JP2003096289A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is free from transparent foreign matters and has excellent transparency, appearance of molded articles, heat resistance, weather resistance, mechanical strength such as elongation at break and impact strength. . SOLUTION: In an aromatic polycarbonate obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound, the number of transparent foreign matters (N:
The unit is particles / g) and the viscosity average molecular weight (Mv) is as follows: (1) or (2): When Mv ≦ 21000, N ≦ exp (6.824 × 10 ⁻⁴ × Mv−8.626) (1) When Mv> 21000, N ≦ exp (8.514 × 10 ⁻⁵ × Mv + 3.916) (2) An aromatic polycarbonate and a heat stabilizer characterized by satisfying a relational expression represented by the following expression: , If necessary UV absorber,
A thermoplastic resin composition comprising a release agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin which is obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound and is excellent in transparency, surface appearance of a molded article, mechanical strength, thermal stability and weather resistance. A composition is provided.

[0002]

2. Description of the Related Art Aromatic polycarbonates are excellent in mechanical properties such as impact resistance and also in thermal properties, electrical properties, transparency, moldability, etc., and are suitable for various mechanical parts, automobile parts, etc. Widely used for purposes. In particular, there are great expectations for optical applications such as optical fibers, lenses, and optical information recording media, and various studies have been actively conducted. In such optical applications, the appearance of a thermoplastic resin composition having a low foreign matter content is particularly desired.

As a method for producing an aromatic polycarbonate, a so-called phosgene method in which an aromatic diol such as bisphenol and phosgene are reacted in an interfacial polycondensation method has been industrialized. However, the phosgene method requires the use of phosgene that is harmful to the human body, requires a solvent such as dichloromethane, which has a high environmental impact,
In addition, it has been pointed out that a problem such as corrosion when the sodium chloride, which is a by-product, is mixed into the polymer when it is used in electronic parts. On the other hand, a method of transesterifying an aromatic diol compound and a carbonic acid diester compound in a molten state to obtain an aromatic polycarbonate while removing low molecular weight substances such as phenol by-produced outside the system is also known as a so-called melt polymerization method or transesterification method. Has been known for a long time. The melt polymerization method has an advantage that an aromatic polycarbonate can be produced without the above-mentioned problems due to the interfacial polycondensation method, while the polymerization is carried out at a higher temperature than the phosgene method. There is a problem that foreign matter such as burned foreign matter and gel-like foreign matter is likely to occur.

In order to solve such a problem, an additive is added to an aromatic polycarbonate obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound, and the mixture is melt-kneaded by an extruder or the like, and then external dust is added. A method of passing through a polymer filter for the purpose of removing burnt foreign matter has been proposed (for example, JP-A-5-239).
No. 334, No. 6-234845, No. 2
000-178355, Japanese Patent No. 3103652, etc.). However, as a result of investigations by the present inventors, even when the polymer filter is passed through, 1
It was found that transparent foreign matters of 0 μm or more were often generated. It was also found that this transparent foreign substance was essentially contained in the polymer and could not be collected even if it was filtered with a filter.

Furthermore, if this transparent foreign substance occurs frequently,
In particular, in optical information recording media such as CD-R and DVD, when not only a recording error is caused, but also when a force is applied to the molded product from the outside, the transparent foreign matter becomes a nucleus of breakage and break elongation and impact strength. And the like, and the mechanical strength such as is deteriorated, and the thermal stability and weather resistance are deteriorated. It was also found that the surface of the film or sheet appears as fish eyes (fish eyes), which significantly impairs the commercial value.

[0006]

DISCLOSURE OF THE INVENTION In the present invention, an aromatic polycarbonate (A) obtained by subjecting an aromatic dihydroxy compound and a carbonic acid diester compound to a melt polymerization reaction under specific conditions is blended with a heat stabilizer (B). In addition, by adding an ultraviolet absorber (C) and a release agent (D) as necessary, the generation of transparent foreign matters and burns is very small, and the mechanical strength, transparency, appearance, heat stability, and weather resistance are improved. An object of the present invention is to provide a thermoplastic resin composition excellent in

[0007]

Means for Solving the Problems The present inventors have found that transparency and mechanical strength are reduced, molding defects are caused, recording errors occur on information recording media, and fish eyes occur on film and sheet surfaces. In order to prevent the generation and mixing of transparent foreign matters and burns, which seriously impair the commercial value of the product, a thorough study was conducted. As a result of the investigation, it was found that the cause of the transparent foreign matter and burns is a side reaction (crosslinking reaction) which occurs at the stage of melt polymerization at high temperature in the presence of an ester exchange catalyst such as an alkali metal compound. By controlling the reaction conditions to a specific amount of catalyst, a specific temperature range, etc., in order to allow the main reaction (polycondensation reaction) activated by the catalyst to proceed while suppressing this side reaction, a transparent foreign substance to the aromatic polycarbonate can be obtained. Moreover, it is possible to suppress the formation and mixing of burns, and the thermoplastic resin composition obtained by adding a heat stabilizer, an ultraviolet absorber, and a release agent to the aromatic polycarbonate obtained in this way can prevent the progress of burns. Preventable, mechanical strength, transparency, appearance, heat stability,
They have found that they have excellent weather resistance, and have completed the present invention.

That is, the gist of the present invention is that in an aromatic polycarbonate obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound, the number of transparent foreign matters of 10 μm or more (N: unit / g) and viscosity average molecular weight ( Mv) is the following (1) or (2):

[0009]

For Equation 3] Mv ≦ 21000, in the case of ^{N ≦ exp (6.824 × 10 -4} × Mv-8.626) (1) Mv> 21000, N ≦ exp (8.514 × 10 -5 × Mv + 3.916) (2)

The heat stabilizer (B) is added to 100 parts by weight of the aromatic polycarbonate (A) satisfying the relational expression.
0.0001 to 1.0 part by weight is further mixed, and further, an ultraviolet absorber (C) and a release agent (D) are mixed in to provide a thermoplastic resin composition.

The present invention will be specifically described below. Aromatic Polycarbonate (A) A carbonic acid diester compound and an aromatic dihydroxy compound are used as raw materials for melt polymerization when producing the aromatic polycarbonate (A) used in the present invention. [Carbonic acid diester compound] The carbonic acid diester compound as a raw material is represented by the following formula (1).

[0012]

[Chemical 1]

(In the formulae, R and R'have 1 to 18 carbon atoms.
R is an aliphatic group or an aromatic group which may be substituted, and R and R ′ may be the same or different. )

Specific examples of the carbonic acid diester compound represented by the formula (1) include substituted diphenyl carbonates such as dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, diphenyl carbonate and ditolyl carbonate. , Preferably diphenyl carbonate, substituted diphenyl carbonate, and particularly diphenyl carbonate. These carbonic acid diester compounds may be used alone or in combination of two or more. In addition, halogen ions, which may be included as an impurity in the carbonic acid diester compound depending on the production method, not only suppress the cross-linking structure formation reaction which is a side reaction, but also poison the catalyst and cause the polycondensation reaction which is the main reaction. In order to inhibit the halogen ion in the carbonic acid diester compound,
On a weight basis, it is preferably 30 ppb or less, more preferably 20 ppb or less, and especially 10 ppb or less.

Further, the dicarboxylic acid or dicarboxylic acid ester may be used together with the above-mentioned carbonic acid diester compound in an amount of preferably 50 mol% or less, more preferably 30 mol% or less. As such dicarboxylic acid or dicarboxylic acid ester, terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, etc. are used. When such a carboxylic acid or a carboxylic acid ester is used in combination with a carbonic acid diester compound, a polyester carbonate is obtained.

[Aromatic Dihydroxy Compound] Another raw material, an aromatic dihydroxy compound, is represented by the following formula (2):
Indicated by.

[0017]

[Chemical 2]

(In the formula, B is a divalent hydrocarbon group having 1 to 15 carbon atoms, a halogen-substituted divalent hydrocarbon group,
-S- group, -SO ₂ - group, -SO- group, -O- group, or -
CO- group is shown, X is a halogen atom, and has 1 to 14 carbon atoms.
Alkyl group, C6-18 aryl group, C1
Is an oxyalkyl group having 8 to 8 or an oxyaryl group having 6 to 18 carbon atoms. m is 0 or 1 and y is 0-4
Is an integer. )

Examples of the aromatic dihydroxy compound represented by the formula (2) include 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] and 2,2-
Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) ) Phenyl) propane, 2,
2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis ( 4-hydroxy-5-nitrophenyl) methane, 1,
1-bis (4-hydroxyphenyl) ethane, 3,3-
Bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4 , 4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-
2,5-diethoxydiphenyl ether and the like are exemplified. Among these, 2,2-bis (4-hydroxyphenyl) propane is preferable. Moreover, these aromatic dihydroxy compounds can be used individually or in mixture of 2 or more types.

The mixing ratio of the carbonic acid diester compound and the aromatic dihydroxy compound is determined by the desired molecular weight of the aromatic polycarbonate and the amount of terminal hydroxy groups.
The amount of the terminal hydroxy group has a great influence on the thermal stability and hydrolysis stability of the product polycarbonate, and it is necessary to set it to 1000 ppm or less in order to have practical physical properties. Therefore, it is general to use the carbonic acid diester compound in an equimolar amount or more with respect to 1 mol of the aromatic dihydroxy compound, and 1.01 to 1.30 mol, preferably 1.01 to 1.20 mol, and especially 1. It is preferably used in the range of 02 to 1.15 mol.

[Transesterification Catalyst] When the aromatic polycarbonate is produced by the melt polymerization method, a transesterification catalyst is usually used. As the transesterification catalyst, an alkali metal compound and / or an alkaline earth metal compound is mainly used, and an auxiliary boron compound,
It is also possible to use together a basic compound such as a basic phosphorus compound, a basic ammonium compound or an amine compound. These catalysts may be used alone or in combination of two or more.

As the alkali metal compound, lithium,
Inorganic alkali metal compounds such as sodium, potassium, rubidium and cesium hydroxides, hydrogen carbonates, carbonates, acetates, hydrogen phosphates, phenyl phosphates, organic acids such as stearic acid and benzoic acid, methanol , Alcohols such as ethanol, carboxylic acids, organic alkali metal compounds such as salts with phenols such as bisphenol A, and the like. As the alkaline earth metal compound, beryllium,
Inorganic alkaline earth metal compounds such as hydroxides, hydrogen carbonates, carbonates, acetates of calcium, magnesium, strontium and barium, and organic alkaline earth metal compounds such as salts with organic acids, alcohols and phenols Etc.

Specific examples of the basic boron compound include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron and triethylphenyl. Hydrides of boron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc.,
Examples thereof include sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt, barium salt, and strontium salt.

Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine,
Alternatively, a quaternary phosphonium salt or the like can be used.

Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide,
Trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriammonium Examples thereof include phenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide and the like.

Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine,
2-hydroxypyridine, 2-methoxypyridine, 4-
Methoxypyridine, 2-dimethylaminoimidazole,
2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like can be mentioned.

The catalyst amount is usually 0.01 to 10 μmol, preferably 0.05 to 1 μmol, and more preferably 0.1 to 0.5 with respect to 1 mol of the aromatic dihydroxy compound.
It is used in an amount of μmol, particularly preferably 0.2 to 0.35 μmol. If it is less than this amount, the desired molecular weight,
Polymerization activity required for a long time to produce a polycarbonate having a predetermined amount of terminal hydroxy groups cannot be obtained, and if it is more than this amount, the polymer hue is deteriorated and the amount of transparent foreign matter due to a crosslinking structure formation reaction tends to increase. Become. In particular, when an alkali metal compound and / or an alkaline earth metal compound is used, the amount of the metal is preferably 0.01 to 2 μm.
Mol, more preferably 0.05 to 1 μmol, and particularly preferably 0.1 to 0.9 μmol. As for the contribution of the amount of catalyst to the reaction rate, when an alkali metal compound catalyst is used, it is first-order in the main reaction but second-order in the side reaction (crosslinking structure formation), so that Mv is 2000.
In the case of producing a high molecular weight polycarbonate of 0 or more, it is preferable to adopt a method of raising the temperature and decreasing the amount of the catalyst as described later.

[Transparent Foreign Substance] The aromatic polycarbonate (A) according to the present invention is an aromatic polycarbonate obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound, and the number of transparent foreign substances of 10 μm or more (N: unit is number). / G) and the viscosity average molecular weight (Mv)
The following (1) or (2):

[0029]

For Equation 4] Mv ≦ 21000, in the case of ^{N ≦ exp (6.824 × 10 -4} × Mv-8.626) (1) Mv> 21000, N ≦ exp (8.514 × 10 -5 × Mv + 3.916) (2)

This satisfies the relational expression expressed by
Preferably, the following (1 ') or (2'):

[0031]

If Mv ≦ 21000, N ≦ exp (6.52 × 10 ⁻⁴ × Mv−9.087) (1 ′) If Mv> 21000, N ≦ exp (1.115 × 10 ^{− 4} x Mv + 2.179) (2 ')

Which satisfies the relational expression expressed by
More preferably, the following (1 ″) or (2 ″):

[0033]

If Mv ≦ 21000, N ≦ exp (6.52 × 10 ⁻⁴ × Mv-9.78) (1 ″) If Mv> 21000, N ≦ exp (9.796 × 10 ^{− 5} x Mv + 1.855) (2 ")

It is preferable that the relational expression represented by the following is satisfied.

In the present invention, the “number of transparent foreign matters of 10 μm or more” is obtained as follows. That is, a film formed from an aromatic polycarbonate (thickness 70 μm
For m), the total number of transparent foreign matters having a size of 10 μm or more is counted using a stereoscopic microscope (magnification: 200), and the number of foreign matters per 1 g is calculated to be “the number of transparent foreign matters of 10 μm or more”. At the time of measurement, the planar boundary of the transparent foreign substance without nuclei is
It is determined by the difference in refractive index from the periphery, and its size is the maximum distance between two points on the planar boundary. Also,
In the present invention, the “viscosity average molecular weight” is determined as follows. That is, the “viscosity average molecular weight (Mv)” is calculated from the intrinsic viscosity [η] of methylene chloride of an aromatic polycarbonate at a temperature of 20 ° C. by the following formula.

[0036]

[Equation 7] [η] = 1.23 × 10 ⁻⁴ Mv ^0.83

[Crosslinking Structural Unit] The aromatic polycarbonate obtained by melt polymerization has various crosslinking structural units formed on the molecular chain by side reactions such as heat transfer, decarboxylation and dehydration condensation. Typical ones are
Phenyl salicylate structural unit represented by the following formula (3) (hereinafter abbreviated as PSA unit), phenoxybenzoic acid structural unit represented by the following formula (4) (hereinafter abbreviated as PBA unit) and the following formula (5) Diphenyl ether dicarboxylic acid structural unit (hereinafter abbreviated as DCA unit).

[0038]

[Chemical 3]

In the aromatic polycarbonate (A) according to the present invention, the total content of these three types of crosslinked structural units is
It is preferably 2500 ppm or less, more preferably 2000 ppm or less, especially 1500
ppm or less is preferable. When the total content of these three types of structural units is more than 2500 ppm, not only the number of transparent foreign matters in the aromatic polycarbonate increases but also the color tone deteriorates. The content of these cross-linking structural units, the aromatic polycarbonate is dissolved in a deuterated solvent such as deuterated chloroform and directly measured by NMR, or the aromatic polycarbonate is once hydrolyzed, and the main chain carbonate bond is cleaved. After forming the monomer unit, it can be determined by measuring gel permeation chromatography, liquid chromatography, gas chromatography or the like. The total content of such cross-linked structural units (Tc: unit weight ppm) and the above-mentioned number of transparent foreign matters of 10 μ or more (N: unit number / g) are represented by the following formula:

[0040]

If Mv ≦ 21000, N = exp (2.616 × 10 ⁻³ × Tc + 1.518) If Mv> 21000, N = exp (8.109 × 10 ⁻⁴ × Tc + 4.613)

From the fact that a certain proportional relationship represented by the above is shown, it was clearly understood that the origin of generation of the transparent foreign matter was the crosslinked polymer. Therefore, in order to reduce transparent foreign matters, it can be said that it is first necessary to suppress the crosslinking reaction.

Further, since the content of the cross-linking structural unit directly affects the melting characteristics (particularly non-Newtonian property) of the resin, the aromatic polycarbonate (A) according to the present invention is
According to JISK7210, the following formula:

[0043]

[Formula 9] FRR = MVR (260 / 21.6) / MVR
(260 / 2.16)

(In the formula, MVR (260 / 21.6) is
Melt volume flow rate (Melt Volume-Fl) measured under the conditions of 260 ° C. and a load of 21.6 kg.
owRate), and MVR (260 / 2.16)
Indicates a melt volume flow rate measured at 260 ° C. and a load of 2.16 kg. The flow rate ratio (FRR) represented by () is preferably 17 or less, and more preferably 15 or less. If FRR is greater than 17,
It is not preferable because injection molding of a precision molded product becomes difficult.

[Melt Polymerization] The aromatic polycarbonate (A) according to the present invention is prepared from the above-mentioned aromatic dihydroxy compound and carbonic acid diester compound as a raw material, and is melt-polymerized into two steps such as an oligomerization step and a polymerization step. It is manufactured by the above multi-step process. Generally reaction temperature 1
The reaction is carried out while continuously removing the by-produced monophenol compound from the line at 40 to 320 ° C. for a reaction time of 0.1 to 5 hours while increasing the degree of reduced pressure from atmospheric pressure. If necessary, an inert gas such as nitrogen can be circulated. Further, a fractionating tower may be attached to the reactor in order to return the raw materials accompanying the monophenol compound to the reaction tank. The reaction temperature in the oligomerization step is usually 100 to 300 ° C., preferably 180 to 280 ° C., and the reaction pressure is atmospheric pressure to
The range is up to 133 Pa. On the other hand, the reaction temperature in the final stage of the polymerization step is determined by the required performance such as the molecular weight of the aromatic polycarbonate, the color tone, the amount of transparent foreign matter, etc., and is usually 200 to 320 ° C. Since it becomes more vigorous, it is preferable to complete the reaction at the lowest possible temperature. On the other hand, in order to obtain an aromatic polycarbonate having Mv = 20,000 or more, it is necessary to raise the reaction temperature. Therefore, at the stage of the highest reaction temperature, it is usually 250 to 320 ° C., preferably 260 ° C. to 300 ° C.
More preferably 260 to 280 ° C., particularly preferably 2
60 to 275 ° C., especially 260 to 270 ° C. are preferable. Further, since the external heating temperature also affects the formation of the crosslinked structure, it is preferably 320 ° C. or lower, particularly preferably 30.
0 ° C or lower, more preferably 295 ° C or lower, and especially 29
A temperature of 0 ° C or lower is preferable.

The reaction pressure at the final stage of the polymerizing step is also determined by the required performance such as the molecular weight of the aromatic polycarbonate, the color tone and the amount of transparent foreign matter, but in order to obtain the aromatic polycarbonate of the present invention, it is 300 Pa or less. In particular, in order to obtain a high-molecular-weight aromatic polycarbonate having an Mv of 20,000 or more, it is necessary to shorten the time for which the resin is exposed to a high temperature in order to suppress the generation of transparent foreign matter, and therefore, preferably 100 Pa. Hereafter, 70 Pa or less is more preferable, and 50 Pa or less is particularly preferable. The reaction time of each step is appropriately determined depending on the degree of progress of the reaction, but is preferably 0.1 to 10 hours in total in the oligomerization step and the polymerization step, and most preferably 1 to 6 hours. Since the residence time at the highest stage has a great influence on the production of transparent foreign matter, it is preferably 0.1 to 5 hours, more preferably 0.2 to 3 hours, and most preferably 0.3 to 2 hours.

The molecular weight of the aromatic polycarbonate (A) used in the present invention is not particularly limited, but in order to obtain practical physical properties, the viscosity average molecular weight (Mv) is usually 140.
00 to 60,000, preferably 15,000 to 50,000, and particularly 15,000 to 40,000, and particularly 15,000 to 30 from the viewpoint of impact resistance, mechanical strength, and moldability.
000, especially 16000-30000, and even 20
000 to 30,000 is preferable.

The reaction system may be a batch system, a continuous system, or a combination of a batch system and a continuous system. The apparatus to be used may be of any type such as a tank type, a tube type or a tower type. For example, a vertical polymerization tank equipped with various stirring blades, a horizontal uniaxial type polymerization tank or / and a horizontal biaxial type. A type of polymerization tank or the like can be used. The reaction is preferably carried out substantially in the absence of oxygen. For example, the inside of the raw material adjusting tank, the reactor and the piping are replaced with an inert gas such as nitrogen gas before the operation is started. Usually, a molten mixture of an aromatic dihydroxy compound and a carbonic acid diester compound is fed to a vertical reactor. The catalyst may be directly supplied to the first reaction tank on a line different from the raw material, or in a pipe before entering the first reaction tank,
It may be supplied in a state of being mixed with the raw material by a static mixer or the like. If necessary, a solvent for dissolving or suspending the catalyst is used. As a preferable solvent,
Examples include water, acetone, phenol and the like.

The polymerization liquid supply port is preferably located in the liquid phase portion on the side wall of the reaction vessel, and the withdrawal port is preferably located at the bottom portion of the reaction vessel. Further, the method of continuously extracting the reaction solution from each tank is carried out by a method adapted to the physical properties of the reaction solution, such as a method utilizing a head difference, a method utilizing a pressure difference, a method using a liquid feed pump such as a gear pump. Is preferred. In particular, the structure having a retention part is not suitable for the production of the aromatic polycarbonate used in the present invention, and therefore it should be avoided as much as possible.

In the aromatic polycarbonate used in the present invention, when a transesterification catalyst such as an alkali metal compound is used in the production by melt polymerization, the catalyst remaining in the aromatic polycarbonate is neutralized. To
An acidic compound, especially a sulfur-containing acidic compound, is used as a catalyst metal 1.
0.5 to 10 equivalents, preferably 1 to 5 equivalents, relative to the atoms can be added. That is, with respect to the weight of the aromatic polycarbonate, usually 0.01 to 20 ppm,
Preferably 0.1 to 10 ppm, more preferably 3 to
Add 7 ppm.

Examples of the sulfur-containing acidic compound are sulfonic acid, sulfinic acid and their ester derivatives, and specifically, p-toluenesulfonic acid, benzenesulfonic acid and dodecylbenzenesulfonic acid, their methyl and ethyl. , Butyl, t-butyl, octyl, dodecyl, phenyl, benzyl, phenethyl and other esters,
Examples thereof include benzenesulfinic acid, toluenesulfinic acid, and naphthalenesulfonic acid. Of these compounds,
P-toluenesulfonic acid ester or benzenesulfonic acid ester is preferable, and two or more kinds of these compounds may be used. Further, it is preferable to use an alkali metal salt of these compounds in combination with these compounds, because the dispersibility is improved and the deactivating effect is enhanced. As the amount to be used in combination,
It is preferable to use the alkali metal salt in an amount of about 0.3 to 3 times the weight of the non-alkali metal salt.

The sulfur-containing acidic compound can be added to the aromatic polycarbonate by any method. For example, the sulfur-containing acidic compound can be added to and dispersed in the molten or solid state aromatic polycarbonate, either directly or diluted with a diluent. Specifically, it can be fed and mixed in a polycondensation reactor, a transfer line from the reactor, or an extruder, and usually fed into the extruder. It is also possible to mix with aromatic polycarbonate or pellets, flakes, powders, etc. of the other polymer with a mixer or the like, and then feed the mixture to an extruder for kneading. Of these, to the flakes of aromatic polycarbonate, the stock solution of the sulfur-containing acidic compound was added, and after mixing with a mixer or the like,
It is preferably added as a masterbatch. Further, at the time of addition, it is preferable to accurately control the addition amount using a weight feeder or the like.

Heat Stabilizer (B) Examples of the heat stabilizer (B) used in the present invention include hindered phenol compounds, phosphorus compounds, sulfur compounds, epoxy compounds and hindered amine compounds. Among these, at least one heat stabilizer selected from hindered phenol compounds and phosphorus compounds is preferably used.

The hindered phenol compound is preferably represented by the following formula (6).

[0055]

[Chemical 4]

(In the formula (6), R ¹ and R ² have 1 to 1 carbon atoms.
0 hydrocarbon groups, which may be the same or different, and Y is a functional group selected from an ester group, an ether group, an amide group and / or a carbon atom which may contain a phosphorus atom. Z is a hydrocarbon group having 1 to 6 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, a sulfur atom or a single bond, and g is an integer of 1 to 4. Show. )

Specifically, n-octadecyl-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] , Pentaerythrityl-tetrakis [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- {β- (3 -T-butyl-4
-Hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5-methyl) -4-Hydroxyphenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-t-butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, N,
N'-hexamethylenebis (3,5-di-t-butyl-
4-hydroxy-hydrocinnamide) and the like. Among these, n-octadecyl-3- (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3-
(3 ′, 5′-t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5>
-Methylphenyl) propionyloxy} ethyl]-
2,4,8,10-Tetraoxaspiro [5,5] undecane is preferred.

The phosphorus compound is preferably a trivalent phosphorus compound, particularly at least 1 in the phosphite ester.
Phosphite esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms, or tetrakis (2,4
It is preferably at least one selected from -di-t-butylphenyl) -4,4'-biphenylene-diphosphonite. Specific examples of the phosphite include:
4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-ditridecyl) phosphite, 1,1,
3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane, trisnonylphenylphosphite, dinonylphenylpentaerythritol diphosphite, tris (2,4-di-t-butyl) Phenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite,
Di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) fluorinated phosphite, 2, 2'-methylene-bis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, phosphite ester consisting of monononylphenol and dinonylphenol, Further, the above formula (6)
Examples thereof include the phosphite ester having the hindered phenol shown in. In the present invention, as the phosphorus compound, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-diphosphonite, or tris (2,4-di-t-butylphenyl) phosphite, 2 , 2'-Methylene-bis (4,6-di-t-butylphenyl) octyl phosphite is preferred.

The heat stabilizer (B) is blended in an amount of 0.0001 to 100 parts by weight of the aromatic polycarbonate (A).
It is 1.0 part by weight, preferably 0.4 part by weight or less. If it exceeds 1.0 part by weight, there are problems such as deterioration in hydrolysis resistance, and the compounding amount of the heat stabilizer (B) is 0.0.
If it is less than 001 parts by weight, the effect is small and it is not preferable. The blending ratio when the heat stabilizer (B) is used in combination can be arbitrarily determined, and which is used or used in combination is appropriately determined depending on the application of the aromatic polycarbonate and the like. For example, phosphorus compounds are generally highly effective in residence stability under high temperature during molding of aromatic polycarbonate, and heat stability during use of molded articles, and phenol compounds are generally aromatic polycarbonates such as heat aging resistance. It has a high effect on the heat stability during use after forming as a molded product. Further, the combined use of the phosphorus compound and the phenol compound enhances the effect of improving the coloring property.

The thermoplastic resin composition in which the heat stabilizer (B) is blended with the aromatic polycarbonate (A) according to the present invention is in accordance with JIS K7210 and has the following formula:

[0061]

[Formula 10] FRR = MVR (260 / 21.6) / MV
R (260 / 2.16)

(Where MVR (260 / 21.6) is
Melt volume flow rate (Melt Volume-Fl) measured under the conditions of 260 ° C. and a load of 21.6 kg.
owRate), and MVR (260 / 2.16)
Indicates a melt volume flow rate measured at 260 ° C. and a load of 2.16 kg. The flow rate ratio (FRR) represented by () is preferably 17 or less, and more preferably 15 or less. If FRR is greater than 17,
It is not preferable because injection molding of a precision molded product becomes difficult.

Other Additives In the thermoplastic resin composition of the present invention, at least one selected from the ultraviolet absorber (C) and the release agent (D), if necessary.
Seeds of additives can be included. Examples of the ultraviolet absorber (C) include inorganic ultraviolet absorbers such as titanium oxide, cerium oxide and zinc oxide, as well as organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds and triazine compounds. In the present invention, among these, organic ultraviolet absorbers are preferable, and particularly, benzotriazole compound, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy]-. Phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5-
(Octyloxy) phenol, 2,2 '-(1,4-phenylene) bis [4H-3,1-benzoxazine-4-
ON] and [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester.

The benzotriazole compound is represented by the following formula (7) and methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl)-
A condensate with 4-hydroxyphenyl] propionate-polyethylene glycol is preferred.

[0065]

[Chemical 5]

(In formula (7), R ^{3 to} R ⁶ represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Q 3
¹ and Q ² represent a hydrocarbon group which may contain a hydrogen atom, a nitrogen atom having 1 to 40 carbon atoms and / or an oxygen atom. )

Specific examples of the benzotriazole compound of the formula (7) include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3,5-di-).
t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2
-(3-t-Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'-
Hydroxy-5′-t-octylphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α) -Dimethylbenzyl) phenyl] -2H-benzotriazole, [methyl-3-
[3-t-butyl-5- (2H-benzotriazole-
2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate, and further a compound represented by the following formula (8) and the like can be given.

[0068]

[Chemical 6]

Of these, particularly preferred are 2-
(2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, the above formula (5). 2- (4,
6-diphenyl-1,3,5-triazin-2-yl)
-5-[(hexyl) oxy] -phenol, 2-
[4,6-bis (2,4-dimethylphenyl) -1,
3,5-triazin-2-yl] -5- (octyloxy) phenol.

The amount of the ultraviolet absorber (C) compounded is 5 parts by weight or less, preferably 1 part by weight or less, based on 100 parts by weight of the polycarbonate. If it exceeds 5 parts by weight, there is a problem such as mold contamination during injection molding. The ultraviolet absorber is 1
The seeds can be used, but a plurality of them can be used in combination.

As the releasing agent (D), an aliphatic carboxylic acid, an aliphatic carboxylic acid ester, a number average molecular weight of 200 to
It is at least one compound selected from 15,000 aliphatic hydrocarbon compounds and polysiloxane-based silicone oils. Among these, at least one selected from aliphatic carboxylic acids and aliphatic carboxylic acid esters is preferably used.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid or tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Of these, preferred aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferred. Specific examples of such an aliphatic carboxylic acid include palmitic acid, stearic acid, valeric acid,
Examples thereof include caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, glutaric acid, adipic acid and azelaic acid.

As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same one as the above aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Of these alcohols, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol,
Examples include neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like.
These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin. Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate and pentaerythritol tetrastearate.

The compounding amount of the releasing agent (D) is 5 parts by weight or less, preferably 1 part by weight or less, relative to 100 parts by weight of the polycarbonate. If it exceeds 5 parts by weight, there are problems such as deterioration in hydrolysis resistance and contamination of the mold during injection molding. The releasing agent may be used alone or in combination of two or more.

In addition, in the present invention, water addition, dyes, pigments, antistatic agents, antifogging agents, organic / inorganic fillers, flame retardants, which are known techniques within the range not impairing the object of the present invention,
Other thermoplastic resins and the like can be added. These additives can be added simultaneously with the heat stabilizer (B), the ultraviolet absorber (C), the mold release agent (D), or the like, or when added in a vented extruder, As described above, it may be added at the same time as the acidic compound added for the purpose of catalyst neutralization, but it is preferable to add and knead the acidic compound first and then add and knead the other additives.

[0076]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist. The analysis of the aromatic polycarbonate (A) and the raw materials thereof according to the present invention was performed by the following measuring method.

(1) Chloride ion content in diphenyl carbonate About 5 g of diphenyl carbonate (DPC) was precisely weighed and added to 10 mL of toluene, dissolved at 60 ° C., and then ultrapure water (ion-exchanged water containing no chlorine ion). Add 10 mL,
100 using a magnetic stirrer in a constant temperature room at 23 ° C
After stirring at 0 rpm for 10 minutes, the aqueous phase was separated, and the chloride ion in the aqueous phase was quantified by ion chromatography. The analysis result shows that the weight of chlorine ion relative to the weight of DPC is p
It is expressed in pb.

(2) Viscosity average molecular weight (Mv) Aromatic polycarbonate was used as a concentration (C) of 0.6 g / dl methylene chloride solution, and the specific viscosity (ηsp) measured at a temperature of 20 ° C. using an Ubbelohde viscometer Both formulas below

[0079]

[Equation 11] ηsp / C = [η] (1 + 0.28ηsp) [η] = 1.23 × 10 ⁻⁴ Mv ^0.83

Was calculated using. (3) Crosslinking structural unit Hydrolysis treatment: After dissolving 1 g of aromatic polycarbonate in 100 ml of methylene chloride, 18 ml of 28% sodium methoxide methanol solution, 80 m of methanol
1 and then 25 ml of pure water, and then 1 at room temperature.
It was stirred for a period of time for complete hydrolysis. Then, 1N hydrochloric acid was added, and the methylene chloride layer was separated to obtain a hydrolyzate.

Liquid phase chromatography: Dissolve 1 g of the hydrolyzate obtained in 10 ml of acetonitrile,
It was measured by reverse phase liquid chromatography. Reversed-phase liquid chromatography uses a mixed solvent consisting of acetonitrile and a 10 mM ammonium acetate aqueous solution as an eluent, and an acetonitrile / 10 mM ammonium acetate aqueous solution ratio starts from 20/80 and is gradient to 80/20 under a column temperature of 40. The measurement is carried out at ℃, the detection is carried out using a UV detector with a wavelength of 280 nm (manufactured by Shimadzu Corporation, trade name: SPD-6A), and the quantification is BPA.
Each peak area was converted to a BPA-converted weight from the calibration curve of, and determined as the weight with respect to the polymer weight before hydrolysis.
In addition, the identification of the peak is performed by LC-manufactured by Agilent Corporation.
MS (trade name: Agilent-1100) and JEOL NMR (trade name: AL-400) were used.

(4) Number of transparent foreign matters of 10 μm or more (N: unit / g) Aromatic polycarbonate is 6 at 120 ° C. in a nitrogen atmosphere.
After drying for more than an hour, uniaxial 30 manufactured by Isuzu Kako Co., Ltd.
Using a mm extruder, a film having a thickness of 70 μm is formed, and 5 test pieces in a 9 cm × 50 cm area (about 4 g) are cut out, and a stereoscopic microscope is used to remove transparent foreign matter (= fish Marking) and a magnification of 200
The size and number were measured in double. At the time of measurement, the plane boundary of the transparent foreign substance without nuclei was determined by the difference in refractive index from the surroundings, and the size was the maximum distance between two points on the plane boundary line. The total number of transparent foreign matters having a size of 10 μm or more was counted, and the number of foreign matters per 1 g was calculated to be “the number of transparent foreign matters of 10 μm or more”. (5) Film appearance inspection The film obtained in (4) above was visually observed and evaluated.

Example 1 Bisphenol A and diphenyl carbonate were mixed in a nitrogen gas atmosphere at a constant molar ratio (DPC / BPA = 1.0).
50) and heated to 140 ° C. to obtain a molten mixture. This is fed through a raw material introduction tube heated to 140 ° C.
Under a nitrogen atmosphere at atmospheric pressure, the solution was continuously supplied into the first vertical stirring polymerization tank controlled at 220 ° C. The liquid level was kept constant while controlling the valve opening degree provided in the polymer discharge line at the bottom of the tank so that the average residence time was 60 minutes. At the same time when the supply of the raw material mixture was started, an aqueous cesium carbonate solution as a catalyst was continuously supplied at a ratio of 0.60 μmol to 1 mol of bisphenol A.

The polymerization liquid discharged from the bottom of the tank was successively and continuously supplied to the second, third and fourth vertical stirring polymerization tanks and the fifth horizontal stirring polymerization tank. During the reaction, the liquid level was controlled so that the average residence time in each tank was 60 minutes, and at the same time, by-produced phenol was distilled off. The polymerization conditions of the second to fifth polymerization tanks are as follows:
20 ° C, 13332Pa), 3rd polymerization tank (240 ° C, 2
000 Pa), the fourth polymerization tank (270 ° C., 67 Pa), and the fifth polymerization tank (285 ° C., 27 Pa) were set to high temperature, high vacuum, and low stirring speed as the reaction proceeded. The production rate of aromatic polycarbonate is 50 kg / Hr. The viscosity average molecular weight of the thus obtained aromatic polycarbonate, the number of transparent foreign matters having a size of 10 μm or more, and the crosslinked structure content were measured and shown in Table 1. In addition, Table 1 shows the mixing ratio of the above bisphenol A and diphenyl carbonate,
The temperature, pressure, residence time, catalyst concentration, etc. of each polymerization tank are shown together.

Next, the aromatic polycarbonate obtained from the fifth polymerization tank was introduced into a twin-screw extruder (L / D = 42, barrel temperature 240 ° C.) with a gear pump in a molten state, and the first supply was performed. 7 butyl p-toluenesulfonate through the mouth
After adding ppm, and further adding the heat stabilizer shown in Table 1 from the second supply port, the mixture was pelletized through a leaf disk type polymer filter. This polymer filter has 135 leaf disks made of woven wire mesh with an absolute filtration accuracy of 10 μm attached to the center post. Before passing the polymer melt, the flow rate is 5 ml / min, 36 hours, and 280 ° C. under nitrogen atmosphere. The temperature was raised and used. The results of evaluating the obtained thermoplastic resin composition pellets by the following methods are shown in Table 2.

(6) Flow Rate Ratio (FRR) Using a melt indexer manufactured by Takara Kogyo Co., Ltd., the thermoplastic resin composition pellets were heated at 260 ° C. under a load of 21.6 kg.
Melt flow volume MVR per unit time measured under the conditions
(260 / 21.6) and 260 ° C, load 2.16kg
Melt flow volume MVR per unit time (26
0 / 2.16) and the flow rate ratio (FRR) was calculated by the following equation.

[0087]

[Expression 12] FRR = MVR (260 / 21.6) / MV
R (260 / 2.16)

(7) Initial hue: The thermoplastic resin composition pellets were dried at 120 ° C. for 4 hours, and then injection molding machine (trade name: M15) manufactured by Meiki Seisakusho Co., Ltd.
0A-IISJ) and a 3 mm thick molded product at 320 ° C.
Injection molding under the condition of molding cycle of 1 minute, spectroscopic colorimeter (Nippon Denshoku Industries Co., Ltd., trade name: SE2000)
The YI value was measured with. The larger the YI value, the more the coloring. (8) 320 ° C heat resistance test Thermoplastic resin composition pellets were dried at 120 ° C for 4 hours, and then injection molding machine (trade name: M15) manufactured by Meiki Seisakusho Co., Ltd.
0AII-SJ) and a 3 mm thick molded product at 320 ° C.
Injection molding was performed under the conditions of a molding cycle of 10 minutes, and the molded product of the fifth shot under these conditions was measured for YI by a transmission method with a spectroscopic colorimeter (trade name: SE2000) manufactured by Nippon Denshoku Industries Co., Ltd. Burnt dust was visually observed and evaluated in the following three grades. ○ No burnt trash △ Some burnt trash × Many burnt trash

(9) Elongation at break, impact strength After drying the thermoplastic resin composition pellets at 120 ° C. for 4 hours, an injection molding machine (trade name: M15) manufactured by Meiki Seisakusho Co., Ltd.
0AII-SJ) at 320 ° C. for 1 minute of molding cycle according to ASTM D1822 1.6 mm
A thickness L type tensile impact test piece and a type 1 tensile test piece having a thickness of 3.2 mm according to the regulations of ASTM D638 were molded, and the impact strength and the elongation at break were measured. (10) The fish-eye thermoplastic resin composition pellets of the sheet are melt-kneaded by an extruder with a vent having a screw diameter of 65 mm set to a temperature of 280 ° C., and passed through a T-die having a width of 600 mm set to 275 ° C.
The sheet was cooled while being sandwiched between two polishing rolls having a surface temperature set to 130 ° C., a sheet having a thickness of 0.5 mm was extruded, fish eyes were visually observed, and the following three grades were evaluated. ○: No fish eye △: A little fish eye ×: Many fish eyes (11) Weather resistance test The molded piece whose initial hue was measured in (7) above was subjected to a black panel temperature of 63 ° C using a xenon weather meter. Was treated for 600 hours, and the YI after the treatment was measured.

Examples 2 to 3 Bisphenol A and diphenyl carbonate are shown in Table 1.
Mixed in a molar ratio of, the temperature, pressure, residence time of each polymerization tank,
The same operation as in Example 1 was carried out except that the kind and concentration of the catalyst, the kind and the addition amount of the heat stabilizer to be added were carried out under the conditions of Table 1. The evaluation results of the obtained thermoplastic resin composition pellets are shown in Table 2. However, in Example 3, in the evaluation of the fish eye of the sheet, the set temperature at the time of melt kneading was set to 29.
The temperature was set to 5 ° C. and the temperature of the T die was set to 285 ° C. Comparative Example 1 The same operation as in Example 2 was performed except that the heat stabilizer was not added. The evaluation results of the obtained thermoplastic resin composition pellets are shown in Table 2.

Comparative Examples 2 to 3 Bisphenol A and diphenyl carbonate are shown in Table 1.
Mixed in a molar ratio of, the temperature, pressure, residence time of each polymerization tank,
Example 1 except that the catalyst type and concentration were set as shown in Table 1.
The same operation was performed. The evaluation results of the obtained thermoplastic resin composition pellets are shown in Table 2.

[0092]

[Table 1]

[0093]

[Table 2]

The heat stabilizers 1 to 4 used as the heat stabilizers A and B in Table 1 are as follows. [Heat Stabilizer A (Hindered Phenol Compound)] Heat Stabilizer 1: n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate (trade name: IRGANOX 1076, Ciba Specialty Chemicals Co., Ltd.) Heat Stabilizer 2: Pentaerythrityl-Tetrakis [3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] (trade name: IRGANOX10
10, Ciba Specialty Chemicals) [Heat Stabilizer B (Phosphorus Compound)] Heat Stabilizer 3: Tris (2,4-di-t-butylphenyl) phosphite (trade name: ADEKA STAB 2112, Asahi Denka Co., Ltd.) Heat stabilizer 4: 2,2'-methylene-bis (4,6-di-
t-Butylphenyl) octyl phosphite (trade name:
HP10, manufactured by Asahi Denka Co., Ltd.

Examples 4 to 6 In addition to the compositions of Examples 1 to 3, a UV absorber was added.
According to the above, the same operation as in Example 1 was performed, except that the addition was performed from the second supply port of the twin-screw extruder. The evaluation results of the obtained thermoplastic resin composition pellets are shown in Table 3. However,
In Example 6, in the fish eye evaluation of the sheet, the set temperature at the time of melt-kneading was 295 ° C, and the set temperature of the T die was 285 ° C. Comparative Examples 4 to 6 A UV absorber was added to the compositions of Comparative Examples 1 to 3 in Table 3.
According to the above, the same operation as in Comparative Examples 1 to 3 was performed, except that the addition was performed from the second supply port of the twin-screw extruder. The evaluation results of the obtained thermoplastic resin composition pellets are shown in Table 3.

[0096]

[Table 3]

UV1 to UV3 used as ultraviolet absorbers in Table 3 are as follows. UV1: 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole (trade name: Seesorb 7
09, manufactured by Cypro Kasei Co., Ltd. UV2: 2- [2-hydroxy-3,5-bis (α, α)
-Dimethylbenzyl) phenyl] -2H-benzotriazole (trade name: TINUVIN234, manufactured by Ciba Specialty Chemicals) UV3: [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester (trade name: Sanduvor PR25, Clariant (Made by the company)

Examples 7 to 9 The same operation as in Example 1 except that a releasing agent was further added to the compositions of Examples 1 to 3 from the second feed port of the twin-screw extruder according to Table 4. I went. The evaluation results of the obtained thermoplastic resin composition pellets are shown in Table 4. However, Example 9
Then, in the fisheye evaluation of the sheet, the set temperature at the time of melt-kneading was 295 ° C. and the set temperature of the T die was 285.
℃ was made. Comparative Examples 7 to 9 The same operations as in Comparative Examples 1 to 3 were performed, except that a release agent was further added to the compositions of Comparative Examples 1 to 3 from the second supply port of the twin-screw extruder according to Table 4. went. The evaluation results of the obtained thermoplastic resin composition pellets are shown in Table 4.

[0099]

[Table 4]

In Table 4, the release agents 1 to 5 used as the release agent are as follows. Release agent 1: Glycerin monostearate (trade name: Riquemal S-100A, manufactured by Riken Vitamin Co., Ltd.) Release agent 2: Pentaerythritol tetrastearate (trade name: Unistar H-476, manufactured by NOF Corporation) ) Release agent 3: Beeswax (trade name: Golden brand, manufactured by Miki Chemical Industry Co., Ltd.) Release agent 4: Pentaerythritol distearate (Product name: Unistar H-47 6D, manufactured by NOF Corporation) Release agent 5: stearic acid (trade name: Unistar NAA180, manufactured by NOF CORPORATION)

[0101]

EFFECTS OF THE INVENTION According to the present invention, since transparent foreign matter is prevented from being mixed into a product, transparency, appearance of a molded product can be improved, and further, thermal stability, weather resistance, elongation at break, impact strength. A thermoplastic resin composition excellent in mechanical strength such as is obtained.

Continued front page    (72) Inventor Takao Tayama             1-1 Kurosaki Castle Stone, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation (72) Inventor Yamamoto Tadashi             1-1 Kurosaki Castle Stone, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation (72) Inventor Narutoshi Hyodo             1-1 Kurosaki Castle Stone, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation (72) Inventor Hideki Kinoshita             1-1 Kurosaki Castle Stone, Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture               Within Mitsubishi Chemical Corporation F-term (reference) 4J002 AE052 CG011 CG021 CG031                       CH052 DE097 DE107 DE137                       EF057 EF067 EF087 EH037                       EH047 EH077 EH087 EH097                       EH117 EJ046 EJ066 EL126                       EP026 EU177 EU187 EU196                       EU237 EV076 EV246 EW066                       EW116 FD052 FD057 FD066                       FD162 FD167

Claims (7)

[Claims] 1. An aromatic polycarbonate obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound, wherein the number of transparent foreign matters (N:
The unit (piece / g) and the viscosity average molecular weight (Mv) are as follows (1) or (2): ## EQU1 ## When Mv ≦ 21000, N ≦ exp (6.824 × 10 ⁻⁴ × Mv− 8.626) (1) When Mv> 21000, N ≦ exp (8.514 × 10 ⁻⁵ × Mv + 3.916) 100 weight of aromatic polycarbonate (A) satisfying the relational expression represented by (2) 0.00 parts of heat stabilizer (B)
A thermoplastic resin composition containing 01 to 1.0 parts by weight. 2. The thermoplastic resin composition according to claim 1, which has a flow rate ratio (FRR) represented by the following formula of 17 or less according to JIS K 7210. [Formula 2] FRR = MVR (260 / 21.6) / MVR
(260 / 2.16) 3. The total content of crosslinked structural units is 2500 p.
The thermoplastic resin composition according to claim 1 or 2, wherein the aromatic polycarbonate (A) having a pm or less is used. 4. The thermoplastic resin according to any one of claims 1 to 3, wherein the heat stabilizer (B) is at least one compound selected from hindered phenol compounds and phosphorus compounds. Composition. 5. The thermoplastic resin according to claim 1, which contains at least one additive selected from an ultraviolet absorber (C) and a release agent (D). Resin composition. 6. The ultraviolet absorber (C) is a benzotriazole compound, 2- (4,6-diphenyl-1,3,5-).
Triazin-2-yl) -5-[(hexyl) oxy]
-Phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5
-(Octyloxy) phenol, 2,2 '-(1,4-
Phenylene) bis [4H-3,1-benzoxazine-4
-One], [(4-methoxyphenyl) -methylene]-
The thermoplastic resin composition according to claim 5, which is at least one compound selected from propanedioic acid-dimethyl ester. 7. The thermoplastic resin composition according to claim 5, wherein the release agent (D) is at least one compound selected from aliphatic carboxylic acids and aliphatic carboxylic acid esters. .