JPH048760A - Polycarbonate composition and its production) - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate composition having excellent moldability and giving a molded article having excellent mechanical properties, heat- resistance and hue by kneading an aromatic polycarbonate with a specific polyester in molten state. CONSTITUTION:The objective composition can be produced by melting and kneading (A) 60-95 pts.wt. (preferably 65-95 pts.wt.) of an aromatic polycarbonate, preferably a polymer produced by the melt-polycondensation reaction of an aromatic dihydroxyl compound with a carbonic acid diester and having a terminal hydroxyl content of >=5mol% (especially 5-95mol%) and (B) 40-5 pts.wt. (preferably 35-5 pts.wt.) of a polyester of formula I [X is direct bond, group of formula 11 (R<1> and R<2> are H or univalent hydrocarbon group), etc.; (n) is 2-50] and composed of an aliphatic dicarboxylic acid unit and an aromatic dihydroxyl compound unit and preferably having an intrinsic viscosity of 0.03-0.8dl/g (measured in methylene chloride at 20 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a polycarbonate composition and a method for producing the same. The present invention also relates to a polycarbonate composition with improved resin fluidity and excellent moldability, and a method for producing a polycarbonate composition that can efficiently obtain this polycarbonate composition.

TECHNICAL BACKGROUND OF THE INVENTION Polycarbonate has excellent mechanical properties such as impact resistance, as well as excellent heat resistance and transparency, and is therefore widely used in various applications.

However, polycarbonate has poor fluidity and poor moldability for boat fishing. Therefore, for the purpose of improving the fluidity of polycarbonate, polyester carbonate in which polyester units are introduced into polycarbonate has been proposed.

As a method for producing such a polyester carbonate, for example, a method utilizing a melt polycondensation reaction of an organic dicarboxylic acid, a diaryl carbonate, and an organic diacid group is known.

However, in this method, although the organic dicarboxylic acid with poor thermal stability is used, the reaction is usually carried out at a temperature of 250°C or higher, so it maintains sufficient mechanical properties and heat resistance that it should originally have. A problem is that it is difficult to produce polycarbonate of satisfactory hue.

This problem still exists even when an organic dicarboxylic acid ester is used in place of the organic dicarboxylic acid. That is, in the above method, when an organic dicarboxylic acid ester is used instead of an organic dicarboxylic acid to produce a polyester carbonate that maintains sufficient mechanical properties and heat resistance, the hue of the resulting polyester carbonate deteriorates. There is a problem with this.

On the other hand, as a method for producing polyester carbonate, a method in which organic dicarboxylic acid esters are directly reacted (interfacial method) is also known, but it is difficult to obtain polyester carbonate with a good hue even by this method, and furthermore, this method However, there is a problem in that it is difficult to obtain a copolymer having an aliphatic group with a short chain length.

Therefore, polycarbonate obtained by conventional manufacturing methods has a poor balance of mechanical properties, heat resistance, and hue, and has poor moldability. The hue is good,
Moreover, a polycarbonate molded material with improved moldability is desired.

OBJECT OF THE INVENTION The present invention aims to solve the problems associated with the prior art, and is capable of forming a molded article with excellent mechanical properties and heat resistance as well as a good hue. Moreover, it is an object of the present invention to provide a polycarbonate composition that has improved resin fluidity and excellent moldability, and a method for producing a polycarbonate composition that can efficiently obtain this polycarbonate composition.

Summary of the Invention The polycarbonate composition according to the present invention comprises 60 to 95 parts by weight of an aromatic polycarbonate, an aliphatic dicarboxylic acid unit and an aromatic trihydroxy group compound -〇-1-s--5o.
- or -S O2-, R1 and R2 are hydrogen atoms or monovalent hydrocarbon groups, and R3 is a divalent hydrocarbon group.

Furthermore, even if the aromatic nucleus has a monovalent hydrocarbon substituent,
Often n is an integer from 2 to 50, preferably from 6 to 40, more preferably from 9 to 30. ) is characterized in that it contains 40 to 5 parts by weight of polyester represented by:

Since the polycarbonate composition according to the present invention contains 60 to 95 parts by weight of aromatic polycarbonate and 40 to 5 parts by weight of polyester represented by the above formula [1], Therefore, it is possible to make a molded product with excellent mechanical properties and heat resistance and a good color, and the fluidity of the resin is improved. Excellent moldability.

Further, the method for producing a polycarbonate composition according to the present invention is characterized in that 60 to 95 parts by weight of aromatic polycarbonate and 40 to 5 parts by weight of polyester represented by the above formula [1] are kneaded in a molten state. There is.

In the method for producing a polycarbonate composition according to the present invention,
Since 60 to 95 parts by weight of aromatic polycarbonate and 40 to 5 parts by weight of polyester represented by formula [1] are kneaded in a molten state, decomposition of the organic dicarboxylic acid as in conventional methods is not caused, Therefore, polycarbonate retains sufficient mechanical properties and heat resistance inherent to polyester carbonate, can be made into molded products with good hue, and has improved resin fluidity and excellent moldability. A composition can be obtained efficiently.

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate composition and method for producing the same according to the present invention will be specifically described below.

The polycarbonate composition according to the present invention contains an aromatic polycarbonate and a polyester represented by the above formula [1] in a specific ratio.

In such an aromatic polycarbonate, the content of hydroxyl groups based on all terminals may be usually 0 mol%, but it is preferably 5 mol% or more, more preferably 5 to 95 mol%.
It is.

In an aromatic polycarbonate having hydroxyl group terminals in the above ratio among all terminals of the aromatic polycarbonate, the hydroxyl group terminals serve as active sites when mixed with polyester to produce a polycarbonate composition.

Therefore, when the hydroxyl group content of the aromatic polycarbonate is within the above range, the transesterification reaction between the aromatic polycarbonate and the polyester in the composition proceeds more appropriately, resulting in excellent mechanical properties and heat resistance. It is more preferable in order to obtain a polycarbonate composition which can be made into a molded article with good color and good hue, and has improved resin fluidity and excellent moldability.

Further, the aromatic polycarbonate has a sodium content of 1.0 ppm or less, preferably 0.0 ppm or less.
It is desirable that the chlorine content is 5 ppm or less, and the chlorine content is 20 ppm or less, preferably 10 ppm or less.

Note that the sodium content can be determined by atomic absorption spectrometry and inductively coupled plasma emission spectrometry.

In addition, the chlorine content in this specification refers to chlorine present as an acid such as hydrochloric acid or as a salt such as sodium chloride or potassium chloride, or the content of chlorine in an organic compound such as phenyl chloroformate or methylene chloride. It can be measured by analysis such as ion chromatography.

In this way, the sodium content is 1.0 ppm or less, preferably 0.5 ppm or less, and the chlorine content is 20 ppm or less.
ppm or less, preferably 1 oppm or less, the aromatic polycarbonate has 0 hydroxyl group terminals among all its terminals.
Although it may be mol %, preferably 5 mol % or more, more preferably 5 to 95 mol %, the content is excellent in heat resistance and water resistance and is less likely to be colored.

Such aromatic polycarbonate has an initial hue, when the total content of alkali metals other than sodium, such as lithium, potassium, and cesium, or alkaline earth metals, such as beryllium, magnesium, and calcium, is 1-ppm or less. It is preferred because it has excellent water resistance and heat resistance.

Further, the aromatic polycarbonate has an intrinsic viscosity [η] of 0.3 to 1.0 when measured in methylene chloride at 20°C. Odl/
It is preferable that it is g.

The above-mentioned aromatic polycarbonate can be produced by, for example, directly reacting an aromatic trihydroxy compound with phosgene (interfacial method), or transesterifying an aromatic trihydroxy compound and a carbonic acid diester (interfacial method). Among them, the latter method is preferable because it has the advantage that aromatic polycarbonate can be obtained at low cost.

Hereinafter, a preferred method for producing the above-mentioned aromatic polycarbonate by subjecting an aromatic trihydroxy compound and a carbonic acid diester to a transesterification reaction (polycondensation reaction) will be described in detail.

In this method for producing aromatic polycarbonate, the following formula [2], R and R2 are used as the aromatic trihydroxy compound.
is a hydrogen atom or a monovalent hydrocarbon group, and R3 is a divalent hydrocarbon group.

Further, the aromatic nucleus may have a monovalent hydrocarbon substituent. ) are preferably used. Specifically, such aromatic trihydroxy compounds include bis(4-hydroxyphenyl)methane, 1,1-bis(
4-hydroxyphenyl)ethane, 2,2-bis(4-
hydroxyphenyl)propane, 2.2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2.2-bis(4-hydroxy-1-methylphenyl)propane, 1.1-bis (4
-hydroxy-1-butylphenyl)propane, 2.2
-bis(hydroxyphenyl)alkanes such as bis(4-hydroxy-3-bromophenyl)propane, 1.
1-bis(4-hydroxyphenyl)cyclopentane,
Bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane, 4.4'-dihydroxydiphenyl ether, 4.4
Dihydroxyaryl ethers such as '-dihydroxy-33'-dimethylphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3, 3'
Dihydroxydiarylsulfoxides such as -dimethyldiphenylsulfoxide, dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone, and 4,4'-dihydroxy 33'-dimethyldiphenylsulfone are used.

Among these, 2,2-bis(4-hydroxydiphenyl)propane is particularly preferred.

Specific examples of the carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, his(chlorophenyl) carbonate, m-cresyl carbonate,
dinaphthyl carbonate, his(diphenyl) carbonate, diethyl carbonate, dimethyl carbonate,
Dibutyl carbonate, dicyclohexyl carbonate, etc. are used.

Among these, diphenyl carbonate is particularly preferred.

Further, the carbonic acid diester as described above may contain dicarboxylic acid or dicarboxylic acid ester in a proportion of preferably 50 mol % or less, more preferably 30 mol % or less. As such dicarboxylic acids or dicarboxylic acid esters, terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate are used.

When such a dicarboxylic acid or dicarboxylic acid ester is used in combination with carbonic acid diester, an aromatic polyester carbonate can be obtained.

The carbonic acid diester as described above is preferably used in an amount of 1.01 to 1.30 mol, preferably 1.02 to 1.20 mol, per 1 mol of the aromatic trihydroxy compound.

In order to adjust the terminal hydroxyl group content of the resulting aromatic polycarbonate when melt polycondensing the aromatic trihydroxy compound and the carbonic acid diester as described above,
Phenols or diester carbonate may be present in the reaction system as an end-capping agent.

The phenols used as the terminal capping agent are desirably those having 10 to 40 carbon atoms, preferably 15 to 40 carbon atoms, and such phenols are used in an amount of 0.5 to 20 mol based on the aromatic trihydroxy compound. %, preferably 1-1
It is present in a proportion of 5 mol%.

Specifically, the following compounds are used as the above-mentioned phenols having 10 to 40 carbon atoms.

on-butylphenol m-n-butylphenol p-n-butylphenol 0-isobutylphenol m-isobutylphenol p-isobutylphenol o-t-butylphenol m-1-butylphenol pt-butylphenol on-pentylphenol m-n-pentylphenol p”n-pentylphenol o-n-hexylphenol m-n-hexylphenol p-n-hexylphenol 0-cyclohexylphenol 0-cyclohexylphenol p-cyclohexylphenol 0-phenylphenol m-phenylphenol p-phenylphenol o-n-nonylphenol m-n-nonylphenol p-n-nonylphenol 0-cumylphenol m-cumylphenol p-cumylphenol 0-Naphthylphenol m-naphthylphenol p-naphthylphenol 26-di-1-butylphenol 25-di-t-butylphenol 2.4-di-megabutylphenol 35-di-1-butylphenol 25-Dicumylphenol 3.5-Dicumylphenol chroman derivative for example Monohydric phenol.

Among these phenols, 2 with two aromatic nuclei
Nuclear phenols are preferred, especially p-cumylphenol,
Preferred are p-phenylphenol and the like.

In addition, when carbonic acid diester is used as the terminal capping agent, carbonic acid diester having 13 to 16 carbon atoms or carbonic diester having 17 to 50 carbon atoms is preferably added to the aromatic trihydroxyl group compound at 0% It is present in a proportion of .5 to 20 mol%, more preferably 1 to 15 mol%.

Examples of the carbonic diester having 13 to 16 carbon atoms include those having 13 to 16 carbon atoms among the diphenyl carbonates mentioned above.
diphenyl carbonate can also be used. Therefore, the carbonic acid diester used as a raw material for diphenyl carbonate, phenyltolyl carbonate, ditolyl carbonate, etc., and the diphenyl carbonate used as the terminal capping agent may be the same compound.

In addition, carbonate diesters having 17 to 50 carbon atoms include:
Usually, the general formula % formula % (wherein A is a group having 6 to 25 carbon atoms, and B is a group having 1 carbon number
It is a group of 0 to 25, and the sum of the carbon numbers of A and B is 49 or less. ) is used.

As the above-mentioned carbonic acid diester, specifically, for example, the following compounds are used.

(In the formula, R1 is a hydrocarbon group having 3 to 36 carbon atoms.) (In the formula, R and R3 may each be the same,
They may also be different, R2 is a hydrocarbon group having 1 to 19 carbon atoms, R3 is a hydrocarbon group having 3 to 19 carbon atoms, and R2 is a hydrocarbon group having 3 to 19 carbon atoms.
The sum of the carbon numbers of and R3 is 37 or less. ) (In the formula, R4 is a hydrocarbon group having 1 to 30 carbon atoms, and R5 is a hydrocarbon group having 1 to 20 carbon atoms.) (In the formula, R6 is a hydrocarbon group having 4 to 37 carbon atoms. It is a hydrogen group.) (In the formula, R and R8 may each be the same,
They may also be different, and R7 is a hydrocarbon group having 1 to 30 carbon atoms, and R8 is a hydrocarbon group having 3 to 20 carbon atoms. ) More specifically, the carbonic acid diesters as mentioned above include carbbutoxyphenylphenyl carbonate, methylphenylbutylphenyl carbonate, ethylphenylbutylphenyl carbonate, dibutyldiphenyl carbonate, biphenyl carbonate, ditolyl carbonate, and cumylphenylphenyl carbonate. , dicumylphenyl carbonate, naphthylphenylphenyl carbonate, dinaphthylphenyl carbonate, carphopropoxyphenylphenyl carbonate, carboheptoxy 1-butylphenylphenyl carbonate, carboprotoxyphenylmethylphenylphenyl carbonate, chromanil Phenyl carbonate and ditolyl carbonate are preferably used.

In addition, among the above-mentioned aromatic carbonate raw materials and sealants, it is preferable that the total chlorine content in diester carbonate and diphenyl carbonate is 20 ppm or less because an aromatic polycarbonate with a good hue can be obtained. .

In this way, in order to reduce the chlorine content in diester carbonate and diphenyl carbonate to 20 ppm or less, the pH of these raw materials is 6.0 to 9.0, preferably 7.0 to 7.0.
8.5, more preferably 7.0 to 8.0, and may be washed with warm water at a temperature of 78 to 105°C, preferably 80 to 100°C, and even more preferably 80 to 90°C.

Weakly basic solutions used for cleaning as mentioned above include:
For example, aqueous solutions of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, and the like are used. Among these, aqueous solutions of sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like are particularly preferred.

Further, it is preferable that the carbonic acid diester and diphenyl carbonate are washed with warm water as described above, and then further distilled before use.

Furthermore, the total sodium ion content contained in the raw materials is preferably 1.0 ppm or less, more preferably 0.5 ppm or less. When the sodium ion content is less than or equal to the above amount, an aromatic polycarbonate with even less coloring can be obtained.

The sodium ion content contained in the starting material is
Determined by atomic absorption spectrometry and inductively coupled plasma emission spectrometry.

In order to reduce the sodium ion content contained in the above starting materials to below the above values, distillation, recrystallization,
A purification method such as an adduct method with phenol may be employed.

When producing an aromatic polycarbonate by melt polycondensing such an aromatic trihydroxyl compound and a carbonic acid diester, a catalyst containing an alkali metal compound and/or an alkaline earth metal compound can be used. It is desirable to use a catalyst containing (a) an alkali metal compound and/or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and at least one of (cl) boric acid or a boric acid ester.

(a) Specific examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, and sodium stearate. , potassium stearate, sodium borohydride, lithium borohydride, sodium borohydride, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, phenol Sodium salts, potassium salts, lithium salts, etc. are used.

(Specifically, alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, Barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, barium stearate, magnesium stearate, strontium stearate, and the like are used.

(b) As the nitrogen-containing basic compound, specifically, tetramethylammonium hydroxide (M e 4NOH
), tetraethylammonium hydroxide (E t
4NOH), tetrabutylammonium (M e )
R2
Primary amines represented by NH (in the formula R1 is an alkyl group such as methyl or ethyl, or an aryl group such as phenyl or tolyl), or ammonia, tetramethylammonium borohydride (M e N B H4)
, tetrabutylammonium borohydride (Bu
N B H4), tetrabutylammonium tetra7 x neylborate (B u N B P h
t, ), basic salts such as tetramethylammonium tetraphenylborate (M64NBPh4), etc. are used.

Among these, tetraalkylammonium hydroxides are particularly preferred.

In addition, as (C) boric acid or boric acid ester, boric acid or general 2B (OR) (OH) 3, (wherein R is alkyl such as methyl or ethyl, aryl such as phenyl, etc., and n is 1.2 or 3) is used.

Specifically, such boric acid esters include trimethyl borate, triethyl borate, tributyl borate,
Trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, trinaphthyl borate, etc. are used.

The above-mentioned (a) alkali metal compound and/or alkaline earth metal compound is an aromatic trihydroxy compound 1
10 to 1o-3 mol, preferably 10 to 10-4 mol, more preferably 10
and (b) the nitrogen-containing basic compound in an amount of from 10 to 10-1 mol, preferably from 10 to 10-2 mol.
Used in molar amounts.

And (C) boric acid or boric acid ester is 1o-8 to 10 mol, preferably 10 to 1o-2 mol, more preferably 1
It is used in amounts of 0 to 1 o-4 mol.

In this way, a catalyst that combines (a) an alkali metal compound and/or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (C) either boric acid or boric acid ester has a high polymerization rate. Aromatic polycarbonates with high molecular weight can be produced with activity, and the resulting aromatic polycarbonates have excellent heat resistance and water resistance, as well as improved color tone and excellent transparency. .

Also, (a) an alkali metal compound and/or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (C)
A catalyst containing a combination of boric acid or a boric acid ester has even higher catalytic activity and can produce a high molecular weight aromatic polycarbonate. Furthermore, it has excellent heat resistance and water resistance, further improved color tone, and excellent transparency.

The polycondensation reaction between an aromatic trihydroxy compound and a carbonate diester can be carried out under the same conditions as the conventionally known polycondensation reaction conditions between an aromatic trihydroxy compound and a carbonate diester. For this, the first stage reaction is 80~
Both are reacted at a temperature of 250°C, preferably Zoo to 230'C1, more preferably 120 to 190°C, for 0 to 5 hours, preferably 0 to 4 hours, and still more preferably 0.25 to 3 hours at normal pressure. Next, the reaction temperature is raised while reducing the pressure in the reaction system to react the aromatic trihydroxy compound with the carbonic acid diester.Finally, the aromatic trihydroxy compound is reacted with the carbonic diester at a temperature of 240 to 320 T:: under a reduced pressure of 1 mmHg or less. Polycondensation of a hydroxyl compound and a carbonic acid diester is carried out.

The reaction between the aromatic trihydroxy compound and the carbonic acid diester as described above may be carried out continuously or batchwise. Further, the reaction apparatus used in carrying out the above reaction may be a tank chamber, a front type, or a base type.

The polyester constituting the polycarbonate composition according to the present invention together with the aromatic polycarbonate as described above is composed of an aliphatic dicarboxylic acid unit and an aromatic dihydroxy compound unit, and has the formula [1] % formula % S, R and R2 is a hydrogen atom or a monovalent hydrocarbon group, and R3 is a divalent hydrocarbon group.

Further, the aromatic nucleus may have a monovalent hydrocarbon substituent, and n is an integer of 2 to 50, preferably 6 to 40, and more preferably 9 to 30. ) is a polyester represented by

Specifically, the aliphatic dicarboxylic acid units in the formula [1] include units such as succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, brassylic acid, and dodecanoic acid. Can be mentioned.

Further, the aromatic dihydroxy compound unit in the formula [1] is specifically, bis(4-hydroxyphenyl),
Bis(4-hydroxy-1-methylphenyl), bis(
Examples include units such as 4-hydroxy-1-butylphenyl), bis(4-hydroxy-3-butylphenyl), and bis(hydroxyaryl).

The polyester represented by the above formula [1] has an intrinsic viscosity [η] of 0.03 to 0 as measured in methylene chloride at 20°C.
．． 80 dl 7g, preferably 0.05-0.70
dl/g, more preferably 0.10 to 0.60 dl!
/g is desirable.

If the intrinsic viscosity [η] of the polyester represented by the formula [1] is within the above range as measured in methylene chloride at 20°C, the polycarbonate composition containing such a polyester will have good impact resistance, etc. It is possible to make a molded product with even better mechanical properties and heat resistance, and even better hue, and furthermore, the moldability is further improved.

There are no particular limitations on the method for producing the polyester represented by the formula [1], and an example thereof is a melt polycondensation reaction between a diphenyl ester of an aliphatic dicarbonate and an aromatic trihydroxy compound.

In the polycarbonate composition according to the present invention, the content ratio of the aromatic polycarbonate as described above and the polyester represented by the formula [1] (aromatic polycarbonate/polyester represented by the formula [1]) is 60 ~95 parts by weight/40-5 parts by weight, preferably 65 parts by weight
~95 parts by weight/35-5 parts by weight, more preferably 70 parts by weight
~93 parts by weight/'~7 parts by weight.

By having the content ratio of the aromatic polycarbonate and the polyester represented by the above formula [1] within the above range, it is possible to make a molded product with excellent mechanical properties and heat resistance as well as a good hue. Moreover, the fluidity of the resin is improved, and a polycarbonate composition with good moldability can be obtained.

Furthermore, the polycarbonate composition according to the present invention may contain pigments, dyes, reinforcing agents, fillers, flame retardants, heat resistant agents, stabilizers, oxidative deterioration inhibitors, weathering agents, and mold release agents, within the scope of the invention. , a crystal nucleating agent, a plasticizer, a fluidity improver, an antistatic agent, etc.

Such reinforcing agents and fillers (hereinafter referred to as reinforcing fillers) include oxides and silicates of metals such as aluminum, iron, nickel, and titanium, such as mica, aluminum silicate, talc, titanium dioxide, and wollastonite. , tubaculite, potassium titanate, titanate whiskers, glass flakes, glass beads, glass fibers, carbon filaments, polymer fibers, and the like. These reinforcing fillers can be appropriately selected and used alone or in combination.

Among these reinforcing fillers, reinforcing fillers made of glass are preferred, and mixtures containing glass, such as glass and talc, glass and mica, glass and aluminum silicate, are preferably used. Additionally, when glass filaments are used, filaments produced by mechanical stretching are preferred, and the diameter of the filaments is preferably 0.00012 to 0.00075 inches.

In any case, the various reinforcing fillers mentioned above are usually present in the polycarbonate composition in an amount of 1 to 60% by weight, preferably 5 to 60% by weight.
It is desirable to use it in a proportion of 50% by weight.

Further, examples of the above-mentioned flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, and antimony compounds, which are usually used as flame retardants for polycarbonate.

The above flame retardants are usually present in polycarbonate compositions at 0.
001-200% by weight, preferably 0.005-150
It is desirable to use it in a proportion of % by weight.

Specific examples of the stabilizer or oxidative deterioration inhibitor include hindered phenol, phosphite, metal phosphate, metal salt phosphite, and the like.

The above-mentioned stabilizers or oxidative deterioration inhibitors are usually 0.01 to 1% by weight, preferably 0.01 to 1% by weight, preferably 0.01 to 1% by weight in the polycarbonate composition.
It is desirable to use it in a proportion of 1 to 0.5% by weight.

The polycarbonate composition according to the present invention has a light transmittance of 75% or more, preferably 80% or more, and a glass transition point (T g
) is different from the raw material aromatic polycarbonate and polyester.

The polycarbonate composition according to the present invention having such features can be made into a molded product with excellent mechanical properties, heat resistance, and color, and has improved resin fluidity and moldability. For example,
It can be suitably used for electrical, electronic parts, automobile parts, mechanical parts, household goods, and the like.

Next, the method for producing the polycarbonate composition according to the present invention will be described in detail.

In the method for producing a polycarbonate composition according to the present invention, 60 to 95 parts by weight of the above aromatic polycarbonate and 40 to 5 parts by weight of the polyester represented by the above formula [1]
Parts by weight are kneaded in a molten state to allow the transesterification reaction to proceed.

By kneading 60 to 95 parts by weight of aromatic polycarbonate and 40 to 5 parts by weight of polyester represented by the above formula [1] in a molten state and allowing the transesterification reaction to proceed, it has excellent mechanical properties and heat resistance. It is possible to efficiently produce a polycarbonate composition which can be made into a molded article with good color and good hue, and has improved resin fluidity and excellent moldability.

This transesterification reaction usually proceeds under the following conditions.

That is, the reaction temperature is usually 240 to 320°C, preferably 260 to 300°C, more preferably 260 to 280°C.
It is ℃.

The reaction pressure is usually 0.1 to 760 mm) Ig, preferably 0.1 to 10 mnHg, more preferably 0.1 to 2 mn
l(g.

Reaction time is usually 1 minute to 5 hours, preferably 30 minutes to
It is 5 hours, more preferably 30 minutes to 3 hours.

In the method for producing a polycarbonate composition according to the present invention, the content of hydroxyl groups relative to all terminals in the aromatic polycarbonate may be usually 0 mol%, but preferably 5 mol% or more, more preferably 5 to 5 mol%. 95
It is desirable to use an aromatic polycarbonate that is mol %.

By using aromatic polycarbonate in which the content of hydroxyl groups to all terminals is in the above ratio, it is possible to form a molded product with excellent mechanical properties and heat resistance, as well as a good hue, and the flow of the resin is reduced. A polycarbonate composition having improved properties and excellent moldability can be efficiently produced.

As such an aromatic polycarbonate, an aromatic polycarbonate obtained by a melt polycondensation reaction of an aromatic trihydroxy compound and a carbonic acid diester can be particularly preferably used.

In addition, as the above aromatic trihydroxy compound, 20°C
Intrinsic viscosity [η] measured in methylene chloride of 0.03
~0. A polyester of 80 dl 7 g can be used particularly preferably.

In the method for producing a polycarbonate composition according to the present invention, the reaction mode of the above transesterification reaction may be either a batch type or a continuous type. Further, the reactor used for kneading the above aromatic polycarbonate, the polyester represented by the above formula [1], and further appropriately selected additives as necessary in a molten state is a tank. It may be a mold or an extruder mold.

The polycarbonate composition obtained by the method for producing a polycarbonate composition according to the present invention has a light transmittance of 75.
% or more, preferably 80% or more, and the glass transition point (Tg) measured using a DSC (differential scanning calorimeter) is different from that of the raw material aromatic polycarbonate and polyester.

According to the method for producing a polycarbonate composition according to the present invention, 60 to 95 parts by weight of aromatic polycarbonate and 40 to 5 parts by weight of polyester represented by the formula [1] are kneaded in a molten state. It is possible to efficiently obtain the polycarbonate composition according to the present invention, which can be made into a molded product having excellent properties, heat resistance, and hue, and has improved resin fluidity and moldability. can.

Effects of the Invention According to the polycarbonate composition according to the present invention, 60 to 95 parts by weight of aromatic polycarbonate and the formula [1]
Since it contains 40 to 5 parts by weight of polyester represented by At the same time, it is possible to provide a polycarbonate composition that can be made into a molded article with a good hue, has improved resin fluidity, and has excellent moldability.

Further, according to the method for producing a polycarbonate composition according to the present invention, in order to knead 60 to 95 parts by weight of aromatic polycarbonate and 40 to 5 parts by weight of polyester represented by the formula [1] in a molten state, It is possible to provide a method for producing a polycarbonate composition that does not cause decomposition of an organic dicarboxylic acid as in conventional methods and can therefore efficiently produce a polycarbonate composition that has the above advantages.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

The physical properties of the polycarbonate compositions and molded products thereof obtained in the following Examples were measured as follows.

Intrinsic viscosity [η] in methylene chloride (0.5 dl/g)
It was measured using an Ubbelohde viscometer at 20°C.

Light transmittance: ASTM D l003 j: Accordingly, 3
Measurement was performed using a press plate of Sonotsum.

The measurement was carried out using NDH-2011 manufactured by Hayes Nippon Denshoku Kogyo ■.

Lutointex (Mll: JIS K-721
0) According to the method, 280°C, load i11. 2kg (7
) was measured under the following conditions.

Izot impact strength: Measured in accordance with ASTM D 256 using a 63.5X 12.7X 2 (rear notch) injection test piece.

Glass transition temperature (Tg): MOD manufactured by PerkinElmer
It was determined by differential thermal analysis of the resin using an EL DSC-2 differential scanning calorimeter at a heating rate of 10° C. per minute.

Hue (Yl): The Lab value of a 2-inch thick press sheet was determined by Co1orand Co1o+Delle from Nihon Heavy Industries ■.
It was measured by a transmission method using +ence Meter ND-IHI DP, and the b value was used as a measure of yellowness.

Example 1 Diphenyl adipate (synthesized by reaction of adipic acid chloride and phenol, then heated at 192°C 10.9II
A colorless and transparent product obtained by vacuum distillation under IIIHg) and bisphenol A were mixed at a molar ratio of 1:1, and the mixture was stirred at a temperature of 180° C. for 30 minutes under reflux in a nitrogen stream to uniformly melt the mixture.

To this, 2.5 x 10-
4 moles of tetramethylammonium hydroxide and 0.05×10' moles of lithium hydroxide were added and the temperature was raised to 200°C. The pressure was gradually reduced to 200-8 g, and after 2 hours, the pressure was further gradually reduced to 0.5 + m++ l (g) and the reaction was allowed to proceed for 2 hours. of polyester was obtained.

The obtained polyester was colorless and transparent.

Next, in a glass reactor equipped with a stirring device, polycarbonate (Lexan 141 manufactured by Japan GE Plastics Co., Ltd.)
, [η]=0.50dn/g, terminal hydrogen group content 0%)
75 parts by weight and 25 parts by weight of the above polyester,
It was melted at 70°C and stirred at 270°C for 2 hours under a reduced pressure of 0.5 mmHH to carry out transesterification, [η] = 0.
A colorless and transparent polymer with a yield of 40 dn/g was obtained.

Table 1 shows the physical properties of the obtained polymer.

Example 2 Diphenyl dodecanoate (a colorless and transparent substance synthesized by the reaction of dodecanoic acid and diphenyl carbonate and then recrystallized with toluene) and bisphenol A were mixed at a molar ratio of 1:1, and the mixture was heated under reflux in a nitrogen stream. The mixture was stirred at a temperature of 180° C. for 30 minutes to uniformly melt the mixture.

To this, 2.5XIO per mole of bisphenol A.
Add 2 moles of tetramethylammonium hydroxide and 0.05 x 10' moles of lithium hydroxide;
The temperature was raised to 00°C. The pressure was gradually reduced to 200mm) Ig, and after 2 hours, the pressure was further gradually reduced to 0.5■Hg.
The reaction was carried out for a period of time to obtain 7 g of polyester having an intrinsic viscosity [η] of 0 and 38 dJ as measured in methylene chloride at 20°C.

The obtained polyester was colorless and transparent.

Next, in a glass reactor equipped with a stirring device, polycarbonate (Lexan 141 manufactured by Japan GE Plastics Co., Ltd.)
, [η] = o, 50d//g, terminal hydrogen group content 0%
) 85 parts by weight and 15 parts by weight of the above polyester,
Melt at 270℃, under reduced pressure of 0.5mmHH, 270℃
Stir for 2 hours to perform transesterification, [η] = 0
．． A colorless and transparent polymer with a weight of 51 dl/g was obtained.

Table 1 shows the physical properties of the obtained polymer.

Example 3 Bisphenol A (manufactured by Japan GE Plastics Co., Ltd. >0
．． 440 kg-mol and diphenyl carbon-1-(
0.446 kg-mol (manufactured by GE) was placed in a 250-liter stirring tank, and after purging with nitrogen, it was dissolved at 140°C. Next, the temperature was raised to 180°C, and 0.0% of boric acid was added.
011 gmol was added and stirred for 30 minutes. Next, 0.11% of tetramethylammonium hydroxide was used as a catalyst.
g-mol and 0.00044 g-mol of sodium hydroxide were added, and the temperature was raised to 240°C while the pressure was gradually lowered to 2Q mmHg. The temperature and pressure were kept constant, the amount of distilled phenol was measured, and when no more phenol was distilled out, the pressure was returned to atmospheric pressure with nitrogen. The time required for the reaction was 2 hours. The intrinsic viscosity [η] of the obtained reaction product was 0. It was 14 dl 7g.

Next, this reactant was pressurized using a gear pump and fed into a centrifugal thin film evaporator to proceed with the reaction. The temperature and pressure of the thin film evaporator were controlled at 295° C. and 21111 IHg, respectively. The prepolymer extracted from the lower part of the evaporator with a gear pump was passed through a die into a strand in a nitrogen atmosphere, and cut into pellets with a cutter. The intrinsic viscosity [η] of this prepolymer was 0.35 dn/g.

Next, this prepolymer was heated to 0.2 mmHH at 290°C.
2-shaft horizontal stirring polymerization tank (L/D=6
, stirring blade rotation diameter 150 mm, internal volume 40 liters) using an extruder at a rate of 40 kg/hour, and polymerization was carried out for a residence time of 30 minutes. The intrinsic viscosity [η] of the obtained polymer was 0.
50 dn/g, and the terminal hydroxyl group content was 30 mol%.

Thereafter, in Example 2, the terminal hydroxyl group content was 0 mol%.
, [η] = 0.50 dl/g was carried out in the same manner as in Example 1, except that the polycarbonate obtained as described above was used instead of the polycarbonate with [η] = 0.
．． A colorless and transparent polymer was obtained at 54 dn/g.

Table 1 shows the physical properties of the obtained polymer.

Comparative Example 1 Diphenyl adipate (synthesized by reaction of adipic acid chloride and phenol, 192°C 10°9Il)
A colorless and transparent substance obtained by distillation under reduced pressure at IIIHg), Schifnyl carbonate, and bisphenol A were mixed at a molar ratio of 0.2/0.86:1, and the mixture was heated at a temperature of 180°C under reflux in a nitrogen stream for 30 minutes. The mixture was stirred for a minute to uniformly melt the mixture.

To this, 2.5 x 104 per mole of bisphenol A
Add 20 moles of tetramethylammonium hydroxide and 0.05×10' moles of lithium hydroxide.
The temperature was raised to 0°C. The pressure was gradually reduced to 200 mmHg for 1 hour, and the temperature was further increased to 240°C, and the temperature was increased to 200 mmffg for 2 hours.
0 minutes, gradually reduce the pressure to 150 nmHg for 20 minutes, further reduce the pressure to 100 + nmHg for 20 minutes, 15 mmHg
After reducing the pressure to
Finally, the pressure was reduced to 0.5 wn Hg and the reaction was carried out for 3 hours to obtain 7 g of polyester carbonate with an intrinsic viscosity [η] of 0.36 di as measured in methylene chloride at 20°C.

The obtained polyester carbonate was brown in color.

Table 1 shows the physical properties of the obtained polymer.

Example 4 In Example 2, instead of diphenyl dodecanoate,
The procedure was carried out in the same manner as in Example 2, except that diphenyl sebacate (a colorless and transparent substance synthesized by the reaction of sebacic acid and diphenyl carbonate and then recrystallized with toluene) was used, and the intrinsic viscosity [η] was 0. 31 dl 7g of polyester was obtained.

The obtained polyester was colorless and transparent.

In a glass reactor equipped with a stirring device, polycarbonate (Japan GE Plastics Co., Ltd., Lexan 141,
[η Coco 0.50 dl 7g, terminal hydroxyl group content 0 mol%] 85 parts by weight and 15 parts by weight of the above polyester were melted at 270°C and stirred at 270°C for 2 hours under reduced pressure of 0.5-8g. to perform transesterification and obtain the intrinsic viscosity [η]
A colorless and transparent polymer with a concentration of 0.52 dl/g was obtained.

Table 1 shows the physical properties of the obtained polymer.

Example 5 In Example 4, instead of polycarbonate having a terminal hydroxyl group content of 0 mol% and an intrinsic viscosity [η] of 0.50 dl/g, a polycarbonate having a terminal hydroxyl group content obtained by the method of Example 3 was used. 30 mol%, intrinsic viscosity [η is 0.50 dl! Example 4 was carried out in the same manner as in Example 4, except that a polycarbonate of 0.56 dl/g was used to obtain a colorless and transparent polymer with an intrinsic viscosity [η of 0.56 dl/g.

Table 1 shows the physical properties of the obtained polymer.

Contents of amendment 1. Case Description 1990 Patent Application No. 111,014 1990 4
Patent application 2 filed on April 26th, title of invention Polycarbonate composition and its manufacturing method 3, relationship with the amended case Patent applicant name Japan GE Plastics Co., Ltd. 4, agent (zip code 141) 3rd floor, Araku Building, 2-19-2 Nishigotanda, Tokyo Parts Ward [Telephone: 03-491-3161] 8199 Patent Attorney Shun Suzuki, -115 Date of amendment order 1゛-2 Details subject to voluntary amendment Column 1) “Detailed Description of the Invention” of the book, page 41, lines 5-6 of the specification, rO,5d
Correct i/gJ to rO,5g/dIJ.

2) In the second line of page 42 of the specification, the text "r2mm thickness" will be corrected to "r3mm thickness."

3) In the second line of page 42 of the specification, the phrase "rLab value" will be corrected to "X value, Y value, Z value."

4) On page 42, lines 5 and 6 of the specification, the phrase "b value was used as a measure of yellowness" was replaced with "Yellowness index (YI) was calculated.

I will correct it.

5) On page 44, line 19 of the specification, rO, 440
Correct "kg mol" to "rO, 440 kmol".

6) On page 44, line 20 of the specification, ro, 446
Correct "kg-mol" to "ro, 446 kilomol".

7) In the 3rd to 4th lines of page 45 of the specification, rO,00
Correct "11 g-mol" to "ro, 0011 mole".

8) On page 45, line 6 of the specification, rO,11g-
Correct "mol" to rO, 11 moles j.

9) On page 45, line 7 of the specification, ro, OO
"O44 g-mol" means "rO,00044 mole"
I will correct it.

Claims (8)

[Claims] (1) 60 to 95 parts by weight of aromatic polycarbonate;
It consists of an aliphatic dicarboxylic acid unit and an aromatic dihydroxyl compound unit, and has the following formula [1] ▲Mathematical formula, chemical formula, table, etc.▼[1] (In formula [1], X is a direct bond, ▲Mathematical formula, chemical formula , there are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -O
-, -S-, -SO- or -SO_2-, and R^
1 and R^2 are hydrogen atoms or monovalent hydrocarbon groups, and R^3 is a divalent hydrocarbon group. Further, the aromatic nucleus may have a monovalent hydrocarbon substituent, and n is an integer of 2 to 50. ) A polycarbonate composition comprising 40 to 5 parts by weight of a polyester represented by: (2) The intrinsic viscosity [η] (measured value in methylene chloride at 20°C) of the polyester represented by the above formula [1] is 0.
The polycarbonate composition according to claim 1, wherein the polycarbonate composition has a molecular weight of 0.03 to 0.80 dl/g. (3) The polycarbonate composition according to claim 1 or 2, wherein the aromatic polycarbonate has a terminal hydroxyl group content of 5 mol% or more. (4) The polycarbonate composition according to any one of claims 1 to 3, wherein the aromatic polycarbonate is an aromatic polycarbonate obtained by a melt polycondensation reaction of an aromatic dihydroxy compound and a carbonic acid diester. . (5) 60 to 95 parts by weight of aromatic polycarbonate;
A method for producing a polycarbonate composition, which comprises kneading 40 to 5 parts by weight of the polyester represented by the formula [1] in a molten state. (6) The polyester has an intrinsic viscosity [η] of 0.03 to 0.80 dl measured in methylene chloride at 20°C.
6. The method for producing a polycarbonate composition according to claim 5, wherein a polyester having a weight of /g is used. (7) The method for producing a polycarbonate composition according to claim 5 or 6, wherein an aromatic polycarbonate having a terminal hydroxyl group content of 5 mol % or more is used as the aromatic polycarbonate. (8) The polycarbonate composition according to any one of claims 5 to 7, wherein the aromatic polycarbonate is an aromatic polycarbonate obtained by a melt polycondensation reaction of an aromatic dihydroxy compound and a carbonic acid diester. manufacturing method.