JP2003147185A - Aromatic polycarbonate composition, moldings, and molding method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate composition excellent in heat resistance represented by hue stability in a molding process, to provide moldings item and a molding method. SOLUTION: This aromatic polycarbonate composition contains an aromatic polycarbonate, a phosphorus-oxo acid condensate, and an ester of a 10-25C aliphatic carboxylic acid and a 2-10C aliphatic alcohol. A molded item excellent in hue can be obtained by molding the composition at high temperature.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate composition having excellent heat resistance stability and a molded product thereof.

More specifically, the present invention relates to an aromatic polycarbonate composition having good heat resistance and suitable for applications requiring transparency and hue stability, and a molded product thereof.

[0003]

BACKGROUND OF THE INVENTION Aromatic polycarbonates and resin compositions thereof have been used for a wide range of applications, but especially for lenses, prisms, optical discs, sheets, films and the like because of their excellent optical properties, transparency and mechanical properties. Used in large quantities.

In particular, optical molded products such as lenses and optical disks, and resins and resin compositions which are raw materials of the molded products are required to have excellent transparency, hue and hue stability during molding. .

Therefore, it has been proposed to add various additives such as a heat resistance stabilizer to the aromatic polycarbonate at the time of polymerization or molding to improve hue stability under heat load while maintaining excellent transparency and hue. It is a well-known fact that many additives have been used in the past and that each of these additives has a tentative effect.

The hue change during heating of the polycarbonate is influenced by a trace amount of impurities such as metal elements present in the resin, and among them, the alkali metal element and the alkaline earth metal element have a great influence even by a trace amount, and the hue changes. Often worsens.

Therefore, for example, when an alkali metal or an alkaline earth metal is used as a catalyst at the time of polymerization, it is of course necessary to remove or inactivate the metal after the polymerization, but when molding at high temperature. In addition, JP-A-7-126505 and EP-90.
As disclosed in 5.178, hue stability can be improved by adding an acidic compound such as phosphoric acid or phosphorous acid as a heat resistance stabilizer.

On the other hand, in the case of molding an optical disk, in order to accurately transfer the signal stamped on the stamper onto the aromatic polycarbonate substrate, the resin temperature during the molding of the disk should be raised to improve the fluidity of the resin. Has been done.

Further, in recent years, the resin temperature at the time of molding has been further increased to 350 to 400 ° C. along with the increase of the recording density of the optical disk, and the above-mentioned conventionally proposed additives are often not sufficiently effective. It's starting.

For these reasons, it has been strongly desired to develop an aromatic polycarbonate composition which is improved in transparency and hue required for aromatic polycarbonate as an optical disk material in recent years, and further in hue stability during molding. ing.

[0011]

An object of the present invention is to provide an aromatic polycarbonate composition having excellent heat resistance stability, a molded product thereof, and a molding method.

More specifically, it is an object of the present invention to provide an aromatic polycarbonate composition having excellent heat resistance represented by hue stability during heat-molding, a molded product thereof, and a molding method.

Still another object and advantage of the present invention are:
It will be apparent from the following description.

[0014]

That is, one embodiment of the present invention is an aromatic polycarbonate obtained by reacting an aromatic dihydroxy compound with a carbonate-forming compound,
An aromatic polycarbonate composition comprising a phosphorus oxo acid condensate, and an ester of an aliphatic carboxylic acid having 10 to 25 carbon atoms and an aliphatic alcohol having 2 to 10 carbon atoms.

The above aromatic polycarbonate has a viscosity average molecular weight of 10,000 to 100,000, a melt viscosity stability of 0.5% or less, and a terminal OH group concentration with respect to the total number of terminals. It is desirable that it is 3 to 95 mol%.

In this case, the above-mentioned physical properties of the aromatic polycarbonate mean the physical properties of the aromatic polycarbonate before being added to the aromatic polycarbonate composition, but they are so large under the usual conditions for producing the aromatic polycarbonate composition. Since there is no change in the physical properties, if the physical properties of the aromatic polycarbonate separated and taken out from the aromatic polycarbonate composition are within the above range, it can be judged that it belongs to the category of the present invention.

Another aspect of the present invention is a molded product represented by a disk substrate, which is molded from the above aromatic polycarbonate composition, and a molding method.

The present inventors have made phosphorus aromatic acid condensate present in an aromatic polycarbonate resin to maintain excellent transparency and hue while maintaining heat stability during heat molding, especially at high temperature molding. It has been found that the improvement of the above can be achieved, and the present invention has been reached. Here, in the present invention, the heat resistance stability of the aromatic polycarbonate composition is represented by the hue stability under heat load, and is evaluated by that.

Further features of the present invention will be clarified in the embodiments of the invention described below.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to tables, formulas, examples and the like. It should be noted that these tables, formulas, examples and the like and explanations exemplify the invention of the present application and do not limit the scope of the invention of the present application. It goes without saying that other embodiments may belong to the scope of the present invention as long as they match the gist of the present invention.

In the aromatic polycarbonate obtained by reacting the aromatic dihydroxy compound and the carbonate-forming compound, the phosphorus oxo acid condensate is allowed to exist,
It is possible to obtain an aromatic polycarbonate composition and a molded product which are excellent in heat resistance typified by hue stability during heat molding. As described above, it is clear from the study by the inventors of the present invention that the addition of phosphoric acid has some effect on the improvement of the hue stability of polycarbonate under heat processing, while the phosphorous acid condensate shows even higher effect. Became.

(Polyphosphoric acid structure) The phosphorus oxo acid condensate of the present invention can be prepared by the method described in Inorganic Chemistry Book IV-6, Maruzen Co., Ltd.
P. 180 'is defined as a condensed phosphoric acid, which is a group of compounds containing pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, ultraphosphoric acid and a group of compounds containing heteropolyphosphoric acid, wherein phosphorus oxo acid or phosphorus oxo acid and hetero acid The compound may have any structure as long as it is a compound formed by dehydration condensation of and.

Polyphosphoric acid generally has a chain structure, but it may have a branched or cyclic structure. Specifically, diphosphoric acid,
Chain triphosphate, cyclic triphosphate, chain tetraphosphate, cyclic tetraphosphate, branched tetraphosphate, chain pentaphosphate, cyclic pentaphosphate,
Branched pentaphosphate, chain hexaphosphate, cyclic hexaphosphate, branched hexaphosphate, chain heptaphosphate, cyclic heptaphosphate, branched heptaphosphate, chain octaphosphate, cyclic octaphosphate , Branched octaphosphoric acid, chained nine phosphoric acid, cyclic nine phosphoric acid, branched nine phosphoric acid, chain decaphosphoric acid, cyclic decaphosphoric acid, branched decaphosphoric acid, or a mixture thereof.

Examples of metaphosphoric acid include cyclic trimetaphosphoric acid, tetrametaphosphoric acid, and long-chain metaphosphoric acid.

Each of these may be used alone,
Moreover, you may use these mixtures. Among these phosphorus oxo condensates, metaphosphoric acid and polyphosphoric acid are usually present as a mixture of condensed phosphoric acids having different degrees of condensation and molecular structures. Thus, when used as a mixture of one or more of the above condensed phosphoric acids. Or each may be used alone.

Of these, polyphosphoric acid containing a mixture of linear condensed phosphoric acids having different degrees of condensation is preferably used because it has a high effect of improving heat stability and is available at a low cost.

Specific examples of the heteropolyphosphoric acid include phosphotungstic acid and phosphomolybdic acid.

The condensation degree (n) of the phosphorus oxo acid condensate of the present invention may be any value, but it is preferable to use one having an average value in the range of 1 to 100, more preferably 1 to 50. , And more preferably 1 to 20. The value of n at this time is an average value, and a component in which n exceeds this value may be included.

N defined as the average value is ICP
It can be determined from the concentration of elemental phosphorus obtained by elemental analysis such as optical emission analysis, and the value is usually represented by a real number including a decimal point.

If n exceeds 100, the compatibility with the aromatic polycarbonate may decrease.

The phosphorus oxo acid condensate of the present invention usually has two or more acidic hydrogens, in which case a part of them may be esterified, and the site of esterification is at any position in the phosphorus oxo acid condensate. It may be a part.

Examples thereof include esters obtained by reaction with alcohols and phenols. Examples thereof include mono- or poly-methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, t-butyl ester, Examples thereof include benzyl ester, phenyl ester, and alkyl-substituted phenyl ester.

Specifically, diphosphoric acid monomethyl ester, triphosphoric acid monomethyl ester, triphosphoric acid dimethyl ester, tetraphosphoric acid monomethyl ester, tetraphosphoric acid dimethyl ester, tetraphosphoric acid trimethyl ester, pentaphosphoric acid monomethyl ester, Pentamethyl dimethyl ester, Pentaphosphoric acid trimethyl ester, Pentaphosphoric acid tetramethyl ester, Trimetaphosphoric acid monomethyl ester, Trimetaphosphoric acid dimethyl ester, Tetrametaphosphoric acid monomethyl ester, Tetrametaphosphoric acid dimethyl ester, Tetrametaphosphoric acid trimethyl ester, Diphosphoric acid Monoethyl ester, triphosphoric acid monoethyl ester, triphosphoric acid diethyl ester, tetraphosphoric acid monoethyl ester, tetraphosphoric acid diethyl ester, tetraphosphoric acid triethyl ester, pentaphosphoric acid monoethyl ester, pentaphosphoric acid Acid diethyl ester, pentaphosphoric acid triethyl ester, pentaphosphoric acid tetraethyl ester, trimetaphosphoric acid monoethyl ester, trimetaphosphoric acid diethyl ester, tetrametaphosphoric acid monoethyl ester, tetrametaphosphoric acid diethyl ester, tetrametaphosphoric acid triethyl ester, diphosphoric acid Monopropyl ester, triphosphoric acid monopropyl ester, triphosphoric acid dipropyl ester, tetraphosphoric acid monopropyl ester, tetraphosphoric acid dipropyl ester, tetraphosphoric acid tripropyl ester, pentaphosphoric acid monopropyl ester, pentaphosphoric acid diphosphate Propyl ester, triphosphoric acid pentapropyl ester, pentaphosphoric acid tetrapropyl ester, trimetaphosphoric acid monopropyl ester, trimetaphosphoric acid dipropyl ester, tetrametaphosphoric acid monopropyl ester, tetrame Phosphoric acid dipropyl ester, tetrametaphosphoric acid tripropyl ester, diphosphoric acid monoisopropyl ester, triphosphoric acid monoisopropyl ester, triphosphoric acid diisopropyl ester, tetraphosphoric acid monoisopropyl ester, tetraphosphoric acid diisopropyl ester, tetraphosphoric acid triisopropyl ester Isopropyl ester, pentaphosphoric acid monoisopropyl ester, pentaphosphoric acid diisopropyl ester, pentaphosphoric acid triisopropyl ester, pentaphosphoric acid tetraisopropyl ester, trimetaphosphoric acid monoisopropyl ester, trimetaphosphoric acid diisopropyl ester, tetrametaphosphoric acid monoisopropyl ester, tetramethaline Acid diisopropyl ester, tetrametaphosphoric acid triisopropyl ester, diphosphoric acid monobutyl ester, triphosphoric acid monobutyl ester, triphosphoric acid Dibutyl ester, tetraphosphoric acid monobutyl ester, tetraphosphoric acid dibutyl ester, tetraphosphoric acid tributyl ester, pentaphosphoric acid monobutyl ester, pentaphosphoric acid dibutyl ester, pentaphosphoric acid tributyl ester, pentaphosphoric acid tetrabutyl ester, trimetaphosphoric acid Monobutyl ester, trimetaphosphoric acid dibutyl ester, tetrametaphosphoric acid monobutyl ester, tetrametaphosphoric acid dibutyl ester, tetrametaphosphoric acid tributyl ester, diphosphoric acid mono (t-butyl) ester, triphosphoric acid mono (t-
Butyl) ester, triphosphoric acid di (t-butyl) ester, tetraphosphoric acid mono (t-butyl) ester, tetraphosphoric acid di (t-butyl) ester, tetraphosphoric acid tri (t-butyl) ester
Ester, pentaphosphoric acid mono (t-butyl) ester, pentaphosphoric acid di (t-butyl) ester, pentaphosphoric acid tri (t-butyl) ester, pentaphosphoric acid tetra (t-butyl) ester, trimetaphosphoric acid mono ( t-butyl) ester, trimetaphosphoric acid di (t-butyl) ester, tetrametaphosphoric acid mono (t-butyl) ester, tetrametaphosphoric acid di (t-butyl) ester, tetrametaphosphoric acid tri (t-)
Butyl) ester, diphosphoric acid monobenzyl ester, triphosphoric acid monobenzyl ester, triphosphoric acid dibenzyl ester, tetraphosphoric acid monobenzyl ester, tetraphosphoric acid dibenzyl ester, tetraphosphoric acid tribenzyl ester, pentaphosphoric acid monoester Benzyl ester, pentaphosphoric acid dibenzyl ester, pentaphosphoric acid tribenzyl ester, pentaphosphoric acid tetrabenzyl ester, trimetaphosphoric acid monobenzyl ester, trimetaphosphoric acid dibenzyl ester, tetrametaphosphoric acid monobenzyl ester, tetrametaphosphoric acid dibenzyl ester, Tetrametaphosphoric acid tribenzyl ester,
Diphosphoric acid monophenyl ester, triphosphoric acid monophenyl ester, triphosphoric acid diphenyl ester, tetraphosphoric acid monophenyl ester, tetraphosphoric acid diphenyl ester, tetraphosphoric acid triphenyl ester, pentaphosphoric acid monophenyl ester, pentaphosphoric acid Diphenyl ester, pentaphenyl triphenyl ester, pentaphosphoric tetraphenyl ester, trimetaphosphoric acid monophenyl ester, trimetaphosphoric acid diphenyl ester, tetrametaphosphoric acid monophenyl ester, tetrametaphosphoric acid diphenyl ester, tetrametaphosphoric acid triphenyl ester, and these A mixture of

In the phosphorus oxo acid condensate of the present invention, a part of the acid may be replaced with a cation species to form an acid salt. Examples thereof include metal salts represented by alkali metal and / or alkaline earth metal salts such as sodium salt, potassium salt, lithium salt, cesium salt, rubidium salt and magnesium salt, and onium salts such as ammonium salt.

Specifically, monosodium diphosphate salt,
Triphosphate monosodium salt, triphosphate disodium salt,
Monosodium tetraphosphate, disodium tetraphosphate,
Trisodium tetraphosphate, pentasodium pentaphosphate, disodium pentaphosphate, trisodium pentaphosphate, tetrasodium pentaphosphate, monosodium trimetaphosphate, disodium trimetaphosphate, tetrametaphosphate Monosodium salt, disodium tetrametaphosphate, trisodium tetrametaphosphate, monopotassium diphosphate, monopotassium triphosphate, dipotassium triphosphate, monopotassium tetraphosphate, dipotassium tetraphosphate , Tripotassium tetraphosphate, monopotassium pentaphosphate, dipotassium pentaphosphate, tripotassium pentaphosphate, tetrapotassium pentaphosphate, monopotassium trimetaphosphate, dipotassium trimetaphosphate, monotetrametaphosphate Potassium salt, tetrametaphosphoric acid dipotassium salt,
Tetrametaphosphoric acid tripotassium salt, diphosphoric acid monolithium salt, triphosphoric acid monolithium salt, triphosphoric acid dilithium salt, tetraphosphoric acid monolithium salt, tetraphosphoric acid dilithium salt,
Trilithium tetraphosphate, monolithium pentaphosphate, dilithium pentaphosphate, trilithium pentaphosphate, tetralithium pentaphosphate, monolithium trimetaphosphate,
Dilithium trimetaphosphate, monolithium tetrametaphosphate, dilithium tetrametaphosphate, trilithium tetrametaphosphate, monocesium diphosphate, monocesium triphosphate, dicesium triphosphate, monocesium tetraphosphate Salt, disescium tetraphosphate, tricesium tetraphosphate, monocesium pentaphosphate, disesium pentaphosphate, tricesium pentaphosphate, tetracesium pentaphosphate, monocesium trimetaphosphate, discesium trimetaphosphate , Tetrametaphosphoric acid monocesium salt, tetrametaphosphoric acid dicesium salt, tetrametaphosphoric acid tricesium salt, diphosphoric acid monorubidium salt, triphosphoric monorubidium salt, triphosphoric dilubidium salt, tetraphosphoric monorubidium salt, tetraphosphoric acid Zirbidium salt, trirubidium tetraphosphate salt, penta Acid monorubidium salt, diphosphorus pentaphosphate salt, trilubidium pentaphosphate salt, tetrarubidium pentaphosphate salt, monorubidium trimetaphosphate salt, dirubidium trimetaphosphate salt, monorubidium tetrametaphosphate salt, zirbidium tetrametaphosphate salt, tetra Trilubidium metaphosphate, monomagnesium triphosphate, monomagnesium tetraphosphate, monomagnesium pentaphosphate, dimagnesium pentaphosphate, monomagnesium trimetaphosphate, monomagnesium tetrametaphosphate, diphosphate Monoammonium salt, triphosphoric acid monoammonium salt, triphosphoric acid diammonium salt, tetraphosphoric acid monoammonium salt, tetraphosphoric acid diammonium salt, tetraphosphoric acid triammonium salt, pentaphosphoric acid monoammonium salt,
Pentaammonium pentaphosphate, triammonium pentaphosphate, tetraammonium pentaphosphate, monoammonium trimetaphosphate, diammonium trimetaphosphate,
Examples include tetrametaphosphoric acid monoammonium salt, tetrametaphosphoric acid diammonium salt, tetrametaphosphoric acid triammonium salt and mixtures thereof.

Further, in order to obtain the aromatic polycarbonate composition of the present invention having good heat stability, the content of the phosphorus oxo acid condensate is 1 × 10 ⁻³ to 100 parts by weight of the aromatic polycarbonate as a phosphorus element. The range is preferably 1 × 10 ³ parts by weight, more preferably 1 × 10 ^-2 to 1 × 1.
It is in the range of 0 ² parts by weight, more preferably 1 × 10 ^-2 to 10 parts by weight.

In principle, the larger the amount of the phosphorus oxo acid condensate used, the greater the effect of improving the heat resistance stability, and less than 1 × 10 ⁻³ parts by weight as a phosphorus element based on 100 parts by weight of the aromatic polycarbonate. However, if the amount is more than 1 × 10 ³ parts by weight, the resulting aromatic polycarbonate composition often has an adverse effect on the hue, transparency, and mechanical properties, which is not preferable.

The phosphorous acid condensate of the present invention may be used in combination of two or more kinds, if desired. In this case, the total amount of phosphorus element contained in all the phosphorus oxo acid condensates used is preferably within the above range.

It is disclosed in DE1019674 that the addition of condensed phosphoric acid to polycarbonate has an effect of suppressing a decrease in molecular weight due to humidity under heating and melting. This is due to the effect of dehydration in the polymer by such an acid. Is brought about by.

On the other hand, the neutralization of the alkali metal or alkaline earth metal contained in the catalyst with a basic acid and the inactivation by coordination with the oxygen donor or interaction with the oxygen donor are phosphorus oxo in the present invention. It is considered to be the main action of the acid, and the phosphorus oxo acid condensate in the present invention has the effect of improving the heat resistance stability by a different action.

(Polymer Production Method, Raw Material) The aromatic polycarbonate in the present invention may have any structure as long as it is formed by reacting an aromatic dihydroxy compound and a carbonate-forming compound.

For example, the main repeating unit is the following formula (1)

[0043]

[Chemical 2]

(R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group,
Or an aryl group, W is R ¹ , R ² , R ³ and / or
Alternatively, a single bond which may be bonded to R ⁴ to form a ring, an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, and 6 to 20 carbon atoms.
Is a cycloalkylene group having 6 to 20 carbon atoms, a cycloalkylidene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylenearylenealkylene group having 6 to 20 carbon atoms. The structure represented by () is mentioned as a preferable example.

Among them, good transparency, hue and mechanical strength are obtained, and raw materials of high purity are easily available at low cost.
From the viewpoint of production cost, an aromatic polycarbonate whose main repeating unit is represented by the following formula (2) can be preferably used.

[0046]

[Chemical 3]

The aromatic polycarbonate composition of the present invention may be produced by any method using an aromatic dihydroxy compound and a carbonate-forming compound as raw materials, for example, a phosgene method such as an interfacial polymerization method, a melt polymerization method, a solid phase weight method. It can be produced by any legal method.

The aromatic dihydroxy compound used as a raw material may have any structure, but for example, a compound represented by the following formula (3) is preferably used.

[0049]

[Chemical 4]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, and W is R ¹ , R ² or A single bond which may be bonded to R ³ and / or R ⁴ to form a ring, an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, and 6 to 6 carbon atoms.
A cycloalkylene group having 20 carbon atoms, a cycloalkylidene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylenearylenealkylene group having 6 to 20 carbon atoms. ) Specific examples of the aromatic dihydroxy compound represented by the formula (3) include bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) propane,
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2- Bis (4-hydroxy-
3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 4,4′-dihydroxyphenyl-1,1′-m-diisopropylbenzene, 4,4′-dihydroxyphenyl-9,9-fluorene , Bis (4-hydroxyaryl) alkanes, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) )
-3,3-dimethyl-5-methylcyclohexane, 1-
Methyl-1- (4-hydroxyphenyl) -4- (dimethyl-4-hydroxyphenyl) methyl-cyclohexane, 4- [1- [3- (4-hydroxyphenyl) -4
-Methylcyclohexyl] -1-netylethyl] -phenol, 4,4 '-[1-methyl-4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol, 2,2,2', 2'- Tetrahydro-3,3
3 ', 3'-tetramethyl-1,1'-spirobis-
Bis (hydroxyaryl) cycloalkanes such as [1H-indene] -6,6′-diol, bis (4-
Hydroxyphenyl ethers, bis (4-hydroxy-3,5-dichlorophenyl) ether, 4,4′-dihydroxy-3,3′-dimethylphenyl ether, and other dihydroxyaryl ethers, 4,4′-dihydroxydiphenyl sulfide , 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, etc., dihydroxydiaryl sulfides 4,4′-dihydroxydiphenyl sulfoxide, 4,
Dihydroxy diaryl sulfoxides such as 4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone,
4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc., dihydroxydiaryl sulfones, 4,4′-dihydroxydiphenyl-3,3′-isatin, etc., dihydroxydiaryl isatins,
3,6-dihydroxy-9,9-dimethylxanthene,
And dihydroxydiarylxanthenes.

In addition to the compound represented by the above formula (3), as an aromatic dihydroxy compound, resorcin, 3-methylresorcin, 3-ethylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3 Dihydroxybenzenes such as cumylresorcin, hydroquinone, 2-methylhydroquinone, 2-ethylhydroquinone, 2-butylhydroquinone, 2-t-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, 4,4 ′ -Dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl, etc. Dihydroxydiphenyls are also preferably used.

Among them, 2,2-bis (4-hydroxyphenyl) propane is preferable as a monomer because of its stability as a monomer, the availability of a small amount of impurities contained therein, and the easy availability.

In the aromatic polycarbonate of the present invention, various monomers are used for the purpose of controlling the optical properties such as controlling the glass transition temperature, improving the fluidity, increasing the refractive index or reducing the birefringence. It goes without saying that it is possible to contain one kind or two or more kinds according to need.

Specific examples thereof include aliphatic dihydroxy compounds such as ethylene glycol, 1,
4-butanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol,
1,10-decanediol, diethylene glycol, tetraethylene glycol, polyethylene glycol, polytetramethylene glycol, etc., or dicarboxylic acids such as succinic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, cyclohexanedicarboxylic acid, terephthalic acid , Or oxyacids, for example,
Examples thereof include p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, lactic acid and the like.

In the interfacial polymerization method, examples of the carbonate bond-forming compound include carbonyl halides such as phosgene and haloformate compounds.

In the melt polymerization method, a carbonate bond-forming compound is a carbonic acid diester, specifically diphenyl carbonate, ditolyl carbonate or bis (2-
Aromatic carbonic acid diesters such as chlorophenyl) carbonate, m-cresylcarbonate, dinaphthylcarbonate and bis (4-phenylphenyl) carbonate can be mentioned.

In addition, aliphatic carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate can be used if desired.

Of these, diphenyl carbonate is preferred as the one from the viewpoint of reactivity, stability of the obtained resin against coloration, and cost.

The aromatic polycarbonate of the present invention can be produced by reacting such a carbonate bond-forming compound with the above aromatic dihydroxy compound by a known method.

In the solid phase polymerization method, the aromatic polycarbonate oligomer having a low molecular weight produced by the above-mentioned interfacial polymerization method or melt polymerization method is crystallized, and the polymerization is advanced in a solid state at high temperature, normal pressure or, if desired, reduced pressure. By
The aromatic polycarbonate of the present invention can be used.

Further, in the above-mentioned method for producing an aromatic polycarbonate, a polyester carbonate produced by using a dicarboxylic acid derivative such as dicarboxylic acid, dicarboxylic acid halide, dicarboxylic acid or ester together with phosgene or carbonic acid diester is also applicable. Can be used in inventions.

Examples of the dicarboxylic acid or dicarboxylic acid derivative include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, terephthalic acid chloride, isophthalic acid chloride, diphenyl terephthalate and diphenyl isophthalate, succinic acid, glutaric acid, adipic acid, suberin. Acids, azelaic acid, sebacic acid, decanedioic acid, dodecanenic acid, adipic acid chloride, suberic acid chloride, azelaic acid chloride, sebacic acid chloride, diphenyl azelate, diphenyl sebacate, diphenyl dodecanedioate, diphenyl dodecanoate, etc. Aliphatic dicarboxylic acids, cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-
Cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid chloride, 1,2-cyclobutanedicarboxylic acid chloride, 1,3-cyclobutanedicarboxylic acid chloride, 1,2-cyclopentanedicarboxylic acid chloride,
1,3-cyclopentanedicarboxylic acid chloride, 1,2
-Cyclohexanedicarboxylic acid chloride, 1,3-cyclohexanedicarboxylic acid chloride, 1,4-cyclohexanedicarboxylic acid chloride, cyclopropanedicarboxylic acid diphenyl, 1,2-cyclobutanedicarboxylic acid diphenyl, 1,3-cyclobutanedicarboxylic acid diphenyl, 1, Diphenyl 2-cyclopentanedicarboxylate,
1,3-Cyclopentanedicarboxylic acid diphenyl, 1,
2-Cyclohexanedicarboxylate diphenyl, 1,3-
Examples thereof include alicyclic dicarboxylic acids such as diphenyl cyclohexanedicarboxylic acid and diphenyl 1,4-cyclohexanedicarboxylic acid.

When producing the aromatic polycarbonate of the present invention, a polyfunctional compound having three or more functional groups in one molecule can be used in combination with the above dihydroxy compound. As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferably used.

Specifically, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2 ', 2 "-
Tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-α, α ′, α ″ -tris (4-hydroxyphenyl) -1,4-diethylbenzene, α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
3,5-triisopropylbenzene, phloroglysin,
4, 6. Dimethyl-2,4,6-tris (4-hydroxyphenyl) -heptane-2,1,3,5-tris (4
-Hydroxyphenyl) benzene, 2,2-bis [4,
4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid and the like can be mentioned.

Of these, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are preferably used. it can.

When a polyfunctional compound is used in combination, for example, for the purpose of increasing the melt viscosity of the aromatic polycarbonate, the polyfunctional compound is 0.03 mol or less, preferably 0.00005 to 1 mol, relative to 1 mol of the aromatic dihydroxy compound.
0.02 mol, more preferably 0.0001 to 0.0
It is selected in the range of 1 mol.

(OH Termination) The number of terminal OH groups of the aromatic polycarbonate composition of the present invention is 3 to the total number of terminals.
If it is 95 mol%, good heat resistance stability can be obtained, and haze during injection molding can be reduced.

It is conventionally known that the lower the concentration of terminal hydroxyl groups, the better the heat resistance stability is, but in the aromatic polycarbonate composition of the present invention, the number of terminal hydroxyl groups is 3 to 60 relative to the total number of terminals. Good heat stability can be obtained in the range of mol%.

When the content is preferably 3 to 45 mol%, more preferably 3 to 36 mol%, and particularly preferably 3 to 27 mol%, good haze during molding and heat resistance can be obtained.

The terminal hydroxyl group concentration is preferably lower than this range, but in the aromatic polycarbonate of the present invention, even if it is reduced to less than 3 mol%, the heat stability is not further improved. Further, when the terminal hydroxyl group is introduced in an amount of more than 95 mol%, color deterioration of the molded product, which is presumed to be caused by an oxidation reaction, and a decrease in molecular weight occur particularly during heat processing,
It is not preferable for the purpose of the present invention.

The aromatic polycarbonate according to the present invention has a viscosity average molecular weight of 10,000 to 100,000.
Is preferred. If it is less than 10,000, the physical properties of the aromatic polycarbonate are insufficient. Again 100,000
If it exceeds, the problem of deterioration of moldability tends to occur.

(Melt Viscosity Stabilizer) Although aromatic polycarbonate is unstable to thermal decomposition reaction or hydrolysis reaction, it is preferable that the aromatic polycarbonate has melt viscosity stability of 0.5% or less. It is important for achieving the object of the invention. It is more preferably 0.3% or less, still more preferably 0.1% or less, and particularly preferably 0%.

When the melt viscosity stability exceeds 0.5%, in addition to poor hue stability during melt polymerization or molding, the mechanical properties are stable under high humidity conditions and when the molded product is used for a long period of time. Defects are likely to occur, in particular, the impact resistance is remarkably lowered, and it becomes unusable for practical use.

The aromatic polycarbonate of the present invention preferably has a melt viscosity stability of 0.5% or less.
This can be achieved by, for example, adding a specific amount of the melt viscosity stabilizer to the aromatic polycarbonate after the polycondensation reaction.

As the melt viscosity stabilizer used in the present invention, as described in JP-A-8-59975, phosphonium sulfate, ammonium sulfate sulfate, sulfuric acid, phosphonium sulfonate, ammonium salt, sulfonate and And / or a sulfuric acid compound such as sulfonic acid and a sulfonic acid compound.

Specific examples of the sulfuric acid compound and the sulfonic acid compound include tetrabutylphosphonium sulfate,
Sulfate di (tetrabutylphosphonium) salt, Octylsulfonic acid tetrabutylphosphonium salt, Octylsulfonic acid di (tetrabutylphosphonium) salt, Decylsulfonic acid tetraphosphonium salt, Decylsulfonic acid di (tetraphosphonium) salt, Benzenesulfonic acid tetramethyl Phosphonium salt, benzenesulfonic acid di (tetramethylphosphonium) salt, benzenesulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid di (tetrabutylphosphonium) salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid di (tetrabutyl) Phosphonium) salt, decyl sulfonic acid tetramethyl ammonium salt, decyl sulfonic acid di (tetramethyl ammonium) salt, benzene sulfonic acid tetraethyl ammonium salt Nzensuruhon di (tetraethylammonium) salt, and the like.

Examples of the sulfonic acid and sulfonic acid ester include aromatic sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid, aliphatic sulfonic acids such as dodecyl sulfonic acid, hexadecyl sulfonic acid and nonyl sulfonic acid, and benzene sulfone. Methyl acid, ethyl benzene sulfonate, butyl benzene sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, ethyl p-toluene sulfonate, butyl p-toluene sulfonate, phenyl p-toluene sulfonate, etc. are exemplified. .

Preferably, an ester compound is used rather than sulfonic acid itself.

The melt viscosity stabilizer is effective for the aromatic polycarbonate produced by the interfacial polymerization method, but is particularly effective for the aromatic polycarbonate produced by the melt polymerization method or the solid phase polymerization method. is there.

In these cases, 0.7 to 100 equivalents are preferably used per equivalent of the alkali metal and / or alkaline earth metal in the alkali metal compound and / or alkaline earth metal compound remaining in the aromatic polycarbonate. Is 0.8 to 30 equivalents, more preferably 0.
By using 9 to 20 equivalents, particularly preferably 0.9 to 10 equivalents, the melt viscosity stability of the aromatic polycarbonate can be suppressed to 0.5% or less. When a melt viscosity stabilizer is used, it is preferable to subject the aromatic polycarbonate to a reduced pressure treatment when or after the melt viscosity stabilizer is added.

(Release Agent) The aromatic polycarbonate composition of the present invention contains an ester of an aliphatic carboxylic acid having 10 to 25 carbon atoms and an aliphatic alcohol having 2 to 10 carbon atoms as a releasing agent.

Under the high temperature conditions often applied to aromatic polycarbonate compositions according to the present invention,
The aromatic polycarbonate composition comprises a phosphorus oxo acid condensate, an aliphatic carboxylic acid having 10 to 25 carbon atoms and 2 to 2 carbon atoms.
When the ester of 10 with the aliphatic alcohol is contained at the same time, good mold releasability and good heat stability can be achieved at the same time.

For the purpose of simultaneously achieving good releasability and good heat stability, the molding temperature of the aromatic polycarbonate composition according to the present invention is preferably 300 ° C. or higher, more preferably 330 ° C. or higher. , 350 ° C or higher is more preferable. The upper limit is preferably 420 ° C. This is because if the temperature exceeds 420 ° C, the strength of the hair molding may be significantly reduced, and it may not be practically used.

Here, the molding temperature means the cylinder temperature of the molding machine. If the cylinder is divided into several temperature zones, the substantially lowest temperature among them can be the criterion.

This agent is an aromatic polycarbonate 100
It is preferable to contain the ester in an amount of 0.00005 to 0.2 part by weight per part by weight. -The range for obtaining better releasability is preferably 0.005 to 0.15 parts by weight, more preferably 0.0075 to 0.1 parts by weight, per 100 parts by weight of the aromatic polycarbonate, It is particularly preferably in the range of 0.01 to 0.1 part by weight.

If the amount of this ester component is less than 0.005 part by weight, the desired releasability cannot be obtained. In principle, the higher the content, the better the releasability, but 0.2
When it exceeds the weight part, the releasability is not increased so much, and on the other hand, the surface property of the molded product is deteriorated and the mold is contaminated, which is not preferable.

The aliphatic carboxylic acid having 10 to 25 carbon atoms in the present invention includes aliphatic linear or branched carboxylic acid. Also included are saturated or unsaturated carboxylic acids.

Two or more carboxylic acids may be present in the molecule. As such aliphatic carboxylic acid, specifically, lauric acid which is a linear carboxylic acid, myristic acid, palmitic acid, stearic acid, behenic acid, and branched fatty acid isodecanoic acid, isotridecanoic acid, isomyristic acid, Isopalmitic acid, isostearic acid,
Examples include isoarachidic acid and isohexacoic acid. Other unsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid, 5,8,11,14-eicosatetraenoic acid, 4,7,10,13,16,19-docosahexaenoic acid and the like are exemplified. . Among these, especially lauric acid,
Palmitic acid, stearic acid, and isostearic acid exhibit good mold release properties and are preferably used.

The term "aliphatic alcohol having 2 to 10 carbon atoms" as used in the present invention includes an aliphatic linear or branched alcohol and a saturated or unsaturated alcohol. Two or more hydroxyl groups may be present in the molecule, and it is preferably a polyhydric alcohol in order to obtain good releasability. Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,
3-propylene glycol, 1,4-butanediol,
Glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, or 1,4-
Butenediol, sorbitol, sorbitan,
Examples are sucrose and the like. Of these, glycerol and pentaerythritol show particularly good mold release properties,
Preferably used.

Specific examples of esters of these aliphatic carboxylic acids and aliphatic alcohols include esters of at least one of the above aliphatic carboxylic acids and at least one of the aliphatic alcohols. When the aliphatic alcohol is a polyhydric alcohol, two or more ester bonds may be present. For example, in the case of an aliphatic trihydric alcohol, any of monoester, diester and triester with a carboxylic acid is the above. Included in esters.

Specific examples of the ester of an aliphatic carboxylic acid and an aliphatic polyhydric alcohol include ethylene glycol monoisopalmitate, ethylene glycol distearate, propylene glycol dioleate, propylene glycol monoisomyristate, 1,4 -Butanediol diisopalmitate, 1,4-butenediol diisostearate, 1,4-butenediol monostearate, 1,4-butenediol distearate, glycerol monolaurate, glycerol dilaurate, glycerol trilaurate Rate, glycerol monomyristate, glycerol dimyristate, glycerol trimyristate, glycerol monostearate, glycerol distearate, glycerol tristearate,
Glycerol monobehenate, glycerol dibehenate, glycerol tribehenate, glycerol monoisomyristate, glycerol diisomyristate, glycerol triisomyristate, glycerol monoisostearate, glycerol diisostearate, glycerol triisostearate Rate, glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monolinoleate, glycerol monopalmitate, glycerol dipalmitate, glycerol tripalmitate, glycerol monostearate, glycerol distearate, glycerol tristearate, glycerol Monoisopalmitate, glycerol diisopalmitate, glycerol triisopalmitate, green Roll monoisostearate, glycerol diisostearate, glycerol triisostearate, glycerol stearate isopalmitate, glycerol trimyristate, glycerol tribehenate, trimethylolpropane monostearate, trimethylolpropane monobehenate, Trimethylolpropane monoisopalmitate, trimethylolpropane monooleate, trimethylolpropane dipalmitate, trimethylolpropane diisostearate, trimethylolpropane tristearate, trimethylolpropane triisomyristate, trimethylolpropane trioleate, Pentaerythritol monopalmitate, pentaerythritol dipalmitate, pentaerythritol tripalmitate, Pentaerythritol tetra palmitate, pentaerythritol monoisostearate palmitate, pentaerythritol diisopropyl triisostearate palmitate, pentaerythritol triisopalmitate Tate,
Pentaerythritol tetraisopalmitate, pentaerythritol trioleate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, pentaerythritol tetraisopalmitate, pentaerythritol diolate distearate Other examples include sorbitan monostearate and sucrose diisostearate.

Among these, glycerol monolaurate, glycerol monopalmitate, glycerol monostearate, glycerol monoisostearate, pentaerythritol tetralaurate, pentaerythritol tetrapalmitate, pentaerythritol tetrastearate, pentaerythritol tetralate. Esters of isostearates are preferably used.

In addition, the release agents exemplified below may be used in combination, if desired.

That is, as a hydrocarbon type release agent, natural,
Synthetic paraffin waxes, polyethylene wax, fluorocarbons, etc., fatty acid-based release agents such as higher fatty acids such as stearic acid, oxyfatty acid such as hydroxystearic acid, etc., fatty acid amide-based release agents such as ethylenebisstearylamide Amide, alkylene fatty acid amides such as erucic acid amide, alcohol-based releasing agents such as stearyl alcohol, cetyl alcohol and other aliphatic alcohols, polyhydric alcohols such as polyglycol, polyglycerol, trimethylolpropane . Other polysiloxanes can also be used. These may be used alone or in combination of two or more.

(Stabilizer) Further, the aromatic polycarbonate composition of the present invention may contain a heat stabilizer in order to prevent a decrease in molecular weight and a deterioration in hue. Examples of such heat stabilizers include hypophosphorous acid, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and examples thereof include trisnonylphenylphosphite, trisoctylphenylphosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (2,6)
-Di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene diphosphite, tetrakis (2,6-di-t-)
Butylphenyl) 4,4′-biphenylenediphosphite, trimethylphosphate, dimethylphenylphosphate, diethylphenylphosphate, methyldiphenylphosphate, ethyldiphenylphosphate, distearylpentaerythritoldiphosphite, didodecylpentaerythritoldiphosphite, bis ( 2,4-di-t-butyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl) 4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butyl-phenyl) pentaerythritol diphosphite, diphenyloctylphosphite, diphenylde Sylphosphite, phenyl-didecylphosphite, diphenyldecylphosphite, tridecylphosphite, triphenylphosphite, (2,4-di-t-butyl-6,6'-methylene-
Phenyl) octyl phosphite, di (nonylphenyl) dinonylphenyl-phosphite 4,4'-biphenylenediphosphinic acid tetrakis (2,4-di-ter)
t-butylphenyl), dimethyl benzenephosphonate and the like. You may use these heat stabilizers individually or in mixture of 2 or more types. The blending amount of such a heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, more preferably 0.001 to 1 part by weight based on 100 parts by weight of the aromatic polycarbonate composition of the present invention.
001-0.1 weight part is more preferable.

(Filler) Furthermore, it is possible to add an inorganic or organic filler to the aromatic polycarbonate composition of the present invention in order to improve the rigidity etc. within a range not impairing the object of the present invention.

Examples of such inorganic fillers include talc, mica, glass flakes, glass beads, calcium carbonate,
Examples thereof include plate-like or granular inorganic fillers such as titanium oxide, and fibrous fillers such as glass fibers, glass milled fibers, wollastonite, carbon fibers, and metal-based conductive fibers.

On the other hand, examples of the organic filler include aramid fiber, crosslinked acrylic particles, crosslinked silicone particles and the like.

The content of these inorganic and organic fillers is preferably 1 to 150 parts by weight, more preferably 3 to 100 parts by weight, based on 100 parts by weight of the aromatic polycarbonate composition of the present invention. The filler usable in the present invention may be surface-treated with a silane coupling agent or the like.
By this surface treatment, good results are obtained such that the decomposition of the aromatic polycarbonate is suppressed.

Other resins may be added to the aromatic polycarbonate composition of the present invention as long as the object of the present invention is not impaired. Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, polybutylene terephthalate, etc. Polyester resin, amorphous polyarylate resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile /
Examples thereof include resins such as butadiene / styrene copolymer (ABS resin), polytacrylate resin, phenol resin, and epoxy resin.

(Other Additives) The aromatic polycarbonate of the present invention has heat resistance stability superior to conventional ones,
Furthermore, when molding various molded articles using this, conventionally known processing stabilizers, heat resistance stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, flame retardants, release agents depending on the application. A quencher, a metal deactivator, a metal soap, a nucleating agent, or an organic or inorganic coloring agent such as a dye or a pigment may be added.

(Use) The aromatic polycarbonate of the present invention may be used for any purpose, for example, electronic / communication equipment, OA equipment, lenses, prisms, optical disk substrates,
Optical parts such as optical fibers, home electric appliances, lighting members, electronic and electrical materials such as heavy electric members, vehicle interior and exterior, precision machinery,
Mechanical materials such as insulation materials, medical materials, safety / protection materials, sports / leisure goods, household goods and other miscellaneous goods materials, containers /
It can be suitably used as a packaging material, a display / decoration material, and the like. Among them, the optical disk substrate is the most preferable example, for example, compact disk (CD), C
D-ROM, CD-R, CD-RW, magneto-optical disk (MO), digital versatile disk (DVD-
ROM, DVD-Video, DVD-Audio, D
VD-R, DVD-RAM, DVD-RW, etc.) substrates and the like.

The sheet obtained from the aromatic polycarbonate composition of the present invention has excellent adhesiveness and printability,
Utilizing its characteristics, it is widely used for electric parts, building material parts, automobile parts, etc.

Specifically, various window materials, that is, glazing products for window materials such as general houses, gymnasiums, baseball domes, vehicles (construction machinery, automobiles, buses, bullet trains, train cars, etc.), and various side wall plates (skydome, skydome, etc.). Top lights, arcades, condominium waistboards, road side walls), window materials for vehicles, etc.
OA equipment display, touch panel, membrane switch, photographic cover, aquarium aromatic polycarbonate resin laminate, front panel of projection TV and plasma display, Frennel lens, optical card, liquid crystal cell in combination with optical disc and polarizing plate, It is useful for optical applications such as a phase difference correction plate.

The thickness of the aromatic polycarbonate sheet is not particularly limited, but is usually 0.1 to 10 mm.
Is preferable, 0.2-8 mm is more preferable, and 0.2-
3 mm is particularly preferred. In addition, such an aromatic polycarbonate sheet is subjected to various laminating treatments for improving weather resistance that adds a new function, scratch resistance improving treatments for improving surface hardness, and various processing treatments such as semi- and opaque processing. May be.

(Addition Method) Any method can be used as a method for adding and blending the phosphorus oxo acid condensate of the present invention to the aromatic polycarbonate after polymerization and a method for incorporating an additive into the aromatic polycarbonate composition of the present invention. Can be adopted.

For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder or the like is appropriately used.

In addition, the phosphorus oxo acid condensate of the present invention, or an aliphatic carboxylic acid having 10 to 25 carbon atoms and 2 to 2 carbon atoms
Additives such as esters with fatty alcohols or other stabilizers of 10 as master pellets produced by melt-mixing into resin as it is and / or at a predetermined concentration, and / or resin pellets or dry blend with resin powder It may be added as a master powder produced by and / or in the form of a solution or slurry in which it is dissolved or dispersed in a solvent or a dispersion medium.

In particular, when a plurality of types of additives are used, handling at the time of addition is easy and the additives are efficiently dispersed in the polymer. Therefore, master pellets or masters using aromatic polycarbonate resin or powder as a medium are used. The method of adding as a powder is preferably applied.
The aromatic polycarbonate composition thus obtained is generally formed into pellets as it is or with a melt-kneading extruder, and then molded by various methods.

[0110]

Industrial Applicability According to the present invention, an aromatic polycarbonate composition having excellent heat stability represented by hue stability during molding and a molded product thereof can be obtained. In addition, a method for molding an aromatic polycarbonate molded article having excellent heat resistance represented by hue stability during molding can be obtained.

[0111]

EXAMPLES The present invention will be described below with reference to examples. In the present invention, the heat resistance stability of the aromatic polycarbonate composition is represented by the hue stability during heat molding,
The amount of change in hue during heating (yellowing degree ΔYI) is used as an index for evaluation.

[Analysis Method] 1) Intrinsic Viscosity [η] of Aromatic Polycarbonate Composition It was measured in methylene chloride at 20 ° C. with an Ubbelohde viscosity tube. The viscosity average molecular weight (Mw) was calculated from the intrinsic viscosity by the following formula.

[Η] = 1.23 × 10 ⁻⁴ × ^0.83 2) Melt viscosity stability Melting measured at 300 ° C. under a nitrogen stream using a RAA type flow analysis device manufactured by Rheometrics. The absolute value of the change in viscosity was measured for 30 minutes, and the amount of change per minute divided by the initial melt viscosity was expressed as a percentage.

For example, the initial melt viscosity is 1,700 P
a · s and the change amount per minute is 8.5 Pa · s, the melt viscosity stability is (8.5 / 1,700) ×
100 = 0.5%.

In order for the long-term stability of the aromatic polycarbonate composition to be good, this value should not exceed 0.5%.

3) Hue stability (yellowness, yellowing before and after retention) A flat plate having a size of 50 mm × 50 mm × 5 mm was set at a cylinder temperature of 35 by an M50B injection molding machine manufactured by Meiki Seisakusho Co., Ltd.
0 ℃, molding cycle 20 seconds, mold temperature 75 ℃, injection pressure 3
Molding was carried out at 00 kg and a clamping force of 50 tons, and the degree of yellowness (YI-A) of this molded product was measured.

Further, in order to evaluate the hue stability during the molding process, the test was conducted under the condition that the heat load was significantly increased.
That is, during the molding step in the above method, the polymer was allowed to stay in the cylinder for 15 minutes and then molded, the yellowness (YI-B) was measured, and the difference between YI-B and YI-A was calculated by measuring the yellowing degree. (ΔYI) was used as an index of hue stability during molding.

The yellowness of the flat plate was measured by measuring the X, Y, and Z values with a Z-1001DP color difference meter manufactured by Nippon Denshoku Co., Ltd., and the YI values (YI-A, YI-B) were determined by the following equation.

YI = (100 / Y) * (1.277X-
1.060Z) As a hue evaluation, the above-mentioned yellowness is a range in which no yellowish tint is visually observed, and when YI-A <2.3, the hue is good, and otherwise, it is determined that the hue is poor, Further, as a heat resistance stability evaluation, when the yellowing degree was ΔYI <1.0, it was determined that the hue stability, that is, the heat resistance stability was good and the others were poor.

[0120]

Examples 1 to 5, Comparative Examples 1 to 3 Phosgene blown tube,
In a reaction tank equipped with a thermometer and a stirrer, 502.8 g (2.21 mol) of bisphenol A, 2.21 L of a 7.2 wt% sodium hydroxide aqueous solution (4.19 mol of sodium hydroxide) and hydro 0.98 g (0.0056 mol) of sodium sulfite was charged and dissolved, and 1.27 L of methylene chloride and 48.5 with stirring.
After adding 80.70 g of a weight% aqueous sodium hydroxide solution (0.98 mol of sodium hydroxide), phosgene 25
0.80 g (0.253 mol) was added at 25 ° C. over 180 minutes to carry out a phosgenation reaction.

After the completion of phosgenation, 17.51 g (0.117 mol) of p-tert-butylphenol, and 4
80.40 g of 8.5 wt% sodium hydroxide aqueous solution
(0.97 mol) and 1.81 mL (0.013 mol) of triethylamine as a catalyst were added, and the reaction was terminated by maintaining the temperature at 33 ° C. and stirring for 2 hours.

The methylene chloride layer was separated from the reaction mixture, and washing with water was repeated 5 times for purification to obtain a viscosity average molecular weight of 15
300 polycarbonate resins were obtained. The terminal OH group concentration is 20% of the total number of terminal groups, and the total terminal group concentration is 230
Equivalent weight / ton polymer.

To 100 parts by weight of the polycarbonate resin, a release agent and a heat stabilizer shown in the table were added, and 2
The mixture was kneaded into pellets with an axial extruder.

As a result, Examples 1 to 5 showed excellent results, especially in the degree of yellowing (ΔYI). In each of the examples and comparative examples, the transparency, hue, haze, and releasability were good under the conditions for obtaining the above YI-A.

Further, each of the polycarbonate compositions produced above was subjected to an elongation at break test piece in accordance with ASTM-D638, a circular flat plate having a thickness of 3 mm and Φ50 mm, and a thickness of 5.
mm-, 120 mm long x 12 mm wide, using a die for molding a connected product of rectangular flat plates, manufactured by Meiki Co., Ltd. DM-
It was molded with a 50B injection molding machine at a cylinder temperature of 380 ° C. (molded plate-a).

Further, after the cylinder temperature was kept at 380 ° C. for 10 minutes in the cylinder of the same injection molding machine, the molding plate-a
A molded plate was prepared in the same manner as in (Molded plate-b).

The elongation at break of the molded elongation at break test piece was evaluated according to the standard ASTM-D638.

Ten test pieces were prepared for one sample, and 2
After conditioning for 50 hours at 3 ° C. ± 2 ° C. and 50 ± 5% RH, measurement was performed in the same atmosphere as this, and evaluation was performed by the average value.

The higher the numerical value of the elongation at break, the higher the strength of the molded product. The larger the retention (R) of the elongation at break before and after the heat treatment (molded plate-a, molded plate-b) shown below, the higher the polymer. Has good heat resistance and has a breaking elongation retention rate R of 50%.
It was evaluated that the stability of mechanical strength due to heat was good if the above was satisfied. The results are shown in Table 1.

As a result, Examples 1 to 5 showed excellent results in terms of numerical values of elongation at break and retention of elongation at break.

R = E2 / E1 × 100 (%) E1: Elongation at break of molded plate-a E2: Elongation at break of molded plate-b

[0132]

[Table 1]

In the table, R1 = glycerin monostearate, P1 = tris (2,4-di-t-butylphenyl) phosphite, P2 = trisnonylphenylphosphite, P3 = tetrakis (2,4-di-). t-butyl-
Phenyl) 4,4'-biphenylenediphosphite, P
4 = trismethyl phosphate, P5 = phosphoric acid, P6 =
Pyrophosphoric acid, P7 = metaphosphoric acid, P8 = polyphosphoric acid (n
= 5.1).

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G11B 7/24 G11B 7/24 526H 7/26 521 7/26 521 H01G 9/04 H01G 9/05 G ( 72) Inventor Wataru Funakoshi 2-1, Hinode-cho, Iwakuni-shi, Yamaguchi Teijin Limited Iwakuni Research Center (72) Inventor Katsushi Sasaki 2-1, Hinode-cho, Iwakuni-shi Yamaguchi Prefecture F-term (in Iwakuni Research Center Teijin Limited) Reference) 4F071 AA50 AA81 AB25 AC10 AF01Y AF43Y AH16 BA01 BB05 BC01 4J002 CG011 CG021 DH056 EH047 EH057 EH097 FD066 FD167 5D029 KA07 KA08 5D121 AA02 DD05

Claims (8)

[Claims] 1. An aromatic polycarbonate obtained by reacting an aromatic dihydroxy compound with a carbonate-forming compound, a phosphorus oxo acid condensate, an aliphatic carboxylic acid having 10 to 25 carbon atoms, and 2 to 10 carbon atoms.
An aromatic polycarbonate composition comprising an ester of the above with an aliphatic alcohol. 2. The aromatic polycarbonate has a viscosity average molecular weight of 10,000 to 100,000, a melt viscosity stability of 0.5% or less, and a terminal OH group concentration of the total number of terminals. The aromatic polycarbonate composition according to claim 1, wherein the aromatic polycarbonate composition is 3 to 95 mol%. 3. The main repeating unit of the aromatic polycarbonate is represented by the following formula (1): (In the formula, R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbons, or 1 carbon atom.
To C20 alkoxy group, C6-20 cycloalkyl group, C6-20 aryl group, C6-20 cycloalkoxy group or C6-20 aryloxy group, and W is R ¹ , a single bond which may form a ring by bonding to R ² , R ³ and / or R ⁴ , an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, and 2 to 2 carbon atoms
It is a 20 alkylidene group, a C6-C20 cycloalkylene group, a C6-C20 cycloalkylidene group, a C6-C20 arylene group, or a C6-C20 alkylenearylene alkylene group. The aromatic polycarbonate composition according to claim 1 or 2, wherein 4. A molded product molded from the aromatic polycarbonate composition according to claim 1. 5. The molded product according to claim 4, wherein the molding temperature is 330 ° C. or higher and 420 ° C. or lower. 6. A disc substrate molded from the aromatic polycarbonate composition according to claim 1. 7. The disk substrate according to claim 6, wherein a molding temperature is 330 ° C. or higher and 420 ° C. or lower. 8. A molding method, characterized in that the molding temperature is maintained at 330 ° C. or higher and molding is performed using the aromatic polycarbonate composition according to any one of claims 1 to 3.