JP2002155198A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition low in deterioration of its color even if molded continuously for a long time, and low in decrease of its molecular weight and formation of a black foreign matter. SOLUTION: This polycarbonate resin composition contains an ester (1) of a polyhydric alcohol and a higher fatty acid, at least one compound (2) selected from the group consisting of phosphorous acid based acid phosphonium salt compound, phosphoric acid based acid phosphonium salt, boric acid based acid phosphonium salt, and condensed phosphoric acid based acid phosphonium salt, and/or at least a compound (3) selected from the group consisting of hypophosphorus acid, phosphorous acid, phosphoric acid, and condensed phosphoric acid in a polycarbonate having a specific viscosity average molecular weight, a specific phenolic end group concentration, and a melt viscosity stability of 0.5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition which accurately reproduces a mold pattern during mold molding such as injection molding and has good releasability from the mold. Thus, the present invention relates to a polycarbonate resin composition which has less deterioration in color tone, lowers molecular weight and generates less black foreign matter and has excellent heat stability even when the resin composition is continuously heat-molded for a long time.

[0002]

2. Description of the Related Art Polycarbonates that are superior to other resins in optical properties such as moldability, mechanical strength, and colorless transparency are audio discs, laser discs (registered trademark),
It is widely used as a material for a recording medium transparent substrate, a transparent sheet, a lens, or the like that records and / or reproduces information using a laser beam such as an optical disk memory or a magneto-optical disk.

As a method for producing a polycarbonate, a method of reacting a dihydroxy compound, particularly an aromatic dihydroxy compound such as bisphenol A, with a phosgene of a carbonate bond-forming precursor (interfacial polymerization method), or a diester carbonate of a carbonate bond-forming precursor There is known a method of transesterifying (melting method) in a molten state.

The method of producing polycarbonate by a transesterification reaction (melting method) does not have the problem of using toxic phosgene or a halogen compound such as methylene chloride as a solvent, and is less expensive than the method of interfacial polymerization. Has the advantage that it can be manufactured, and is considered to be promising in the future.

In the melt polymerization method by transesterification,
In order to increase production efficiency, we will introduce “Plastic Materials Course 17
Usually, a transesterification catalyst is used as described in the literature such as "Polycarbonate", pp. 48-53. As the transesterification catalyst, a catalyst in which a nitrogen-containing basic compound or a phosphorus-containing basic compound and an alkali metal compound are used in combination has good productivity and color tone of a polycarbonate, and has less generation of a branched structure in a polymer molecule. It can be said that the catalyst has good quality in terms of fluidity and the like, and has little generation of foreign substances such as gels.

[0006] Molded polycarbonate articles produced by such a method are used for various purposes. In order to ensure good mold releasability from the mold during molding, a mold release agent typically represented by a higher fatty acid ester is usually used. Is kneaded into the composition.
However, the melt-processed polycarbonate has a problem in stability because it is a metal compound mixed from an alkali metal compound used as a transesterification catalyst, a reaction apparatus, or a raw material.

[0007] In addition, polycarbonate resin compositions containing a release agent represented by a higher fatty acid ester tend to cause problems such as coloring, reduction in molecular weight, and formation of black foreign matter during molding. In particular, when the molding process is continuously performed for a long time, the above-described problem tends to be more remarkable.

In order to solve this problem, a phosphonium sulfonate salt or a phosphite ester is added to a melt-polymerized polycarbonate resin composition containing a fatty acid ester release agent according to the method described in JP-A-8-59975. When a compound or a phenolic antioxidant is used in combination, the above-mentioned problems are considerably improved, but highly precise molds such as optical information recording medium substrates, transparent precision molded products such as optical lenses, and other transparent molded products. For applications requiring pattern transfer and transparency, problems such as coloring, molecular weight reduction, and formation of black foreign matter still remain when molded for a long period of time.

[0009]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide an optical molding material for an optical information recording medium substrate having a precise transferability for accurately reproducing a mold pattern and a good release property. It is a second object of the present invention to provide a resin composition suitable for molding such as, for example, continuous coloring of the composition for a long period of time, stable production of black foreign matter even when subjected to heat molding, a reduction in molecular weight, and the like. The purpose of the present invention is to provide a composition which can be kept at a very low level. Still another object of the present invention is to provide an injection molded product of the above resin composition having good heat stability, especially an optical molding material such as an optical information recording medium substrate, a lens, and a lens cover.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and has a viscosity average molecular weight of 12,000.
~ 40000, polycarbonate having a specific terminal molecular structure, particularly a polycarbonate produced by a transesterification method in the presence of a catalyst containing a nitrogen-containing basic compound or a phosphorus-containing basic compound and an alkali metal compound, a polyhydric alcohol and a carbon number A resin composition comprising a 10 to 22 higher fatty acid and an ester release agent, wherein a phosphorous acid phosphonium salt, a phosphoric acid phosphonium salt,
At least one selected from the group consisting of boric acid-based phosphonium salts and condensed phosphoric acid-based acid phosphonium salts (hereinafter sometimes abbreviated as specific phosphoric acid-based acid phosphonium salts)
A polycarbonate resin composition containing at least one compound selected from the group consisting of phosphoric acid, condensed phosphoric acid, phosphorous acid, and hypophosphorous acid (hereinafter may be abbreviated as a specific phosphoric acid compound). In addition to having good transferability and releasability, the resin composition has good color tone stability, molecular weight stability, low black foreign matter generating ability even when continuously heat-molded, and the resin composition is an injection molded product. ,
In particular, they have found that they are suitable for molding optical information recording medium substrates, lenses, and the like, and have reached the present invention. That is, the present invention is as follows.

1. The main repeating unit derived from the dihydroxy compound and the carbonate bond-forming precursor has the following formula (1)

[0012]

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[R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
A aralkyl group or an aryl group having 6 to 10 carbon atoms, and W is an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, a phenyl-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group. is there. ] And a viscosity average molecular weight of 12000
~ 40000, phenolic terminal group concentration 5 ~ 60 mol%
Per 100 parts by weight of polycarbonate (1) 50 × 10 ^{−4 to} 2000 × 10 ⁻⁴ parts by weight of ester of polyhydric alcohol and higher fatty acid having 10 to 22 carbon atoms (2) Phosphorous acid phosphonium salt (A) At least one compound selected from phosphoric acid-based phosphonium salts (B), boric acid-based acid phosphonium salts (C), and condensed phosphoric acid-based acid phosphonium salts (D) as (A), (B),
0.0 as a total of phosphorus atoms derived from (C) and (D)
1 × 10 ⁻⁴ to 30 × 10 ⁻⁴ parts by weight and / or (3) selected from hypophosphorous acid (A ′), phosphorous acid (B ′), phosphoric acid (C ′), and condensed phosphoric acid (D ′) (A '), (B'), (C '),
0.01 × 1 as the total of phosphorus atoms derived from (D ′)
A polycarbonate resin composition having a melt viscosity stability of 0.5% or less, containing ^0-4 to 30 * ^10-4 parts by weight.

2. For 100 parts by weight of the polycarbonate, a radical scavenger was further added in an amount of 0.1 × 1 in addition to the above components.
0 ^-4 ~5000 × 10 ^-4 polycarbonate resin composition characterized in that it contains parts by weight.

3. Per 100 parts by weight of the polycarbonate, an aromatic phosphite compound (as phosphorus phosphite atom) is further added in an amount of 0.005 × 10 ^{−4 to} 5 in addition to the above components.
A polycarbonate resin composition characterized by containing 0 × 10 ^-4 parts by weight.

4. In addition to the above components, a phosphate compound (as phosphorus atom) is added in an amount of 0.005 × 10 ⁻⁴ to 50 × 10 ⁻⁴ per 100 parts by weight of the polycarbonate.
A polycarbonate resin composition characterized by containing by weight.

5. In addition to the above components, a bluish colorant was further added in an amount of 0.001 × 1 per 100 parts by weight of the polycarbonate.
A polycarbonate resin composition comprising 0 ^-4 to 10 × 10 ^-4 parts by weight.

6. A polycarbonate resin composition, wherein the polycarbonate is obtained by melt polycondensation of a dihydroxy compound and a carbonate bond-forming precursor in the presence of a transesterification catalyst.

[7] When producing a polycarbonate by melt-polymerizing a dihydroxy compound and a carbonate bond-forming precursor in the presence of a transesterification catalyst containing a nitrogen-containing basic compound and / or a phosphorus-containing basic compound and an alkali metal compound, Nitrogen-containing basic compound and / or phosphorus-containing basic compound 20 to 1 mol of compound
A polycarbonate resin composition comprising a transesterification catalyst containing 1,000 (× 10 ⁻⁶ chemical equivalents) and 0.01 to 2 (× 10 ⁻⁶ chemical equivalents) of an alkali metal compound.

An injection-molded product of the polycarbonate resin composition according to any one of 8.1 to 7.

9. An injection molded article wherein the injection molded article is an optical information recording medium substrate.

10. An injection molded product, wherein the injection molded product is a lens or a lens cover.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate according to the present invention preferably has the following formula (1)

[0024]

Embedded image

[R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
0 aralkyl group or an aryl group having 6 to 10 carbon atoms,
W is an alkylidene group having 1 to 20 carbon atoms, an alkylene group, a cycloalkylidene group, a cycloalkylene group, a phenyl-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group. ] Has a main repeating unit represented by the following formula: The polycarbonate has the following formula (2)

[0026]

Embedded image

[R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
0 aralkyl group or an aryl group having 6 to 10 carbon atoms,
W is an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, a phenyl-substituted alkylene group,
It is an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group. ] And a carbonate bond-forming precursor by an interfacial polymerization method or a melting method to produce the compound.

The polycarbonate preferably used in the present invention is obtained by reacting a dihydroxy compound, particularly an aromatic dihydroxy compound, with a carbonate bond-forming precursor by a melt polycondensation method. The effect of the present invention is particularly large when the polycarbonate according to the present invention is an aromatic polycarbonate or the dihydroxy compound is an aromatic dihydroxy compound. In the specification of the present application, various addition amounts are specified as amounts based on the dihydroxy compound, but the amount relation in this case is particularly appropriate when the dihydroxy compound is an aromatic dihydroxy compound. In the presence of a transesterification catalyst among the polycarbonates produced by the melt method, in particular, a) a transesterification catalyst containing a) a nitrogen-containing basic compound and / or a phosphorus-containing basic compound, and b) a transesterification catalyst containing an alkali metal compound. Polycarbonate polycondensed in the presence, the object of the present invention, that is, the stability at the time of molding,
It is preferably used.

As the aromatic dihydroxy compound, specifically, bis (4-hydroxyphenyl) methane, 2,2-
Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane, 4,4 ′-[1,3-phenylenebis (1-
Methylethylidene)] bisphenol, 4,4'-
[1,4-phenylenebis (1-methylethylidene)]
Bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-
Bis (4-hydroxyaryl) alkanes such as methylphenyl) fluorene;

Further, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
-[1- [3- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] -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-
Also preferred are bis (hydroxyaryl) cycloalkanes such as [1H-indene] -6,6′-diol.

Further, dihydroxyaryl ethers such as bis (4-hydroxyphenyl) ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide are also preferably mentioned.

Further, dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide are also preferred.

Dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone;4,4'-dihydroxydiphenyl-3,3'-
Dihydroxydiarylisatins such as isatin;
Examples thereof include dihydroxydiarylxanthenes such as 3,6-dihydroxy-9,9-dimethylxanthene.

Among them, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A, BPA) is more preferable because of its stability as a monomer, and furthermore, it is easy to obtain a small amount of impurities contained therein. It is given as a thing.

In the present invention, control of the glass transition temperature,
Improve fluidity, increase refractive index or reduce birefringence, etc.
For the purpose of controlling optical properties and the like, it is also possible to incorporate one or more kinds of various monomers into the polycarbonate as necessary.

Specific examples thereof include aliphatic dihydroxy compounds such as 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,10
-Decanediol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, diethylene glycol, polytetramethylene glycol, tricyclodecanedi Methanol and the like.

Examples of the aromatic dihydroxy compound include resorcin, hydroquinone, and 2-t which are not included in the above formula (2).
-Butylhydroquinone, 2-phenylhydroquinone, 2
And dihydroxybenzenes such as -cumylhydroquinone and 4,4-dihydroxydiphenyl.

Alternatively, dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, cyclohexanedicarboxylic acid, or oxy acids such as p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, lactic acid And the like.

The carbonate bond forming precursors include:
A carbonyl halide such as phosgene or a haloformate compound is used in the solution method, and a carbonic acid diester is used in the melting method. Specific examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate and the like. In addition, dimethyl carbonate, dicyclohexyl carbonate and the like can be used if desired. Of these, diphenyl carbonate (DPC) is preferred in terms of reactivity, stability against coloring of the obtained resin, and cost.

In the solid-phase polymerization method, a polycarbonate oligomer having a small molecular weight produced by the above-mentioned interfacial polymerization method or the melting method is crystallized, and the polycarbonate which has been polymerized in a solid state at a high temperature (preferably under reduced pressure) is also used. Can be preferably used.

In the production of polycarbonate, dicarboxylic acid, dicarboxylic dihalide,
The agent of the present invention can be effectively used for poly (ester carbonate) which is produced by using a dicarboxylic acid derivative such as dicarboxylic acid diester in combination and contains an ester bond.

Examples of the dicarboxylic acid derivative which is an ester bond forming precursor include aromatic dicarboxylic acid derivatives such as terephthalic acid, terephthalic acid dichloride, isophthalic acid dichloride, terephthalic acid diphenyl and isophthalic acid diphenyl; succinic acid, dodecanoic acid, Aliphatic dicarboxylic acid derivatives such as dimer acid, adipic dichloride, diphenyl decane diacid, diphenyl dodecane diacid; 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic dichloride, cyclopropane dicarboxylic diphenyl, 1,4 And alicyclic dicarboxylic acid derivatives such as diphenyl-cyclohexanedicarboxylate.

A polyfunctional compound having three or more functional groups in one molecule can be used together with the aromatic dihydroxy compound represented by the formula (2).
Such polyfunctional compounds include phenolic hydroxyl groups,
Compounds having a carboxy group are preferably used. Specifically, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (-hydroxyphenyl) -1,3,5-triisopropylbenzene, 4,6-dimethyl -2,4,6-tris (4-hydroxyphenyl) -heptane-2,1,3,5-tris (4-hydroxyphenyl) benzene, trimellitic acid, pyromellitic acid and the like.

For example, when a polyfunctional compound is used in combination for the purpose of increasing the melt viscosity of the polycarbonate, it is preferably 0.03 mol or less, more preferably 0.00005 to 0.02 mol, per mol of the aromatic dihydroxy compound. Is selected in the range of 0.0001 to 0.01 mol.

In the method for producing a polycarbonate whose main repeating unit is represented by the above formula (1), in the above-mentioned interfacial polymerization method, a tertiary amine, a quaternary ammonium salt, a quaternary phosphonium salt, a nitrogen-containing heterocyclic compound are used as catalysts. And salts thereof, imino ethers and salts thereof, compounds having an amide group, and the like.

In the interfacial polymerization method, a large amount of an alkali metal compound or an alkaline earth metal compound is used as a scavenger for hydrogen halide such as hydrochloric acid generated during the reaction.
It is preferable to perform sufficient washing and purification so that such impurities do not remain in the polymer after production.

In the melting method and the solid phase polymerization method, the catalyst system is
Although a catalyst system containing an alkali metal compound is preferably used, it is important that the amount of the alkali metal used is 0.01 × 10 ⁻⁶ to 2 × 10 ⁻⁶ chemical equivalent per 1 mol of the dihydroxy compound. is there. Outside of the above range, there are problems that various properties of the obtained polycarbonate may be adversely affected, or a high-molecular weight polycarbonate may not be obtained due to insufficient transesterification reaction.

Examples of the alkali metal compound include a hydroxide, a hydrocarbon compound, a carbonate, a cyanate, a thiocyanate, an organic carboxylate, a boron hydride and a hydrogen phosphate of an alkali metal conventionally known as a transesterification catalyst. Compounds, bisphenols, phenol salts and the like.

Specific examples include sodium hydroxide, lithium carbonate, potassium acetate, rubidium nitrate, sodium nitrite, potassium sulfite, sodium cyanate, sodium thiocyanate, potassium thiocyanate, lithium stearate, sodium borohydride, sodium hydride Examples include lithium boron, sodium phenylated boron, sodium benzoate, dipotassium hydrogen phosphate, disodium salt and dipotassium salt of bisphenol A, monosodium monopotassium salt, and sodium salt of phenol.

It is preferable to use a nitrogen-containing basic compound and / or a phosphorus-containing basic compound together as a cocatalyst.

Specific examples of the nitrogen-containing basic compound include, for example, quaternary ammonium hydroxides having an alkyl, aryl, alkylaryl group and the like such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide. Basic ammonium salts having an alkyl, aryl, or alkylaryl group such as tetramethylammonium acetate, tetraethylammonium phenoxide, tetrabutylammonium carbonate, hexadecyltrimethylammonium ethoxide; tertiary amines such as triethylamine; Basicity such as methylammonium borohydride, tetrabutylammonium borohydride, tetramethylammonium tetraphenylborate And the like.

Specific examples of the phosphorus-containing basic compound include, for example, alkyl such as tetrabutylphosphonium hydroxide, benzyltrimethylphosphonium hydroxide, and hexadecyltrimethylphosphonium hydroxide.
Basic salts such as quaternary phosphonium hydroxides having an aryl or alkylaryl group; tetrabutylphosphonium borohydride; and tetrabutylphosphonium tetraphenylborate.

The nitrogen-containing basic compound and / or
Basic compounds are basic nitrogen atoms or basic phosphorus
Atom is an aromatic dihydroxy compound, 20 moles per 1 mole
10 ^-6~ 1000 × 10^-6Use at a ratio equivalent to chemical equivalent
Is preferred. A more preferable usage ratio is based on the same standard.
30 × 10^-6~ 700 × 10^-6At the rate of chemical equivalent
is there. A particularly desirable ratio is 50 × 10 with respect to the same standard.^-6
~ 500 × 10^-6It is the ratio that becomes the chemical equivalent.

The polycarbonate of the present invention has a melt viscosity stability of 0.5% or less, and has a melt viscosity stability of 0.5% or less.
To achieve the following, a specific amount of the melt viscosity stabilizer (E) is added to the polycarbonate after the polycondensation reaction and, if desired, after the end-capping reaction of the terminal hydroxyl groups. The melt viscosity stability in the present invention is a value obtained by measuring the absolute value of the change in melt viscosity measured at 300 ° C. for 30 minutes at a shear rate of 1 rad / sec under a nitrogen gas stream for 30 minutes, and converting the value into the rate of change per minute. To tell. By using a polycarbonate having such a melt viscosity stability, the polycarbonate resin composition of the present invention can have a melt viscosity stability of 0.5% or less.

In the polycarbonate resin composition having poor melt viscosity stability, in addition to poor stability at the time of molding processing, poor stability of mechanical properties during high-humidity conditions and long-term use of a molded product, particularly resistance to resistance. Impact properties are significantly deteriorated (reduced), and are often not practical.

The melt viscosity stabilizer used in the present invention is:
(E) -1; a sulfonic acid phosphonium salt, an ammonium salt and / or (E) -2; a sulfonic acid and / or a lower ester of sulfonic acid.

Specific examples of the compound represented by the above formula (E) -1 include, for example, tetrabutylphosphonium benzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetramethylammonium decylsulfonate, dodecylbenzene And tetrabutylammonium sulfonate.

As the sulfonic acid (E) -2, aromatic sulfonic acids such as p-toluenesulfonic acid, aliphatic sulfonic acids such as octadecylsulfonic acid, butyl benzenesulfonate, ethyl hexadecylsulfonate, and butyl decylsulfonate. Etc. are exemplified.

Examples of the lower ester of sulfonic acid (E) -2 include alkyl esters such as methyl ester and ethyl ester of the sulfonic acid; aryl esters such as phenyl ester; and aralkyl esters such as benzyl ester.

Preferably, a lower ester of sulfonic acid is used rather than sulfonic acid itself. Such a melt viscosity stabilizer is effective for a polycarbonate produced by an interfacial polymerization method, but reduces the activity of a basic alkali metal compound remaining in a polycarbonate produced by a melt polymerization method or a solid phase polymerization method. It is effective for

With respect to the amount used, the alkali metal element of the basic alkali metal compound catalyst, (E) per one chemical equivalent,
-1 in the compound of 0.7 to 50 chemical equivalents, preferably 0.8 to 20 chemical equivalents, more preferably 0.9 to
-10 chemical equivalents, 0.7 for the compound of (E) -2
By using 20 chemical equivalents, preferably 0.8-10 chemical equivalents, and more preferably 0.9-5 chemical equivalents, the melt viscosity stability of polycarbonate and the resin composition of the present invention is 0.5%. It can be held below.

When the melt viscosity stabilizer (E) -2 is used, it is preferable to apply a vacuum treatment to the polycarbonate subjected to the melt viscosity stabilization treatment. In performing such a decompression process, the type of the processing apparatus is not particularly limited.
On the other hand, when the melt viscosity stabilizer (E) -1 is used, it is not necessary to perform such a vacuum treatment.

The decompression treatment is performed in a vertical tank reactor, a horizontal tank reactor or a vented single-screw or twin-screw extruder at 6.7 to 8 × 10 ³ Pa, preferably 1.3 × 10 ⁴ Pa.
A reduced pressure treatment under reduced pressure of Pa or less is preferable. The reduced pressure treatment time is about 5 minutes to 3 hours in a tank reactor, about 5 seconds to 15 minutes when a twin screw extruder is used, and the treatment temperature is 24 hours.
It can be carried out at 0 ° C to 350 ° C. The decompression treatment can be performed simultaneously with pelletization by an extruder. By performing the above-described reduced pressure treatment, the raw material monomers remaining in the polycarbonate are reduced or completely removed.

In the present invention, the molecular terminal structure of the polycarbonate preferably comprises substantially an aryloxy group and a hydroxyl group, and has a phenolic terminal group concentration of 5 to 60.
% By mole. As the aryloxy group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms is preferably selected. From the viewpoint of thermal stability, the above-mentioned hydrocarbon group substitution is preferably a tertiary alkyl group, tertiary aralkyl group, aryl group or simply a hydrogen atom. A compound having a benzyl-type hydrogen atom can be used when it has a desired purpose such as improvement in stability of active radiation resistance, but it is better to avoid it from the viewpoint of stability against thermal aging and thermal decomposition. Specific examples of preferred aryloxy groups include a phenoxy group and 4-t
-Butylphenyloxy group, 4-t-amylphenyloxy group, 4-phenylphenyloxy group, 4-cumylphenyloxy group and the like.

In a further preferred embodiment, the phenolic terminal group concentration of the polycarbonate is 5 to 60 mol%, more preferably 5 to 55 mol%, based on all terminal groups. Even if the phenolic terminal group concentration is reduced below 5 mol%, further improvement in physical properties is small. It is obvious from the above discussion that the introduction of a phenolic terminal group concentration exceeding 60 mol% is not preferable for the purpose of the present invention.

In the interfacial polymerization method, the phenolic terminal group concentration is within the above range due to the monofunctional compound used as a molecular weight regulator. However, in the melt polymerization method, the terminal hydroxyl group is 50 moles in terms of chemical reaction. % Is easy to produce, so it is necessary to actively reduce the terminal hydroxyl groups. That is, the concentration of the phenolic terminal group within the above range can be achieved by the following known method 1) or 2). 1) Controlling the molar ratio of the raw materials for polymerization: a method of controlling the molar ratio of DPC / BPA at the time of charging the polymerization reaction to set the ratio between 1.02 and 1.10. 2) Terminal blocking method: At the end of the polymerization reaction, the terminal hydroxyl group is blocked with a salicylate-based compound described in the above specification, for example, according to the method described in US Pat. No. 5,696,222.

The amount of the salicylic acid ester compound used is 0.8 to 10 per terminal hydroxyl group and one chemical equivalent before the capping reaction.
Mol, more preferably 0.8 to 5 mol, particularly preferably 0.9 to 2 mol. By adding at such a ratio, 80% or more of the terminal hydroxyl groups can be suitably sealed. Further, when performing the main sealing reaction, it is preferable to use the catalyst described in the above patent. The reduction of the phenolic end group concentration is preferably performed at a stage before deactivating the polymerization catalyst.

Specific examples of the salicylic acid ester compound include 2-methoxycarbonylphenyl-phenylcarbonate, 2-methoxycarbonylphenylarylcarbonate such as 2-methoxycarbonylphenyl-cumylphenylcarbonate, and (2-methoxycarbonylphenyl). (2'-methoxycarbonylphenyl) esters of aromatic carboxylic acids such as benzoate and 4- (O-ethoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester.

The polycarbonate resin composition according to the present invention contains an ester of a polyhydric alcohol and a higher fatty acid having 10 to 22 carbon atoms in order to improve the releasability from a mold during melt molding. In the resin composition, the combined use of the specific phosphoric acid-based phosphonium salt and / or the specific phosphoric acid-based compound of the present invention is effective for achieving the effects of the present invention. The higher fatty acid used may be a saturated compound or an unsaturated compound. One or a mixture of two or more of both compounds may be used. The ester may be a complete ester or a partial ester. A mixture of a complete ester and a partial ester may be used.

The complete ester or partial ester includes a saturated or unsaturated aliphatic mono-, di-, tri- or polyvalent carboxylic acid and a saturated or unsaturated polyhydric alcohol such as ethylene glycol and propylene glycol. Di-, 4-butanediol, diethylene glycol, glycerin, trimethylolpropane, pentaerthritol, 2,2'-dihydroxyperfluoropropanol, neopentylene glycol, etc. Further examples include esters with polyhydric saturated and unsaturated polyhydric alcohols such as methylolpropane.

The saturated or unsaturated aliphatic polycarboxylic carboxylic higher fatty acids include stearic acid, caproic acid, oleic acid, behenic acid, lignoglyceric acid, cerotic acid, mericinic acid, tetratricontanic acid, Adipic acid and the like can be mentioned.

Examples of partial esters from these polyhydric alcohols and higher fatty acids include pentaerythritol tristearate, pentaerythritol distearate, pentaerythritol monooleate, pentaerythritol monobehenate, glycerol monobehenate and glycerol dibehenate Glycerol monolaurate, glycerol dilaurate, glycerol monostearate, glycerol distearate, trimethylolpropane monooleate, trimethylolpropane distearate and the like.

Specific examples of the complete ester include pentaerythritol tetrastearate, glycerol tribehenate, glycerol trilaurate, glycerol tristearate, trimethylolpropane triolate,
And trimethylolpropane tristearate. The preferred amount of these compounds is in the range of 50 × 10 ^{-4 to} 2000 × 10 ^-4 parts by weight, preferably 60 × 10 ^{-4 to} 1000 × 10 ^-4 parts by weight, per 100 parts by weight of the polycarbonate. If the compounding amount is out of the range of the limit value, an unfavorable case may occur for the purpose of the present invention, which is not preferable.

In order to achieve the object of the present invention more preferably, it is preferable to set the content of the partial ester and the complete ester in a specific range. That is, partial ester / complete ester (weight ratio) = 100/0 to 90/10, more preferably 99/1 to 80/20, and still more preferably 98/2 to 75 /.
When it is in the range of 25, the effect of the specific phosphoric acid-based phosphonium salt or the like can be more exhibited, which is preferable.

In the present invention, the following release agents may be used in combination, if desired. That is, natural or synthetic paraffin waxes, polyethylene waxes, hydrocarbon release agents such as fluorocarbons, fatty acid release agents of higher fatty acids such as ditrimethylolpropane, stearic acid and hydroxystearic acid, and fatty acids such as ethylenebisstearylamide Fatty acid amide release agents such as alkylenebisfatty acid amides such as amides and erucamides; aliphatic alcohols such as stearyl alcohol and cetyl alcohol; and alcohol release agents such as polyglycols as polyhydric alcohols. . In addition, polysiloxane and the like can be used if desired.

The amount of the release agent is from 1 × 10 ^{-4 to} 1000 per 100 parts by weight of the polycarbonate of the present invention.
0 × 10 ^-4 parts by weight is preferred. These may be used alone or as a mixture of two or more.

In the present invention, polycarbonate 100
The specific phosphoric acid-based phosphonium salt is preferably contained in the range of 1 × 10 ^{−6 to} 3 × 10 ⁻² parts by weight with ^respect to parts by weight. More preferably, 5 × 10 ⁻⁶ to 2 × 10 ⁻² parts by weight,
More preferably, the content is in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻² parts by weight, and from the viewpoint of the phosphorus content, which is a more appropriate expression, the phosphorus component in the specific phosphonic acid phosphonium salt is determined based on the same standard. 0.01 × 10 ^-4 to 30 × 1
0 ^-4 parts by weight, preferably 0.05 × 10 ^-4 to 15 × 10
^-4 parts by weight, more preferably 0.1 × 10 ^{-4 to} 5 × 10
^-4 parts by weight. If the content of the phosphoric acid phosphonium salt is less than the above lower limit, desired stability cannot be obtained, and if it is more than the upper limit, heat resistance, particularly heat resistance at the time of molding processing is reduced.

Specific examples of the specific phosphoric acid acidic phosphonium salt preferably used in the present invention include the compounds described in the prior application of the present inventors. Specifically, as the phosphoric acid-based phosphonium salt, a phosphoric acid-based diphosphonium salt, a diacid phosphonium phosphate and a phosphonic acid-based phosphonium salt, and as the phosphite-based acid phosphonium salt, a phosphorous acid-based diphosphonium salt or a phosphonic acid-based diacid phosphonium salt. And phosphonic acid acid phosphonium salts and boric acid acid phosphonium salts include boric acid diphosphonium salt, boric acid diacid phosphonium salt, and Toshizo Chitani, "New Edition Inorganic Chemistry"
Nakamaki, ”Sangyo Tosho Co., Ltd., section 3, pages 686-745
Means an acidic phosphonium salt of a condensate such as phosphoric acid or phosphorous acid described in (1).

Specific examples of these compounds include the following. Examples of the phosphoric acid diphosphonium salt include bis (tetrabutylphosphonium) hydrogen phosphate, bis (tetraphenylphosphonium) hydrogen phosphate, bis [tetrakis (2,4-di-t-butylphenyl) phosphonium], phosphoric acid 2 Examples of acidic phosphonium salts include tetramethyl phosphonium dihydrogen phosphate, tetrabutyl phosphonium dihydrogen phosphate, tetraphenyl phosphonium dihydrogen phosphate, trimethyl benzyl phosphonium dihydrogen phosphate, ethyl trimethyl phosphonium dihydrogen phosphate, and acidic phosphonium phosphonate salts. , Hydrogen phenylphosphonate (tetrabutylphosphonium),
Tetraoctylphosphonium hydrogen benzylphosphonate,
And methyltriethylphosphonium hydrogen nonylphosphonate.

Examples of the acid diphosphonium phosphite include bis (tetramethylphosphonium) hydrogen phosphite, bis (tetrabutyl phosphonium) hydrogen phosphite,
Examples of the acidic phosphonium salt include tetramethylphosphonium dihydrogen phosphite, tetrabutyl phosphonium hydrogen phosphite, and tetraphenyl phosphonium diacid hydrogen phosphite.

Examples of the acidic phosphonium phosphonate salt include acidic hydrogen phenylphosphonite (tetrabutylphosphonium), tetramethylphosphonium hydrogen octanephosphonite, and tetrabutylphosphonium hydrogen phosphite.

Examples of the boric acid diphosphonium salt include:
Bis (triethylbenzylphosphonium) hydrogen borate, bis (trimethylbenzylphosphonium) borate hydrogen 2
Examples of the acidic phosphonium salt include tetramethylphosphonium dihydrogen borate and tetrabutyl phosphonium dihydrogen borate.

Examples of the condensed phosphoric acid phosphonium salts include bis (tetramethylphosphonium) monohydrogen hypophosphate, bis (tetrabutylphosphonium) monohydrogen phosphate, tetramethylphosphonium trihydrogen hypophosphate, and pyrophosphorous acid monophosphate. Tetramethylphosphonium hydrogen, tetrabutylphosphonium monohydrogen pyrophosphite, benzyltrimethylphosphonium monohydrogen pyrophosphate, bis (tetrabutylphosphonium) dihydrogen pyrophosphate, tetrabutylphosphonium trihydrogen pyrophosphate, tetraphenyl trihydrogen pyrophosphate Phosphonium, monohydrogen trimetaphosphate bis (tetramethylphosphonium), bis (tetramethylphosphonium) trimetaphosphate, monohydrogen trimetaphosphate (tetramethylphosphonium) (tetraphenylphosphonium), trimetaphosphate 1 Hexadecyltrimethylphosphonium hydrogen, tris monohydrogen tetrametaphosphate (tetramethylphosphonium), tris monohydrogen tetrametaphosphate (tetranonyl phosphonium), bis (tetrabutylphosphonium) dihydrogen tetrametaphosphate, dihydrogen tetrametaphosphate (tetramethyl phosphate An acidic phosphonium salt of phosphonium) (tetraethylphosphonium) or a higher metaphosphoric acid may be used.

These condensed phosphoric acid phosphonium salts are
One or more mixtures may be used. Among these condensed phosphate acidic phosphonium salts, an acidic phosphonium salt from pyrophosphoric acid is exemplified as a preferable one.

Among these specific phosphoric acid acidic phosphonium salts, bis (tetramethylphosphonium) hydrogen phosphate, bis (tetrabutylphosphonium) hydrogen phosphate, tetramethylphosphonium diacid hydrogen phosphate, tetrabutylphosphonium dihydrogen phosphate, Bis (tetrabutylphosphonium) hydrogen phosphate, diacid hydrogen tetramethylphosphonium phosphite, tetrabutyl phosphonium hydrogen phosphite,
Tetramethylphosphonium monohydrogen pyrophosphite, tetrabutylphosphonium monohydrogen pyrophosphite, pyrophosphate 2
Hydrogen bis (tetrabutylphosphonium), pyrophosphoric acid 3
Particularly preferred are tetrabutylphosphonium hydrogen, acidic bis (tetrabutylphosphonium) borate, tetramethylphosphonium dihydrogen borate and the like. Further, in the present invention, various acidic phosphonium salts described below, such as sulfuric acid and sulfurous acid, may be used in combination, if desired.

As the sulfuric acid phosphonium salt, for example,
Examples include tetramethylphosphonium hydrogen sulfate, tetraoctylphosphonium hydrogen sulfate, and diethyldibutylphosphonium hydrogen sulfate.

Examples of the acid sulfonium sulfite include tetrabutylphosphonium hydrogen sulfite, tetraoctylphosphonium hydrogen sulfite, benzyltrimethylphosphonium hydrogen sulfite and the like.

In the present invention, the specific phosphoric acid acidic phosphonium is used.
Specific phosphoric acid compounds used in combination with hypophosphorous acid and phosphorous acid
Acid, phosphoric acid, and condensed phosphorous acid and condensed phosphoric acid
You. These agents form the above-mentioned specific phosphoric acid phosphonium salt.
The effect of reinforcing the use is remarkable. Selected from these groups
100% by weight of at least one compound is polycarbonate
Per part, the total amount of phosphorus atoms derived from the compound is 0.1.
01 × 10^-Four~ 30 × 10 ^-FourPreferably in parts by weight
New More preferably 0.05 × 10^-Four-10 × 10
^-FourParts by weight, particularly preferably 0.05 × 10^-Four~ 5 × 10
^-FourIt is in the range of parts by weight.

When the amount is less than the lower limit of these amounts,
No valid results are obtained. If the content exceeds the upper limit, a problem may occur in the stability of the composition against hydrolysis.

In the composition of the present invention, a radical scavenger is used in an amount of 0.1 × 10 ^{-4 to} 5/100 parts by weight of polycarbonate.
000 × 10 ^-4 parts by weight, preferably 0.5 × 10 ^-4 to 1
000 × 10 ⁻⁴ parts by weight, more preferably 1 × 10 ⁻⁴ to
^Contains a polycarbonate composition containing 500 × 10 ^-4 parts by weight. As such a radical scavenger, Hans Zweif
el, Stabilization of Polymeric Materials (Sp
The antioxidants described in the section on stabilization against thermo-oxidative degradation on pages 41-69 can be used effectively. Among them, a phenolic antioxidant which is a proton (H) -donor or a carbon radical scavenger can be preferably used. The phenolic antioxidant is preferably a phenolic hydroxyl group in which at least one hydrogen at the ortho position of the phenolic hydroxyl group has been replaced by a tertiary carbon atom.

Specific examples thereof include, for example, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate and tetrakismethylene-3- (3 ′, 5 ′). -Di-t-butyl-4-
(Hydroxyphenyl) propionate {methane, triethylene glycol-bis} 3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate
1,6-hexanediol-bis {3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate {, 2,4-bis (n-octylthio) -6- (4-
Hydroxy-3,5-di-t-butylanilino) -1,
3,5-triazinepentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,2-thiodiethylenebis {3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-tert-butylphenol), N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-) Hydrocinnamide), 3,5-di-t-butyl-4-
Hydroxybenzyl phosphonate diethyl ester, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate isooctyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,5,7,8-tetramethyl-2-
(4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6-ol, N, N′-bis {3- (3,5-di-
(t-butyl-4-hydroxyphenyl) propionylhydrazine} and the like.

Of these, n-octadecyl-3-
(4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, tetrakismethylene-3-
(3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate {methane, triethylene glycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 5 , 7-di-t-
Butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one, 5,5-di-t-amyl-3-
(3,4-dimethylphenyl) -3H-benzofuran-
2-one, 5,5-dicumylul-3-phenyl-3H-
Benzofuran-2-one, 2-t-butyl-6- (3-
t-butyl-2-hydroxy-5-methylbenzyl)-
4-Methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate and the like are exemplified as preferable ones.

Conventionally, various aromatic phosphite compounds are known to be effective as antioxidants for various resins such as polycarbonates. However, as described above, polycarbonates having a specific viscosity average molecular weight and a specific terminal hydroxyl group concentration are frequently used. Polycarbonate resin composition comprising an ester release agent of an ester of a polyhydric alcohol and a higher fatty acid, a composition of a specific phosphoric acid acidic phosphonium salt, a specific phosphoric acid compound, and an aromatic phosphite compound is melt-processed. Coloring, molecular weight reduction, good generation of black foreign matter,
This is a new finding that is immeasurable from the prior art range.

The content of the aromatic phosphite compound is 0.005 × 10 5 (as phosphorus atoms in the aromatic phosphite) per 100 parts by weight of the polycarbonate.
^-4 to 50 × 10 ^-4 parts by weight. Preferably 0.
Within a range of 01 × 10 ⁻⁴ to 30 × 10 ⁻⁴ parts by weight, more preferably within a range of 0.1 × 10 ^{−4 to} 20 × 10 ⁻⁴ parts by weight, and particularly preferably 1 × 10 ^{−4 to} 20 ×. It is in the range of 10 ^-4 parts by weight.

An aromatic phosphite compound having a peroxide decomposability of 50% or more has a large effect on the deterioration of color tone during molding. The peroxide decomposability is more preferably 7
0% or more compounds are selected.

Evaluation of peroxide decomposability was performed by evaluating cumene hydroperoxide; 2 × 10 ^-2 mol, and “aromatic phosphite compound”; a chlorobenzene solution of 1 × 10 ^-2 chemical equivalent for 30 minutes at 25 ° C. And the amount of cumene hydroperoxide decomposed by the “aromatic phosphite compound” is divided by the amount by which the “aromatic phosphite compound” can stoichiometrically decompose cumene hydroperoxide. And multiplied by 100. It is determined that the larger this value is, the higher the peroxide decomposition performance is.

Further, the aromatic phosphite compound preferably has a specific water absorbing ability described below. 90% phosphite in petri dish
The value obtained by dividing 100 by the weight gain when the phosphite compound is hydrolyzed by the weight gain after the phosphite compound has been hydrolyzed by RH at 50 ° C. atmosphere is more than 1%. . The water absorption capacity is preferably 20 Hr or more, preferably 20 to 350 Hr, particularly preferably 20 to 30 Hr.
0 Hr. When this value is high, the generation of black foreign matter tends to be remarkable during heat molding for a long time, and when it is too small, the color tone at the time of molding tends to be poor.

The "aromatic phosphite compound" as used in the present invention is a trivalent phosphorus compound having at least one aromatic residue and no active hydrogen bonded to a phosphorus atom via an oxygen atom. Therefore, in addition to the phosphite triester, phosphonous acid diester Note 1 and phosphinous ester Note 1 are also contained in the phosphite compound. [Note) 1; “Modern Organic Synthesis Series; 5 Organic Phosphorus Compounds” (edited by the Society of Synthetic Organic Chemistry) P78] As the “aromatic phosphite compound” in the present invention, specifically, for example, bis (2,2) 4-di-cumylphenyl) pentaerythrityl diphosphite, bis (2,
4-di-t-amylphenyl) pentaerythrityl diphosphite, bis (2,4-di-t-amyl-3-methylphenyl) pentaerythrityl diphosphite,
Bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphite, bis (2,4-di-t-butyl-3-methylphenyl) pentaerythrityl diphosphite, 2,2-methylenebis ( 4,6-di-t-butylphenyl) phosphite, bis (2,4-di-t)
-Amylphenyl) octyl phosphite, bis (2,4-di-cumylphenyl) nonyl phosphite, bis (2,4-di-t-butylphenyl) decyl phosphite, tetrakis (2,4-di-t-butyl) Phenyl) biphenyl-4,4′-diphosphonite,
Tris (2,4-di-t-butylphenyl) phosphite and the like are exemplified. However, it is not limited to these. Among them, bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are exemplified as preferable ones.

In the present invention, the phosphoric acid ester compound is defined as 0.005 × 10 ^-4 to 50% by weight of the phosphoric acid ester compound as a phosphorus atom per 100 parts by weight of polycarbonate.
× 10 ⁻⁴ parts by weight, preferably 0.01 × 10 ⁻⁴ to 50 ×
10 ^-4 parts by weight, more preferably 0.05 × 10 ^-4 to 4
0 × 10 ^-4 parts by weight.

Due to the presence of such a ratio, coexistence with the “aromatic phosphite compound” is exhibited, and during heat molding, the color tone is less deteriorated, the molecular weight is reduced, and the heat resistance is improved with less generation of black foreign matter. Is achieved. A part of the phosphate compound and the aromatic phosphite compound may be bonded to the aromatic polycarbonate molecular chain.

As the phosphoric ester compound used in the present invention, those having the same molecular skeleton as the above-mentioned aromatic phosphite compound are preferably used.

Examples of the phosphate compound include bis (2,4-di-cumylphenyl) pentaerythrityl diphosphate, bis (2,4-di-t-amylphenyl) pentaerythrityl diphosphate, bis (2 ,
4-di-t-amyl-3-methylphenyl) pentaerythrityl diphosphate, bis (2,4-di-t-
Butylphenyl) pentaerythrityl diphosphate, bis (2,4-di-t-butyl-3-methylphenyl) pentaerythrityl diphosphate, 2,2-methylenebis (4,6-di-t-butylphenyl) ) Phosphate, tris (2,4-di-t-amylphenyl) phosphate, tris (2,4-di-cumylphenyl) phosphate, tris (2,4-di-t-butylphenyl) phosphate, tetrakis (2,4 -Di-t-butylphenyl) biphenyl-4,4'-diphosphonate, trimethyl phosphate, triphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, bis (2,3-dibromopropyl) -2,3-dichloro Propyl phosphate, tris (2,3-dibromopropyl) phosphate and the like. However, it is not limited to these. Among these, bis (2,4-di-t-amylphenyl) pentaerythrityl diphosphate, tris (2,4-di-t-butylphenyl) phosphate, trimethyl phosphate and the like are exemplified as preferable ones.

In the polycarbonate resin composition of the present invention, a bluish colorant is used in order to improve the organoleptic sensitivity of the molded article. Specific examples of the high sensitivity include the number of black foreign substances. The bluish colorant is preferably an organic bluish colorant. The bluish colorant has a large tendency to discolor at the time of heat-melt molding. In the composition, the stabilizing effect of the specific phosphoric acid phosphonium salt and the specific phosphoric acid compound of the present invention is obtained. Is big. Specific examples of the bluish colorant include a generic name, Solvent Violet 13 [CA. No. (color index No.) 60725; a trade name, “Macrolex Violet B” manufactured by Bayer AG,
"Dialegin Violet G" manufactured by Mitsubishi Chemical Corporation, "Sumiplast Violet B" manufactured by Sumitomo Chemical Co., Ltd.] Generic name: Solvent Violet 31 [CA. No. 68210; Trade name, "Diaresin Violet D" manufactured by Mitsubishi Chemical Corporation General name: Solvent Violet 33 [CA. No. 60725; trade name, Mitsubishi Chemical Corporation "Diaresin Blue J"] Generic name: Solvent Blue 94 [CA. No. 61500; trade name, Mitsubishi Chemical Corporation "Diaresin" Blue N "] Generic name; Solvent Violet 36 [CA. No. 68210; Trade name," Macrolex Violet 3R "manufactured by Bayer Corporation] Generic name; Solvent Blue 97 [trademark name, Bayer Corporation" Macrolex Blue RR "] Generic name; Solvent Blue 45 [CA.No. 6111 ; Trade name, Sandoz Ltd., "tetrazole Blue RLS"] Others, such as Ciba Specialty Chemicals Inc. of macro Rex Violet and triazole Blue RLS, and the like. Among these, macrolex violet and Triazole Blue RLS are preferred.

These colorants may be used alone,
Or you may use it by mixing. These colorants are usually used in an amount of 0.001 × 10 ⁻⁴ per 100 parts by weight of polycarbonate.
^-10 × 10 ^-4 parts by weight, preferably 0.05 × 10 ^-4
5 × 10 ⁻⁴ parts by weight, more preferably 0.1 × 10 ⁻⁴ to
It can be used in an amount of 3 × 10 ^-4 parts by weight.

In the present invention, a resin composition having excellent durability and stability can be obtained. When molding various molded articles using the resin composition, conventionally known processing stabilizers, heat stabilizers, Antioxidants, acidic substance supplements, UV absorbers,
An antistatic agent, a flame retardant, a light stabilizer, a mold release agent, and the like may be added.

For example, the following general heat stabilizers can be added, if desired, in order to further prevent the molecular weight and the hue from deteriorating. Specific examples of such a stabilizer include conventionally known phosphorus-based stabilizers, organic thioether stabilizers, and hindered amine stabilizers.

As the phosphorus-based stabilizer, in addition to the above-mentioned phosphite compound of the present invention, a phosphorus-based stabilizer exemplified below may be optionally used. As the phosphorus-based stabilizer used in the present invention, for example, those commercially available from stabilizer manufacturers as antioxidants can be used.

For example, as phosphites, bis (nonylphenyl) pentaerythrityl diphosphite, tetra (tridecyl) -4,4′-isopropylidenediphenyl diphosphite, 2-{[2,4,10-tetrakis (1,1-dimethylethyl) dibenzo {d, f} [1,
[3,2] dioxaphosphepin-6-yl] oxy}-
N, N-bis [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin 6-yl] oxy Arylalkyls such as] -ethyl] ethanamine; trialkyl phosphites such as trinonyl phosphite, distearyl pentaerythrityl diphosphite, tris (2,3-dichloropropyl) phosphite; tricyclohexyl phosphite Tricycloalkyl phosphites; triaryl phosphites such as tris (nonylphenyl) phosphite and triphenyl phosphite;

Trialkyl phosphates such as hydrogenated bisphenol A pentaerythrityl phosphate polymer, tridecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2,3-dichloropropyl) phosphate as phosphoric esters; tricyclohexyl Tricyclohealkyl phosphites such as phosphite; triaryl phosphates such as tris (2,4-di-tert-butylphenyl) phosphate and tris (nonylphenyl) phosphate; and other phosphonites.

As organic thioether stabilizers, for example, dilaurylthiodipropionate, dimyristyl-3,
3′-thiodipropionate pentaerythritol-tetrakis (β-laurylthiopropionate) and the like.

As hindered amine stabilizers, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] [Ethyl] -4-
{3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 2- (3,5-Di-tert-butyl-4-)
Bis (1, hydroxybenzyl) -2-n-butylmalonate
2,2,6,6-pentamethyl-4-piperidyl) and the like.

These heat stabilizers can be used alone or in combination.
You may mix and use more than one kind. The amount of the heat stabilizer is 0.00 0.00 parts by weight based on 100 parts by weight of the resin component of the present invention.
The amount is preferably from 01 to 1 part by weight, more preferably from 0.0005 to 0.5 part by weight, and still more preferably from 0.001 to 0.1 part by weight. These may be used alone or as a mixture of two or more.

As the acidic substance scavenger, a compound having one or more epoxy groups in the molecule may be used. Examples of acidic substance scavengers are: epoxidized soybean oil, 3,
4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate cyclohexylmethyl-, 4-epoxycyclohexylcarboxylate bisphenol A diglycidyl ether and the like.

Among these, alicyclic epoxy compounds can be preferably used. In particular, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate can be preferably used. Such an epoxy compound is used in an amount of 1 × 10 ^-4 to 2 per 100 parts by weight of the resin component.
000 × 10 ^-4 parts by weight, preferably 10 × 10 ^-4 to 10
It is added in an amount of 00 × 10 ^-4 parts by weight. These may be used alone or as a mixture of two or more.

Examples of the flame retardant include the following compounds.

Examples of the phosphate compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropenyl phenyl phosphate, and the like.
Tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3-dibromopropyl) phosphate, resorcinol polyphosphate, bisphenol A polyphosphate And the like. Preferably triphenyl phosphate,
Resorcinol polyphosphate and bisphenol A polyphosphate. In the present invention, if desired,
Polytetrafluoroethylene (Teflon (registered trademark)) or the like may be blended as an anti-drip agent.

In order to achieve the desired object of the present invention, various other conventionally known additives can be used. For example, light stabilizers,
As an ultraviolet absorber, 2- (3,5-di-t-butyl-)
Benzotriazole-based compounds such as 2-hydroxyphenyl) benzotriazole, benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone,
Benzoate compounds such as 2,4-di-t-butylphenyl 3,5-di-t-butylphenyl-4-hydroxybenzoate and cyanoacrylate compounds such as 2-cyano-3,3-diphenylacrylate are exemplified. You.

These light stabilizers and ultraviolet absorbers are usually used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 1 important part, more preferably 0.05 parts by weight, based on 100 parts by weight of the resin component.
It can be used in an amount of 1 to 0.5 parts by weight. These agents may be used alone or as a mixture.

In addition, for example, {2,2′-thiobis (4
-T-octylphenolate) quencher such as {-2-ethylhexylamine nickel, N, N '-{3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Metal deactivators such as propionyl hydrazine, metal soaps such as calcium stearate and nickel stearate,
Other dibenzylidene sorbitol, methylene bis
Nucleating agents such as sodium salt of (2,4-di-t-butylphenyl) acid phosphate, quaternary ammonium salts such as (β-lauramidopropyl) trimethylammonium sulfate, sodium dodecylbenzenesulfonate, and sulfonate salts And antistatic agents such as compounds and alkyl phosphate compounds.

In the resin of the present invention, if desired, organic or inorganic coloring agents such as dyes and pigments can be used.

Specific examples of the inorganic colorant include oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as navy blue, and chromates such as zinc chromate. , Sulfates such as barium sulfate,
Examples thereof include carbonates such as calcium carbonate, silicates such as ultramarine blue, phosphates such as manganese violet, carbon such as carbon black, and metal coloring agents such as bronze powder and aluminum powder. Other organic colorants may be used if desired. These colorants may be used alone,
Or you may use it by mixing. These colorants are generally 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × 10 ^{−6 to} 3 parts by weight, more preferably 1 × 1 per 100 parts by weight of the resin component.
It can be used in an amount of 0 ^-5 to 1 part by weight.

Further, inorganic and organic fillers can be added to the polycarbonate of the present invention in order to improve the rigidity and the like as long as the object of the present invention is not impaired. Examples of such inorganic fillers include talc, mica, glass flakes, glass beads, calcium carbonate, titanium oxide and other plate-like or granular inorganic fillers and glass fibers, glass milled fibers, wollastonite, carbon fibers, aramid fibers, Examples include fibrous fillers such as metal-based conductive fibers, and organic particles such as crosslinked acrylic particles and crosslinked silicone particles. The compounding amount of these inorganic and organic fillers is preferably from 1 to 150 parts by weight, more preferably from 3 to 100 parts by weight, based on 100 parts by weight of the resin component of the present invention. The inorganic filler usable in the present invention may be surface-treated with a silane coupling agent or the like. By this surface treatment, good results such as suppression of decomposition of polycarbonate can be obtained.

For the specific purpose, the following thermoplastic resins can be blended with the polycarbonate of the present invention within a range that does not impair the object of the present invention.

As such other resins, for example, polyamide resins, polyimide resins, polyetherimide resins,
Polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, amorphous polyarylate resin, polystyrene resin, acrylonitrile / styrene copolymer ( AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin,
Resins such as phenolic resins and epoxy resins are exemplified.

An injection molded article having good durability and stability can be obtained from the polycarbonate produced in the present invention by an injection molding method or the like. Here, the injection molding method includes an injection compression molding method.

The aromatic polycarbonate resin composition of the present invention has the effect of maintaining the durability of the polymer composition, particularly the long-term durability under severe temperature and humidity conditions, and the effect of charging by applying the above-mentioned specific compounding agent. It provides prevention and is suitable for optical information recording medium substrates. In particular, digital versatile discs (DVD-ROMs) such as compact discs (CD), CD-ROMs, CD-Rs, CD-RWs, magnet optical discs (MO), etc. obtained using the aromatic polycarbonate resin moldings , DVD-Vi
deo, DVD-Audio, DVD-R, DVD-R
A substrate for a high-density optical disk typified by AM or the like has high reliability over a long period of time. In particular, it is useful for a high-density optical disk such as a digital versatile disk. It is also suitable for various lenses and lens covers.

The sheet made of the aromatic polycarbonate resin composition produced in the present invention is a sheet excellent in flame retardancy, antistatic property, adhesiveness and printability, and makes use of its properties to make electric parts, Widely used for building material parts, automobile parts, etc., and specifically, various window materials, ie, glazing products for window materials of general houses, gymnasiums, baseball domes, vehicles (construction machinery, automobiles, buses, bullet trains, train cars, etc.), In addition, various side walls (sky dome, top light, arcade, apartment lumbar, road side wall), window materials for vehicles, etc., displays and touch panels for OA equipment, membrane switches, photo covers, polycarbonate resin laminates for water tanks, projection Liquid crystal cell in combination with front panel of TV and plasma display, Fresnel lens, optical card, optical disk and polarizing plate It is useful for optical applications such as phase correction plate. The thickness of the aromatic polycarbonate composition sheet is not particularly limited, but is usually 0.1 to 10 m.
m, preferably 0.2 to 8 mm, and particularly preferably 0.2 to 3 mm. In addition, various processings (various laminations for improving weather resistance, abrasion resistance improving processing for improving surface hardness, surface graining, semi-finished processing, etc.) for adding a new function to the aromatic polycarbonate composition sheet. And opacity processing).

For blending the additives with the aromatic polycarbonate resin of the present invention, any method is adopted. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder or the like is appropriately used. The aromatic polycarbonate resin composition thus obtained is pelletized as it is or by a melt extruder, and then formed into a sheet by a melt extrusion method.

The polycarbonate resin composition of the present invention comprises:
The components can be produced by mixing the above components by any method, for example, using a tumbler, a blender, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like.

A molded article excellent in flame retardancy, antistatic property, dust adhesion preventing property, durability and stability can be obtained from the polycarbonate produced in the present invention by an injection molding method or the like.

[0131]

EXAMPLES (Analysis) 1) Intrinsic viscosity [η] of polycarbonate: measured in methylene chloride at 20 ° C. using an Ubbelohde viscosity tube. The viscosity average molecular weight Mw was calculated from the intrinsic viscosity by the following formula (3). [Η] = 1.23 × 10 ⁻⁴ Mw ^0.83 (3)

2) Terminal group concentration: 0.02 g of the sample was dissolved in 0.4 ml of chloroform, and the solution was dissolved in ¹ H-NM at 20 ° C.
Using R (EX-270 manufactured by JEOL Ltd.), the terminal OH group concentration (eq / t), the phenoxy terminal group concentration (eq / t),
The phenolic terminal group concentration (mol%) was measured.

3) Melt viscosity stability: Using a rheometrics RAA-type flow analyzer under a nitrogen stream at a shear rate of 1 r
The absolute value of the change in melt viscosity measured at ad / sec. 300 ° C. was measured for 30 minutes, and the rate of change per minute was determined. This value must not exceed 0.5% for good short- and long-term stability of the polycarbonate resin composition.

4) Composition moisture content: about 100 g of a sample was precisely weighed, and then dried at 120 ° C. in a vacuum dryer at 3 Pa or less.
After drying for 0 hr, the moisture content was determined from the weight and the weight loss.

5) Thermal stability during molding process; retention stability and generation of black foreign matter Cylinder temperature 300 ° C, mold temperature 80 from injection molding machine
Hue (color; L, a,
h) (color; L ′, L ′,
a ′, b ′) using a color difference meter (Z-1001 manufactured by Nippon Denshoku Co., Ltd.)
DP) and measured by the following formula (4) ΔE = [(LL) ² + (a−a ′) ² + (bb ′) ² ] ^1/2 (4) To evaluate the retention stability. While the ΔE value is related to the degree of molecular weight reduction, it greatly affects the sensory test of a molded article. If the E value exceeds 3, the hue of the molded article is significantly deteriorated, and there is a high possibility that a molded article with a strong yellow tint is obtained. , 2.0 to less than 2.5; good pass, 2
Less than; judged to be excellent.

The number of black foreign matters generated was 100 mm × 10
After a flat plate of 0 mm × 2 mm is retained at a cylinder temperature of 380 ° C. for 10 minutes from an injection molding machine, the cylinder temperature is reduced to 3 mm.
5 in a flat plate obtained by molding under the conditions of 00 ° C and a mold temperature of 80 ° C.
The total number of black foreign substances in the sheet was visually measured and evaluated. The number of black foreign matters is an important judgment item that directly affects the quality of a molded product itself. 0-2; excellent, 3-5; good, 5
9; good; 10 or more; NG. Immediately after the production of the composition and after storage at room temperature for 3 months.

6) Hydrolysis stability The molded pieces or pellets of the composition were placed in an autoclave.
Treated with pure water at 120 ° C. for 10 hours, the rate of decrease in the viscosity average molecular weight was measured. (Production of aromatic polycarbonate)

Reference Example 1 Production of PC-1 aromatic polycarbonate was carried out as follows.
137 parts by weight of purified bisphenol A and 133 parts by weight of purified DPC as raw materials and 4.1 × 10 ^-5 parts by weight of bisphenol A disodium salt as a polymerization catalyst were placed in a reaction vessel equipped with a stirrer, a rectification tower and a decompression device. And 5 × 10 ⁻³ parts by weight of tetramethylammonium hydroxide were melted at 180 ° C. under a nitrogen atmosphere.

Under stirring, the inside of the reaction tank was kept at 13.33 kPa (1
The pressure was reduced to 00 mmHg, and the reaction was carried out for 20 minutes while distilling off the generated phenol. Next, after the temperature was raised to 200 ° C., the pressure was gradually reduced to 4.00 while phenol was distilled off.
The reaction was performed at 0 kPa (30 mmHg) for 20 minutes. Further, the temperature was gradually raised and reacted at 220 ° C. for 20 minutes, 240 ° C. for 20 minutes, and 260 ° C. for 20 minutes. Thereafter, the pressure was gradually reduced at 260 ° C. and 10 minutes at 2.666 kPa (20 mmHg).
The reaction was continued at 1.333 kPa (10 mmHg) for 5 minutes, and finally 260 ° C./66.7 Pa (0.5 m
(mHg) until the viscosity average molecular weight reached 15,300.

Finally, the viscosity average molecular weight was 15300,
Terminal OH group concentration 130 (eq / t-polycarbonate), phenoxy terminal group concentration 109 (eq / t), phenolic terminal group concentration 54 mol%, melt viscosity stability 1.1
%Met.

Reference Example 2 PC-2 2.62 × 10 ^-2 parts by weight of 2-methoxycarbonylphenylphenyl carbonate (hereinafter abbreviated as SAM in the table) was added to the polycarbonate obtained in Reference Example 1.
Stir at 60 ° C. and 133.3 Pa (1 mmHg) for 10 minutes, and then dodecylbenzenesulfonic acid tetrabutylphosphonium salt (hereinafter abbreviated as DBSP including in the table)
3.6 × 10 ^-4 parts by weight, 260 ° C., 66.7 Pa
(0.5 mmHg) for 10 minutes. The viscosity average molecular weight of the obtained polycarbonate was 15,300, the terminal OH group concentration was 48 (eq / t), and the phenoxy terminal group concentration was 191.
(Eq / t), the phenolic terminal group concentration was 20 mol%, and the melt viscosity stability was 0%.

Reference Examples 3 and 4 PC-3 and 4 The polymerization reaction was continued in the same manner as in Reference Example 1 until the viscosity average molecular weight reached 22,500. Finally, a viscosity average molecular weight of 22,500 and a terminal OH group concentration of 73 (eq.
/ T), terminal phenoxy group concentration 77 (eq / t), phenolic terminal group concentration 49 mol%, melt viscosity stability 1.0
%Met. (PC-3)

The polycarbonate (PC-3) thus obtained was treated in the same manner as in Reference Example 2 to obtain a SAM;
1 × 10 ⁻⁴ parts by weight and 3.6 × 10 ⁻⁴ parts by weight of DBSP were added. Each of the finally obtained polycarbonates had a viscosity average molecular weight of 22,500 and a terminal OH group concentration of 37.
(Eq / t), terminal phenoxy group concentration 113 (eq / t)
t), the phenolic terminal group concentration was 25 mol%, and the melt viscosity stability was 0%. (PC-4)

Reference Example 5 PC-5: Example of Interfacial Polymerization In a 5 liter reaction tank equipped with a phosgene blowing tube, a thermometer and a stirrer, purified bisphenol A, 5
22.8 g (2.21 mol), 7.2% aqueous solution of sodium hydroxide, 2.21 l (4.19 mol of sodium hydroxide) and sodium hydrosulfite, 0.98
g (0.0056 mol) was dissolved therein, and while stirring, methylene chloride, 1.27 l and a 48.5% aqueous sodium hydroxide solution, 80.70 g (sodium hydroxide, 0.98
Mol), 250.80 g of phosgene (0.2
(53 mol) was added at 25 ° C. over 180 minutes to carry out a phosgenation reaction.

After completion of the phosgenation, 17.51 g (0.117 mol) of p-tert-butylphenol and 4
8.5% sodium hydroxide aqueous solution, 80.40 g (0.4%)
97 mol) and triethylamine as a catalyst, 1.81
ml (0.013 mol) was added, and the mixture was maintained at 33 ° C. and stirred for 2 hours to complete the reaction. The methylene chloride layer was separated from the reaction mixture, and purified by repeating washing with water five times. The viscosity average molecular weight was 15,300, and the terminal OH group concentration was 15 (eq /
t), terminal phenoxy group concentration 224 (eq / t), phenolic terminal group concentration 6 mol%, melt viscosity stability 0.1%
Was obtained.

(Preparation of Pellets) [Examples 1-10 and Comparative Examples 1-4] The aromatic polycarbonate resin of the above reference example was added to the aromatic polycarbonate resin of the type and amount shown in Table 1) A) of a polyhydric alcohol and a higher fatty acid. Ester, B) a specific phosphoric acid acidic phosphonium salt, C) a specific phosphoric acid compound,
And D) phosphite and the like. Next, such a composition was subjected to a vent-type twin-screw extruder [KTX- manufactured by Kobe Steel Ltd.]
46], the mixture was melt-kneaded while being deaerated at a cylinder temperature of 240 ° C. to obtain pellets. Table 1 shows the evaluation of stability using the composition.

[0147]

[Table 1]

(Sheet Evaluation Example) Example 11 After the composition of Example 5 was melted, it was supplied in a fixed amount by a gear pump and sent to a T-die of a molding machine. It was melt-extruded into a sheet having a thickness of 2 mm or 0.2 mm and a width of 800 mm by pinching or single-sided touch between the mirror-surface cooling roll and the mirror-surface roll.

A visible light-curable plastic adhesive [Adel BENEFIX PC Co., Ltd.] was applied to one side of the obtained aromatic polycarbonate sheet (2 mm thick), and the same sheet was extruded to one side so that air bubbles did not enter. After laminating, 5,000 mJ / cm ² by a light curing device equipped with a metal halide type dedicated to visible light.
JIS K
As a result of measuring in accordance with-6852 (test method for compressive shear bond strength of adhesive), the bond strength was 10.4 MPa (1
06 kgf / cm ² ).

On the other hand, an ink [Natsuda 70-9132: color] was applied to an aromatic polycarbonate sheet having a thickness of 0.2 mm.
136D smoke] and a solvent [isophorone / cyclohexane / isobutanol = 40/40/20 (wt.
%)], Mixed and printed with a silk screen printer, and dried at 100 ° C. for 60 minutes. There was no transfer failure on the printed ink surface and the printing was good.

Separately, a polycarbonate resin obtained by subjecting 1,1-bis (4-hydroxyphenyl) cyclohexane and phosgene to an ordinary interfacial polycondensation reaction (having a specific viscosity of 0.1%).
895, Tg 175 ° C) 30 parts, Plast as a dye
A sheet (0.2 mm thick) printed with a printing ink obtained by mixing 15 parts of Red 8370 (manufactured by Arimoto Chemical Industries) and 130 parts of dioxane as a solvent was mounted in an injection molding die, and polycarbonate resin pellets (panlite) were mounted. L-
Insert molding was performed at a molding temperature of 310 ° C. using a 1225 Teijin Chemicals Ltd.). An insert molded product having a good printed portion appearance was obtained without any abnormality such as bleeding or blurring in the printed portion pattern of the molded product after the insert molding.

(Evaluation of Polymer Blend Compounds) [Examples 12 to 18] In the above Example 8, the aromatic polycarbonate was further added with 0.05% by weight of trimethyl phosphate, and the following symbols in Tables 2 and 3 indicate the same. After mixing the components uniformly using a tumbler, 30 m
Twin screw extruder with mφ vent (KTX- manufactured by Kobe Steel Ltd.)
30), cylinder temperature 260 ° C, 1.33 kP
a) Pelletizing while degassing at a degree of vacuum of 10 mmHg, drying the obtained pellets at 120 ° C. for 5 hours, and then using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.) to determine the cylinder temperature. Molded pieces for measurement were prepared at 270 ° C. and a mold temperature of 80 ° C., and the results of the following evaluations are shown in Tables 2 and 3.

(Resins and Fillers Used) -1 ABS: Styrene-butadiene-acrylonitrile copolymer; Santac UT-61; Mitsui Chemicals, Inc.
-2 AS: styrene-acrylonitrile copolymer;
Styrac-AS 767 R27; manufactured by Asahi Kasei Corporation-3 PET: polyethylene terephthalate; TR-
8580; Teijin Limited, intrinsic viscosity 0.8-4 PBT: polybutylene terephthalate; TRB
-H: Teijin Limited, intrinsic viscosity 1.07

-1 MBS: Methyl (meth) acrylate-butadiene-styrene copolymer; Kaneace B-
56; Kanebuchi Chemical Industry Co., Ltd.-2E-1: Butadiene-alkyl acrylate-
Alkyl methacrylate copolymer; Paraloid EXL
-3E-2: Composite rubber in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component have an interpenetrating network structure; Metablen S-2001;
Made by Mitsubishi Rayon Co., Ltd.

-1 T: talc; HS-T0.8; average particle diameter L = 5 μm, L / D = 8 -2 G, measured by laser diffraction method, manufactured by Hayashi Kasei Co., Ltd. G: glass fiber; chopped strand ECS
-03T-511; manufactured by Nippon Electric Glass Co., Ltd., urethane focusing treatment, fiber diameter 13 μm −3 W: wollastonite; Psycatek NN-4;
Tomoe Kogyo Co., Ltd., number-average average fiber diameter D = 1.5 μm, average fiber length 17 μm determined by electron microscope observation,
Aspect ratio L / D = 20

WAX: olefin wax obtained by copolymerization of α-olefin and maleic anhydride; Diacarna-P30; manufactured by Mitsubishi Kasei Corporation (maleic anhydride content = 10 wt%)

(Evaluation of Physical Properties of Molded Piece) 1) Flexural Modulus The flexural modulus was measured according to ASTM D790. 2) Notched Impact Value According to ASTM D256, a 3.2 mm thick test piece was used to apply an impact from the notch side using a weight, and the impact value was measured. 3) Fluidity Cylinder temperature 250 ° C, mold temperature 80 ° C, injection pressure 9
The fluidity was measured at 8.1 MPa by Archimedes-type spiral flow (thickness 2 mm, width 8 mm). 4) Chemical resistance A 1% strain was applied to a tensile test piece used in accordance with ASTM D638, and the specimen was immersed in 30 ° C. esso regular gasoline for 3 minutes, and then the tensile strength was measured to calculate the retention.
The retention was calculated by the following equation. Retention (%) = (strength of treated sample / strength of untreated sample) × 100

[0158]

[Table 2]

[0159]

[Table 3]

Example 19 Using the resin composition of Example 5, injection compression molding was performed at a resin temperature of 300.degree. C. and a mold temperature of 80.degree. C. to produce an optical disc substrate as one of optical information recording medium substrates. . The obtained disk was transparent and free of warpage or black foreign matter, and was very preferable as an optical disk substrate.

Example 20 Using the resin composition of Example 5, injection molding was carried out at a resin temperature of 300 ° C. and a mold temperature of 80 ° C. to produce a lens cover. The obtained lens cover was transparent and free of black foreign matters, and was very preferable as a lens cover.

[0162]

According to the present invention, a specific amount of a specific phosphoric acid acidic phosphonium salt and a specific phosphoric acid compound is contained in a polycarbonate resin composition containing an ester of a fatty acid, a polyhydric alcohol and a higher fatty acid. ,
A composition having good heat stability and little color tone deterioration, molecular weight reduction and generation of black foreign matter during molding can be obtained. It is even more effective to include a radical scavenger and an aromatic phosphite having a specific peroxide decomposability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 5/103 5/103 5/50 5/50 5/521 5/521 5 / 524 5/524 5/55 5/55 // B29K 69:00 B29K 69:00 B29L 11:00 B29L 11:00 17:00 17:00 (72) Inventor Yuichi Kageyama 2nd Hinodecho, Iwakuni-shi, Yamaguchi Prefecture No. 1 Teijin Co., Ltd. Iwakuni Research Center (72) Inventor Katsuji Sasaki 2-1 Hinodecho, Iwakuni City, Yamaguchi Prefecture Teijin Co., Ltd. Iwakuni Research Center F term (reference) 4F071 AA50 AA81 AB25 AC15 BB05 BC07 4F206 AA28 AB22 AH37 AH74 AH79 JA03 JA07 JF01 JF02 4J002 CG001 CG011 CG021 DH028 EH046 EJ019 EW049 EW069 EW177 EY017 FD079 FD096 GP01 GS02 4J029 AA09 AB04 AC01 AD01 AD03 BB12A HC01 HC02 HC03 J031J04J05J03J041

Claims (10)

[Claims] A main repeating unit derived from a dihydroxy compound and a carbonate bond-forming precursor is represented by the following formula (1): [R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, W is an alkylidene group, an alkylene group, Cycloalkylidene group, cycloalkylene group, phenyl group-substituted alkylene group, oxygen atom,
It is a sulfur atom, a sulfoxide group, or a sulfone group. ]
In the formula, the viscosity average molecular weight is 12000 to 40000,
Per 100 parts by weight of polycarbonate having a phenolic terminal group concentration of 5 to 60 mol% (1) 50 × 10 ^{−4 to} 2000 × 10 ⁻⁴ parts by weight of an ester of a polyhydric alcohol and a higher fatty acid having 10 to 22 carbon atoms (2 ) At least one compound selected from the group consisting of a phosphorous acid-based phosphonium salt (A), a phosphoric acid-based acid phosphonium salt (B), a boric acid-based acid phosphonium salt (C), and a condensed phosphoric acid-based acid phosphonium salt (D); ),
(B), (C), 0.01 × 10 ⁻⁴ to 30 × 10 ⁻⁴ parts by weight as a total of phosphorus atoms derived from (D) and / or (3) hypophosphorous acid (A ′), phosphorous acid At least one compound selected from (B '), phosphoric acid (C') and condensed phosphoric acid (D ') by (A'), (B '), (C'),
0.01 × 1 as the total of phosphorus atoms derived from (D ′)
A polycarbonate resin composition having a melt viscosity stability of 0.5% or less, containing 0 ^-4 to 30 × 10 ^-4 parts by weight. 2. A radical scavenger is used in an amount of 0.1 × 10 ^{-4 to} 5000 × 10 per 100 parts by weight of the polycarbonate.
The polycarbonate resin composition according to claim 1, wherein the composition contains ^-4 parts by weight. 3. Per 100 parts by weight of the polycarbonate,
The polycarbonate resin composition according to claim 1, wherein the composition contains 0.005 × 10 ⁻⁴ to 50 × 10 ⁻⁴ parts by weight of an aromatic phosphite compound (as a phosphorus phosphite atom). 4. Per 100 parts by weight of the polycarbonate,
Phosphate-based compounds (as phosphorous phosphorus atoms) of 0.0
The polycarbonate resin composition according to claim 1, wherein the composition is contained in an amount of from 0.05 × 10 ⁻⁴ to 50 × 10 ⁻⁴ parts by weight. 5. The method according to claim 1, wherein the bluish colorant is contained in an amount of 0.001 × 10 ⁻⁴ to 10 × 10 ⁻⁴ parts by weight per 100 parts by weight of the polycarbonate. Polycarbonate resin composition. 6. The polycarbonate according to claim 1, wherein the polycarbonate is obtained by melt polycondensation of a dihydroxy compound and a carbonate bond-forming precursor in the presence of a transesterification catalyst. The polycarbonate resin composition according to claim 1 or 2. 7. A melt polymerization of a dihydroxy compound and a carbonate bond-forming precursor in the presence of a transesterification catalyst containing a nitrogen-containing basic compound and / or a phosphorus-containing basic compound and an alkali metal compound, to obtain a polycarbonate. In the production, the nitrogen-containing basic compound and / or the phosphorus-containing basic compound 20 per mole of the dihydroxy compound
To 1000 (× 10 ^-6 chemical equivalent), the polycarbonate resin composition of claim 6, wherein the use of a transesterification catalyst containing an alkali metal compound 0.01 to 2 (× 10 ^-6 chemical equivalent) object. 8. An injection molded product of the polycarbonate resin composition according to claim 1. 9. The injection molded product according to claim 8, wherein the injection molded product is an optical information recording medium substrate. 10. The injection molded product according to claim 8, wherein the injection molded product is a lens or a lens cover.