol. 5. The polycarbonate (C) is represented by the following formula (VI): [In the formula (VI), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 6 carbon atoms, and R ⁷ and R ⁸ are mutually bonded. It may be. R ⁹ and R ¹⁰ are each independently 1 to 5 carbon atoms.
An alkyl group, a halogen atom, and a phenyl group;
q is independently 0, 1 or 2. The polycarbonate resin composition according to any one of claims 1 to 3, comprising a repeating unit represented by the formula: