JPH05239332A - Production of polycarbonate resin composition and its use - Google Patents

Abstract

PURPOSE:To stably obtain the subject composition having excellent residence stability and surface form in high efficiency by adding and kneading resins and additives to a polycarbonate produced by a melt-polycondensation process while the polycarbonate is in molten state and granulating the kneaded mixture by cutting. CONSTITUTION:An aromatic hydroxyl compound [preferably 2,2-bis (4 hydroxyphenyl)propane] and a carbonic acid diester (preferably diphenyl carbonate) are subjected to melt-polycondensation in the presence of a catalyst. The produced polycarbonate (A) is incorporated in molten state with (B) a resin other than the component A (preferably polyester resin, etc.) and/or (C) an additive [preferably butyl p-toluenesulfonate, tris (2,4-di-t-butylphenyl) phosphite, etc.] and the mixture is kneaded. Finally, the obtained composition is granulated by cutting in molten state to obtain the objective composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a polycarbonate resin composition, and more specifically to pellets having excellent retention stability such as thermal stability and hue stability during production and excellent surface properties. The present invention relates to a method for producing a polycarbonate-based resin composition that can efficiently produce a polycarbonate-based resin composition that can be produced, and uses of the polycarbonate-based resin composition.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate has excellent mechanical properties such as impact resistance, heat resistance and transparency, and is widely used in various mechanical parts, optical discs, automobile parts, etc. Has been. Conventionally, such a polycarbonate is produced by a method of directly reacting an aromatic dihydroxy compound such as bisphenol with phosgene (interfacial method) or a method of transesterifying an aromatic dihydroxy compound and a carbonic acid diester (melting method). And is usually obtained as pellets, chips or powder.

By the way, even in the case of polycarbonate having excellent physical properties as described above, further improvement is desired in the properties such as chemical resistance, moldability, and thickness dependency of impact resistance. .. Therefore, conventionally, by adding various other resins, resin compositions or resin modified products in various proportions to polycarbonate, depending on the application,
Attempts have been made to improve properties such as chemical resistance, moldability, or thickness dependence of impact resistance. Further, in order to make up for the disadvantages of a certain resin or resin composition, polycarbonate is often mixed with the resin.

For example, JP-A-2-247248, JP-A-2-202545, and JP-A-2-261.
No. 853, JP-A-2-261860, JP-A-3-199255, JP-A-3-7758 and the like disclose polyesters, aromatic vinyl-diene-vinyl cyanide copolymers, aromatic vinyl series. A resin composition comprising a resin, an olefin resin or an acrylic resin having a functional group, and a polycarbonate is disclosed.

Further, there are known compositions in which various additives are added to polycarbonate or compositions comprising polycarbonate and other resins. As a method for preparing a resin composition comprising such a polycarbonate and other resins and / or additives, generally, these are dispersed and mixed in a high speed mixer such as a turnbull mixer or a Henschel mixer, and then an extruder or a Banbury mixer. A method of melt-kneading with a mixer, a roll or the like is known. At this time, the polycarbonate is supplied in a solid state such as pellets, chips, or powder, but since the polycarbonate has a high melt viscosity, a large shear heat insulation (shear heat) is likely to occur during melt kneading, and a part of the polycarbonate is heated. There was a case where it was decomposed, the molecular weight was lowered, it was colored, and gel was generated. In this way, when the composition is prepared, the excellent properties originally possessed by the polycarbonate may be deteriorated, and a resin composition having desired properties may not be obtained. Further, when the polycarbonate and the other resin and / or the additive are mixed in solids such as pellets, chips, or powders and kneaded, poor dispersion is caused, and it is difficult to obtain a uniform composition. Stable production of a resin composition having a composition is industrially very difficult, and at the same time, the cost tends to increase.

The resin composition obtained by melt-kneading the polycarbonate and other resins and / or additives is usually cooled with water or the like and then cut and granulated. Since the melt viscosity, hardness, etc. of the polycarbonate, additives, and other resins used vary widely, the granulation conditions change accordingly. When trying to do this under a certain condition, for example, when glass fiber or high-viscosity resin is added to polycarbonate, the hardness and the molecular weight become too high, which may make cutting difficult. Further, when a high fluidity resin or a low molecular weight polycarbonate is used, strand breakage easily occurs. Therefore, it is necessary to adjust the cutting conditions every time the content of the resin composition is changed, which tends to reduce the production efficiency during granulation.

Further, in the conventional granulation method, chips or the like of the resin composition may be generated during granulation, or pellets having poor surface properties may be obtained. In this way, if pellets containing cutting chips, etc. or having poor surface properties are used as the molding material, the raw material becomes unstable in the molding machine at the time of molding, the moldability decreases, and the molding efficiency decreases. I will end up. Further, there is a possibility that the cutter may be spilled and mixed during granulation, and thus there was concern about using the resin composition pellets obtained by such a granulation method as a molding material for precision applications.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional techniques, and pellets having excellent thermal stability during production, retention stability such as hue stability, and excellent surface properties. It is an object of the present invention to provide a method for producing a polycarbonate-based resin composition capable of efficiently and stably producing a polycarbonate-based resin composition capable of producing the above, and a use of the polycarbonate-based resin composition.

[0009]

SUMMARY OF THE INVENTION A method for producing a polycarbonate-based resin composition according to the present invention is a method in which an aromatic dihydroxy compound and a carbonic acid diester are melt-polycondensed in the presence of a catalyst, and then the reaction product [A] polycarbonate is While the resin is in a molten state, a resin other than [B] polycarbonate and / or an additive [C] is added and kneaded, and then this polycarbonate resin composition is cut and granulated while in a molten state. It is characterized by doing.

According to the method for producing a polycarbonate resin composition according to the present invention, while the polycarbonate [A], which is a reaction product obtained by melt polycondensation, is in a molten state, a resin other than [B] polycarbonate is used. And / or [C] additive is added and kneaded to form a polycarbonate-based resin composition, and then the polycarbonate-based resin composition is cut and granulated while in a molten state. It is possible to minimize the number of thermal histories received during the production of the resin composition, and to suppress the thermal decomposition of polycarbonate or the like due to shear heat, and thus to efficiently provide a polycarbonate resin composition with little thermal deterioration. It can be manufactured stably.

Further, in the present invention, the polycarbonate resin composition is obtained as pellets having a smooth surface, has excellent surface properties, and easily penetrates into a molding machine during molding,
Excellent moldability. The polycarbonate-based resin composition obtained in the present invention has a small content of cutting chips and foreign substances, and is particularly preferably used for precision applications.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a polycarbonate resin composition according to the present invention will be described in detail below. First, in the present invention, an aromatic dihydroxy compound and a carbonic acid diester are melt-polycondensed in the presence of a catalyst to produce [A] polycarbonate.

The aromatic dihydroxy compound is not particularly limited, but includes a compound represented by the following formula [I].

[0014]

[Chemical 1]

R ¹ and R ² are hydrogen atoms or monovalent hydrocarbon groups, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are a halogen atom or a monovalent hydrocarbon group, and these may be the same or different. p and q represent the integer of 0-4. ) Specific examples of the aromatic dihydroxy compound include the following compounds: bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl)
Butane, 2,2-bis (4-hydroxyphenyl) octane,
Bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-
Bis (4-hydroxy-t-butylphenyl) propane, 2,2
-Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane Bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
-Dihydroxy aryl ethers such as dimethyl phenyl ether, 4,4'-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,
4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and other dihydroxydiaryl sulfoxides, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-
Dihydroxydiaryl sulfones such as dimethyldiphenyl sulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. As the aromatic dihydroxy compound, the following general formula [I
The compound represented by I] can also be used.

[0017]

[Chemical 2]

In the formula, R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof, or halogen, and may be the same or different. n is 0-4
Is an integer. Specific examples of the aromatic dihydroxy compound represented by the above general formula [II] include resorcin and
3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,3,
Substituted resorcins such as 4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, catechol, hydroquinone and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3- t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,5,6 -Substituted hydroquinones such as tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone can be mentioned.

Further, in the present invention, as the aromatic dihydroxy compound, 2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1 'represented by the following general formula is used. -Spirobi- [IH-indene] -6,6'-diol can also be used.

[0020]

[Chemical 3]

These aromatic dihydroxy compounds can be used alone or in combination. Specific examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl. Carbonate etc. are mentioned.

Of these, diphenyl carbonate is particularly preferably used. These carbonic acid diesters may be used alone or in combination. The carbonic acid diester as described above may contain a dicarboxylic acid or a dicarboxylic acid ester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

Examples of such dicarboxylic acid or dicarboxylic acid ester include terephthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as diphenyl terephthalate and diphenyl isophthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, diphenyl sebacate, decanedioic acid Diphenyl, aliphatic dicarboxylic acids such as diphenyl dodecanedioate, cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,
3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclophenyldicarboxylic acid diphenyl, 1,2-cyclobutanedicarboxylic acid diphenyl, 1,3- Cyclobutanedicarboxylic acid diphenyl, 1,2-cyclopentanedicarboxylic acid diphenyl, 1,3-cyclopentanedicarboxylic acid diphenyl, 1,2-cyclohexanedicarboxylic acid diphenyl, 1,3-cyclohexanedicarboxylic acid diphenyl, 1,4-cyclohexanedicarboxylic acid Examples thereof include alicyclic dicarboxylic acids such as diphenyl.

Such dicarboxylic acids or dicarboxylic acid esters may be used alone or in combination.

The above carbonic acid diester is usually used in a proportion of 0.90 to 1 mol of the aromatic dihydroxy compound.
It is desirable to use it in an amount of 1.30 mol, preferably 0.95 to 1.20 mol. By adjusting the carbonic acid diester and the aromatic dihydroxy compound within the above range, a polycarbonate having a desired terminal hydroxyl group concentration can be easily produced.

In the present invention, when producing a polycarbonate, a polyfunctional compound having three or more functional groups in one molecule can be used together with the aromatic dihydroxy compound and the carbonic acid diester as described above. As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferable, and a compound containing three phenolic hydroxyl groups is particularly preferable. Specifically, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2 ', 2 "-tris (4-hydroxyphenyl)
Diisopropylbenzene, α-methyl-α, α ', α'-tris (4-hydroxyphenyl) -1,4-diethylbenzene, α,
α ', α "-Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, 4,6-dimethyl
-2,4,6-tri (4-hydroxyphenyl) -heptane-2,1,
3,5-tri (4-hydroxyphenyl) benzene, 2,2-bis
-[4,4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid and the like can be mentioned.

Of these, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are preferable. The polyfunctional compound is generally used in an amount of 0.03 mol or less, preferably 0.001 to 0.02 mol, and more preferably 0.0, relative to 1 mol of the aromatic dihydroxy compound.
Used in an amount of 01 to 0.01 mol.

In the present invention, first, the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed in the presence of a catalyst to produce a polycarbonate [A].
In the present invention, it is preferable to use (a) an alkali metal compound and / or an alkaline earth metal compound as the catalyst. Examples of such (a) alkali metal compound and alkaline earth metal compound include organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides or alcoholates of alkali metals and alkaline earth metals. And the like are preferable.

More specifically, as the alkali metal compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate , Potassium acetate, lithium acetate,
Sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate. , Dilithium hydrogen phosphate, disodium salt of bisphenol A,
Examples thereof include dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt and lithium salt.

Specific examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate and calcium carbonate. , Barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.

These compounds may be used alone or in combination. Such (a) alkali metal compound and / or alkaline earth metal compound is preferably 1 × 10 ^{−8 with} respect to 1 mol of the aromatic dihydroxy compound.
To 1 × 10 ⁻³ mol, more preferably 1 × 10 ⁻⁷ to 2 ×
Used in an amount of 10 ^-6 mol. (a) When the amount of the alkali metal compound or alkaline earth metal compound used is 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol with respect to 1 mol of the aromatic dihydroxy compound, the polymerization activity can be maintained high. Together with the acidic compound (described later) in an amount that does not adversely affect the properties of the obtained polycarbonate.
Can be added to sufficiently neutralize or weaken the basicity of these compounds.

In the present invention, the catalyst as described above is used.
(a) together with an alkali metal compound and / or an alkaline earth metal compound, (b) a basic compound and / or
(c) A boric acid compound can also be used. like this
Examples of the basic compound (b) include nitrogen-containing basic compounds that are easily decomposable or volatile at high temperatures, and specific examples include the following compounds.

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH ) Such as alkyl, aryl,
Ammonium hydroxides having araryl groups, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, R ₂ NH (wherein R is an alkyl group such as methyl or ethyl, phenyl, toluyl or other aryl groups) Etc.)
Secondary amines represented by RNH ₂ , primary amines represented by RNH ₂ (wherein R is the same as above), imidazoles such as 2-methylimidazole and 2-phenylimidazole,
Alternatively, ammonia, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh). ₄ ) such as basic salts.

Of these, tetraalkylammonium hydroxides, especially electronic tetraalkylammonium hydroxides containing few metal impurities, are preferably used. When the (b) basic compound is used as a catalyst, the (b) basic compound is an aromatic dihydroxy compound 1
It is generally used in an amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol, preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, based on mol.

Examples of the boric acid compound (c) include boric acid and boric acid esters represented by the following general formula. In the formula B (OR) _n (OH) _3-n , R is alkyl such as methyl or ethyl, aryl such as phenyl, and n is 1, 2 or 3.

Specific examples of the borate ester include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. Is mentioned. When boric acid or boric acid ester (c) is used as the catalyst, it is usually 1 × 10 ⁻⁸ to 1 × with respect to 1 mol of the aromatic dihydroxy compound.
10 ⁻¹ mol, preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol,
More preferably, it is used in an amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol.

These are, for example, (a) alkali metal compounds and / or alkaline earth metal compounds and
(b) a combination of nitrogen-containing basic compounds, and (a) an alkali metal compound and / or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c) boric acid or a boric acid ester. Can be preferably used in combination.

As described above, the catalyst obtained by combining (a) the alkali metal compound and / or the alkaline earth metal compound and (b) the nitrogen-containing basic compound in the above-mentioned use amount is sufficient for the polycondensation reaction. It is preferable because the high-molecular-weight polycarbonate can be produced with high polymerization activity by advancing at a high speed. Further, the catalyst in which the above three are used in combination in the above-mentioned use amounts is preferable because it is possible to produce a polycarbonate that is less likely to undergo thermal deterioration such as decrease in molecular weight.

In the presence of such a catalyst, the polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester can be carried out under the same conditions as the conventionally known polycondensation reaction conditions. Specifically, it is 80 to 250 ° C., preferably 1
The aromatic dihydroxy compound is reacted with the carbonic acid diester under atmospheric pressure at a temperature of 00 to 230 ° C., more preferably 120 to 190 ° C. for 0 to 5 hours, preferably 0 to 4 hours, more preferably 0 to 3 hours. .. Next, the reaction temperature is raised while reducing the pressure of the reaction system to carry out the reaction between the aromatic dihydroxy compound and the carbonic acid diester, and finally to 5
mmHg or less, preferably 1 mmHg or less under reduced pressure, 24
A polycondensation reaction between an aromatic dihydroxy compound and a carbonic acid diester is carried out at 0 to 320 ° C.

The polycondensation reaction as described above may be carried out continuously or batchwise. However, in the present invention, the continuous reaction produces a polycarbonate of stable quality at a lower cost. It is possible and preferable. The reactor used for carrying out the above reaction may be of a tank type, a tube type or a column type. The reaction product [A] polycarbonate obtained as described above has an intrinsic viscosity of usually 0.10 to 1.0 dl / g, preferably 0.30 to 0.65 dl when measured in methylene chloride at 20 ° C.
/ G.

As described above, the production method according to the present invention does not use toxic substances such as phosgene and methylene chloride in the melt polycondensation of polycarbonate, and is therefore preferable in terms of environmental hygiene.

In the present invention, when a polycarbonate resin composition is produced, the reaction product [A] polycarbonate obtained as described above is immediately cooled after the polycondensation reaction without cooling, and the following [B] ] A resin other than polycarbonate and / or an additive [C] is added and kneaded. That is, while the [A] polycarbonate, which is the reaction product in the reactor or extruder in the molten state obtained after the completion of the polycondensation reaction, is in the molten state,
A resin other than [B] polycarbonate and / or [C] additive is directly added and kneaded.

This melt-kneading can be carried out under normal pressure, but also under reduced pressure. When the melt-kneading is performed under reduced pressure, it is usually 0.1 mmHg to 730 mmHg, preferably 5 mmHg to 700 mmHg, more preferably 2 mmHg to 700 mmHg.
It is desirable to carry out under a pressure condition of 0 mmHg to 600 mmHg.

Resins other than such a polycarbonate [B] will be described. In the present invention, as resins other than [B] polycarbonate, the above-mentioned JP-A-2-2472 can be used.
48, JP-A-2-202545, JP-A-2
-261853, JP-A-2-261860, JP-A-3-199255, and JP-A-3-775.
Known resins described in Japanese Patent No. 8 and the like can be used.

Specifically, the following resins may be mentioned. Polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, aromatic vinyl resins such as poly α-methylstyrene, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer Polymers and α-olefins such as ethylene / glycidyl methacrylate copolymers α, β
-Polyolefin resins such as unsaturated glycidyl ester copolymers, acrylic resins such as polymethylmethacrylate, diene rubbers such as polybutadiene and polyisoprene, polyvinyl cyanide such as polyacrylonitrile and polymethacrylonitrile, nylon 6, nylon 6
Aromatic vinyl / diene / cyanide vinyl copolymers such as styrene / butadiene / acrylonitrile copolymers such as polyamide resins such as 6 and the like, polyimides and polyamide imide resins.

Further, a resin obtained by introducing a functional group such as an epoxy group, an oxazolinyl group, or an unsaturated carboxyl group into the above resin can also be mentioned. Of these, polyester resins, polyolefin resins, acrylic resins, aromatic vinyl / diene / cyanated vinyl copolymers, etc. are preferably used. These may be used alone or in combination. When used in plurality, they may be added separately or may be added simultaneously.

In the present invention, the resin other than the above-mentioned [B] polycarbonate varies depending on the purpose of the obtained polycarbonate resin composition, but is usually 1 to 2000 parts by weight with respect to 100 parts by weight of the [A] polycarbonate. Used in parts by weight.

Specific examples of the [C] additive used in the present invention include (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, (b) Examples thereof include phosphorus compounds, (C) epoxy compounds, and (D) phenolic stabilizers.

Specific examples of the sulfur-containing acidic compound having a pKa value of 3 or less and the derivative formed from the acidic compound include sulfurous acid, sulfuric acid, sulfinic acid compounds, and sulfonic acid compounds. And derivatives thereof. More specifically, examples of the sulfite derivative include dimethyl sulfite, diethyl sulfite, dipropyl sulfite, dibutyl sulfite, diphenyl sulfite and the like.

Examples of the sulfuric acid derivative include dimethyl sulfuric acid, diethyl sulfuric acid, dipropyl sulfuric acid, dibutyl sulfuric acid and diphenyl sulfuric acid. Examples of the sulfinic acid compound include benzenesulfinic acid, toluenesulfinic acid, and naphtherensulfinic acid.

Examples of the sulfonic acid compounds and their derivatives include compounds represented by the following general formula [III] and their ammonium salts.

[0052]

[Chemical 4]

In the formula, R ⁷ is a hydrocarbon group having 1 to 50 carbon atoms (the hydrocarbon group may be substituted with halogen), and R ⁸ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms ( A hydrocarbon group may be substituted with halogen),
n is an integer of 0-3.

Examples of such sulfonic acid compounds and derivatives thereof include the following compounds. Sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, p-toluene sulfone Sulfonic acid esters such as ethyl acidate, butyl p-toluenesulfonate, octyl p-toluenesulfonate and phenyl p-toluenesulfonate, ammonium sulfonates such as ammonium p-toluenesulfonate.

Further, in addition to the sulfonic acid compound represented by the above general formula [III], trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene,
Examples thereof include sulfonic acid compounds such as methyl acrylate-sulfonated styrene copolymer.

These compounds may be used alone or in combination. In the present invention, as the (a) sulfur-containing acidic compound and the derivative formed from the acidic compound, the sulfonic acid compound represented by the general formula [III] and its derivative are preferably used. Further, in the above general formula [III], compounds in which R ⁷ and R ⁸ are substituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms and n is an integer of 0 to 1 are preferably used. Specifically, benzene sulfonic acid, butyl benzene sulfonate, p-toluene sulfonic acid, ethyl p-toluene sulfonate, and butyl p-toluene sulfonate are preferably used. In the present invention, butyl p-toluenesulfonate is particularly preferably used.

In the present invention, when (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound is used as the [C] additive, ) The compound is usually 0.1 to 10 ppm, preferably 0.1 to the above [A] polycarbonate.
It is used in an amount of 1 to 8 ppm, particularly preferably 0.1 to 5 ppm.

As the (b) phosphorus compound, phosphoric acid,
Phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphorous acid ester can be used. Specific examples of such a phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, and tris (2-chloroethyl). Trialkyl phosphates such as phosphates, tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate And triaryl phosphate.

Examples of the phosphite ester include compounds represented by the following general formula. P (OR) ₃ (In the formula, R represents an alicyclic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. These may be the same or different.) Such a formula As the compound represented by, for example, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, tris (2-ethylhexyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, Tristearyl phosphite, tris (2-chloroethyl) phosphite,
Trialkyl phosphites such as tris (2,3-dichloropropyl) phosphite, tricycloalkyl phosphites such as tricyclohexyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4-di-t-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite, triarylphosphite such as tris (hydroxyphenyl) phosphite, phenyldidecylphosphite, diphenyldecylphosphite,
Examples thereof include arylalkyl phosphites such as diphenylisooctylphosphite, phenylisooctylphosphite, and 2-ethylhexyldiphenylphosphite.

Further, as phosphite, distearyl pentaerythrityl diphosphite, bis (2,4-diester
-t-butylphenyl) pentaerythrityl diphosphite and the like.

These may be used alone or in combination. Among these, as the (b) phosphorus compound, a phosphite represented by the above general formula is preferable, and an aromatic phosphite is more preferable, and especially tris (2,
4-di-t-butylphenyl) phosphite is preferably used.

In the present invention, when the (B) phosphorus compound is used as the [C] additive, the (B) phosphorus compound is usually 10 to 1000 relative to the [A] polycarbonate.
It is used in an amount of ppm, preferably 50 to 500 ppm.

As the (c) epoxy compound, a compound having one or more epoxy groups in one molecule is used. Specifically, epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butyl phenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 3 , 4-Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4- (3 , 4-Epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexylcarboxylate,
3,4-epoxycyclohexyl ethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-
6'-methylsiloxyhexyl carboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, bis-epoxydicyclopentadienyl ether, Bis-epoxy ethylene glycol, bis-epoxy cyclohexyl adipate, butadiene diepoxide,
Tetraphenylethylene epoxide, octyl epoxytalate, epoxidized polybutadiene, 3,4-dimethyl-
1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxy Cyclohexylcarboxylate, N-butyl-2,2
-Dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-
Epoxy-5-methylcyclohexylcarboxylate,
Octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3', 4'-epoxycyclohexylcarboxylate, 4,5-epoxy tetrahydrophthalic anhydride, 3-
t-Butyl-4,5-epoxy tetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy- Examples thereof include cis-1,2-cyclohexyl dicarboxylate.

Of these, alicyclic epoxy compounds are preferably used, and particularly 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate is preferably used.

These may be used alone or in combination of two or more. In the present invention, when such a (c) epoxy compound is used as the [C] additive, the (c) epoxy compound is usually used in an amount of 1 to 2000 ppm, preferably 1 to 2000 ppm, based on the above [A] polycarbonate. 10
Used in amounts of up to 1000 ppm.

As the (d) phenolic stabilizer,
Specifically, n-octadecyl-3- (4-hydroxy-3 ', 5'-di-
t-Butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, 1,1,3-tris (2-methyl-4-
Examples thereof include hydroxy-5-t-butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzyl malonate, and 4-hydroxymethyl-2,6-di-t-butylphenol. These may be used alone or in combination of two or more.

In the present invention, when the (D) phenolic stabilizer is used as the [C] additive, the (D) phenolic stabilizer is usually 10 to 1000 ppm, preferably 50 to 1000 ppm, based on the [A] polycarbonate. 500ppm
Used in an amount of. The above (a), (b),
The additive selected from the group consisting of (C) and (D) is
They may be used alone or in plural. [C]
When a plurality of additives are used, they may be added separately or simultaneously, and the order of addition is not limited.

Among the above [C] additives, (a)
Sulfur-containing acidic compound having a pKa value of 3 or less and /
Alternatively, it is preferable to use a derivative formed from the acidic compound, (b) phosphorus compound or (d) phenol stabilizer because the alkaline catalyst remaining in the polycarbonate resin composition is neutralized or weakened. In addition, when the (a) epoxy compound is added together with the (a) or (b) compound, even if the (a) or (b) compound remains excessively, these react with the (c) epoxy compound and become neutral. To improve the residence stability during melting, suppress the decrease in molecular weight and coloration, and obtain a polycarbonate resin composition with improved quality.

In the present invention, a polycarbonate obtained by adding a resin other than the above [B] polycarbonate and / or an [C] additive while the above reaction product [A] polycarbonate is in a molten state. The resin composition is granulated by cutting while it is in a molten state. In such a step, the resin other than [B] polycarbonate and the [C] additive may be added in either the reactor or the extruder as long as [A] polycarbonate is in a molten state. When both B] and [C] are added, they may be added separately or at the same time, and the addition order is not limited. Specifically, for example, a resin other than [B] polycarbonate and / or [C] additive is added to [A] polycarbonate obtained by polycondensation reaction in a reactor to obtain a polycarbonate resin composition. After forming
Granulate by cutting through the extruder while in the molten state. Further, while the [A] polycarbonate obtained by the polycondensation reaction passes through the extruder from the reactor, a resin other than the [B] polycarbonate and / or an [C] additive is added, and these are kneaded to obtain a polycarbonate. A system resin composition is formed, and is cut and granulated while it is in a molten state.

Cutting of the polycarbonate resin composition in a molten state may be carried out in water or air, but in the present invention, cutting is preferably carried out in water.

In the present invention, as described above, while the reaction product [A] polycarbonate is in a molten state,
[B] A resin other than polycarbonate and / or [C] additive is added and kneaded to form a polycarbonate-based resin composition, and the polycarbonate is cut and granulated while in a molten state. Compared to the case of kneading solid resins together, the number of thermal history received during manufacturing can be minimized, and the thermal decomposition of polycarbonate etc. due to shear heat can be suppressed, so that the thermal decomposition during manufacturing can be suppressed. It is possible to prevent thermal deterioration such as decrease in molecular weight or coloring.
In addition, the gel generation is small, the polycarbonate resin composition can be stably produced at low cost, and the production efficiency is excellent.

Furthermore, the polycarbonate resin composition obtained by the present invention is obtained as pellets having a smooth surface and excellent surface properties. Such pellets easily penetrate into the molding machine at the time of molding and have excellent moldability. Further, in the present invention, it is easy to adjust the cutting conditions, even if the cutting conditions are changed according to the type of the resin composition, the cutting conditions can be easily changed, and the excellent surface properties as described above can be obtained. The pellets can be stably manufactured, and the production efficiency does not decrease during granulation.

The polycarbonate-based resin composition obtained in the present invention preferably contains the above-mentioned [C] additive, and is excellent in retention stability such as heat stability and hue stability during production, and It is also excellent in retention stability when melt-molding a polycarbonate resin composition. Therefore, even when the pellets made of the polycarbonate resin composition are re-melted during molding, thermal decomposition is particularly suppressed and the molecular weight is less likely to decrease. Further, the polycarbonate resin composition is difficult to be colored even if it is remelted.

The polycarbonate resin composition obtained in the present invention has a small amount of foreign matter such as chips and shavings,
A molded product made of the polycarbonate resin composition is suitable for precision molding material applications and optical material applications.

In the present invention, the polycarbonate-based resin composition obtained as described above is added to the following usual heat stabilizers, ultraviolet absorbers, release agents, within the range not impairing the object of the present invention. Colorant, antistatic agent, slip agent,
Other additives [D] such as antiblocking agents, lubricants, antifogging agents, natural oils, synthetic oils, waxes, organic fillers and inorganic fillers may be added. Like this [D]
Other additives may be added to the molten [A] polycarbonate together with the above-mentioned [C] additive, or the once pelletized polycarbonate resin composition may be remelted and added. You can also Remelting is preferably performed under reduced pressure. In the present invention, the additive is preferably added to the molten [A] polycarbonate. Specific examples of [D] other additives are shown below.

Specific examples of such heat-resistant stabilizers include organic thioether-based stabilizers and hindered amine-based stabilizers. Examples of thioether-based stabilizers include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-
Examples thereof include thiodipropionate and pentaerythritol-tetrakis- (β-lauryl-thiopropionate).

These may be used alone or in combination of two or more. Examples of hindered amine stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) sebacate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl- 4-Hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl
-1,2,3-Triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2- (3,5-di-t-butyl -4-hydroxybenzyl) -2
-n-Butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4- Butane tetracarboxylate etc. are mentioned.

These may be used alone or in combination of two or more. These heat resistance stabilizers are 0.001 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, and more preferably 0.005 parts by weight, based on 100 parts by weight of the polycarbonate.
It is preferably used in an amount of 01 to 0.3 part by weight.
Such heat resistance stabilizer may be added in a solid state or a liquid state.

Such a heat stabilizer is preferably added while the [A] polycarbonate is in a molten state while it is cooled from the final polymerization vessel and pelletized. In this way, the polycarbonate resin composition is obtained. Fewer heat history is received. Further, when the heat treatment such as extrusion molding or pelletizing is performed again, the polycarbonate resin composition does not contain decomposition products and low boiling point substances, and the heat resistance stabilizer exerts the conventional effect to suppress thermal decomposition. You can

The ultraviolet absorber may be a general ultraviolet absorber and is not particularly limited. For example, salicylic acid type ultraviolet absorber, benzophenone type ultraviolet absorber, benzotriazole type ultraviolet absorber, cyanoacrylate type ultraviolet absorber. Agents and the like. Specific examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate.

As the benzophenone type ultraviolet absorber,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy -2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n
-Octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4 -Methoxybenzophenone-5-sulfonic acid and the like can be mentioned.

Examples of the benzotriazole type ultraviolet absorber include 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-butyl- Phenyl) benzotriazole, 2- (2'-hydroxy-3'-t
-Butyl-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl-phenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy
-5'-t-octylphenyl) benzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5 ' -Methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like.

Examples of the cyanoacrylate type ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate. These may be used alone or in combination of two or more. These UV absorbers
It is usually used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 1.0 parts by weight, and more preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate [A]. it can.

Further, the release agent may be a general release agent and is not particularly limited. Examples of the hydrocarbon-based releasing agent include natural and synthetic paraffins, polyethylene waxes, fluorocarbons and the like. Examples of the fatty acid-based release agent include higher fatty acids such as stearic acid and hydroxystearic acid, and oxyfatty acids.

Examples of the fatty acid amide type releasing agent include stearic acid amide, fatty acid amides such as ethylene bis stearoamide, and alkylene bis fatty acid amides. Examples of the alcohol-based releasing agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols, polyglycols and polyglycerols.

Examples of the fatty acid ester-based mold release agent include lower fatty acid esters of aliphatic acids such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters, and fatty acid polyglycol esters. Examples of the silicone-based release agent include silicone oils.

These may be used alone or in combination of two or more.

These releasing agents are usually used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight, and more preferably 0.01 to 0.0 part by weight, based on 100 parts by weight of the polycarbonate [A]. It can be used in an amount of 5 parts by weight. Further, the colorant may be a pigment or a dye. The colorant includes an inorganic colorant and an organic colorant, and either one may be used or a combination may be used.

Specific examples of the inorganic colorants include oxides such as titanium dioxide and red iron oxide, hydroxides such as alumina white, sulfides such as zinc sulfide, selenides, ferrocyanides such as navy blue, and zinc chromate. , Chromate such as molybdenum red, sulfate such as barium sulfate, carbonate such as calcium carbonate, silicate such as ultramarine blue,
Examples thereof include phosphates such as manganese violet, carbon such as carbon black, and metal powder colorants such as bronze powder and aluminum powder.

Specific examples of the organic colorant include nitroso type such as naphthol green B, nitro type such as naphthol yellow-S, resole red and bordeaux 10.
Examples thereof include azo colorants such as B, naphthol red, and chromophthal yellow, phthalocyanine colorants such as phthalocyanine blue and fast sky blue, condensed polycyclic colorants such as indanthrone blue, quinaxone violet, and dioxazine violet.

These colorants may be used alone or in combination. These colorants are usually used in an amount of 1 × 10 ^{−6 to} 5 with respect to 100 parts by weight of the [A] polycarbonate.
It can be used in an amount of 1 part by weight, preferably 1 × 10 ^{−5 to} 3 parts by weight, and more preferably 1 × 10 ⁻⁵ to 1 part by weight. Specific examples of the inorganic filler include fibrous reinforcing agents such as glass fiber, carbon fiber and metal fiber, and fillers such as silica, alumina, silica-alumina, clay, glass beads and titania.

[0092]

EFFECTS OF THE INVENTION According to the method for producing a polycarbonate resin composition of the present invention, it is possible to produce pellets which are excellent in retention stability such as thermal stability and hue stability during production and are excellent in surface properties. Such a polycarbonate resin composition can be efficiently and stably produced.

The polycarbonate resin composition obtained by the present invention is suitably used for precision applications and optical applications.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0095]

EXAMPLES In this specification, the intrinsic viscosity [IV] of polycarbonate, the proportion of terminal groups and the moldability of the polycarbonate resin composition are measured as follows.

[Intrinsic viscosity [IV]] 2 in methylene chloride
It measured at 0 degreeC using the Ubbelohde viscometer.

[Ratio of Terminal Group] The ratio of the phenolic terminal group and the hydroxyl group terminal was measured by ¹³ C-NMR.

[Moldability] An injection-molded plate having a thickness of 1 mm and a diameter of 12 mm was molded by a molding cycle of 4 seconds, and the presence or absence of light distortion was measured with a polarizing plate. An injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. was used.

[0099]

Example 1 0.44 kmole of bisphenol A (manufactured by Japan GE Plastics Co., Ltd.) and 0.449 kmole of diphenyl carbonate (manufactured by Any Co.) were charged into a first 250 liter tank-type stirring tank at 140 ° C. And bisphenol A and diphenyl carbonate 0.16 kmol / h to maintain this level.
While feeding 0.163 kilomoles each, the mixed solution was sent to the second 50-liter tank-type stirring tank by 0.16 kilomoles per hour in terms of bisphenol A. The temperature of this tank type stirring tank was maintained at 180 ° C.

Tetramethylammonium hydroxide was added as a catalyst in an amount of 0.04 mol / hour and sodium hydroxide was added in an amount of 0.00016 mol / hour (1 × 10 ⁻⁶ mol / mol-bisphenol A) so that the residence time was 30 minutes. The level was adjusted and stirred.

Next, this reaction solution was heated at the following third temperature of 0.16 kmole per hour in terms of bisphenol A.
The solution was fed to a 50 liter tank type stirring tank at 200 ° C. and 200 mmHg. The level was adjusted so that the residence time was 30 minutes, and stirring was performed while distilling and removing phenol.

Next, this reaction solution was added in an amount of 0.16 kmole per hour in terms of bisphenol A by the following fourth temperature 240.
The solution was transferred to a 50-liter tank-type stirring tank at a temperature of 15 ° C and a pressure of 15 mmHg. The level was adjusted so that the residence time was 30 minutes, and stirring was performed while distilling and removing phenol. The intrinsic viscosity [η] of the reaction product obtained when the reaction became steady was 0.15 dl / g
Met.

Next, the pressure of this reaction product was increased by a gear pump, and 0.16 kmoles per hour of bisphenol A conversion was fed into the centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. Gear pump from the bottom of the evaporator to 270 ℃, 0.2
Biaxial horizontal stirring polymerization tank controlled to mmHg (L /
D = 3, a stirring blade rotating diameter of 220 mm, and an internal volume of 80 liters were fed at a rate of 0.16 kmole (about 40 kg / hour) in terms of bisphenol A per hour to carry out polymerization for a residence time of 30 minutes. At this time, the intrinsic viscosity [IV] of the polymer was 0.35 dl / g, and the ratio of the phenol end group and the hydroxyl end group was 91/9.

Next, in the molten state, this polymer was added to a twin-screw extruder (L / D = 17.5, barrel temperature 265 ° C.) at a gear pump of 0.16 per hour in terms of bisphenol A.
Kilomol (about 40 kg / hour) was fed in each, and 1.8 ppm of butyl p-toluenesulfonate was added to the polycarbonate.
, Tris (2,4-di-t-butylphenyl) phosphite (Mark 2112: manufactured by ADEKA ARGUS CORPORATION) 300ppm, n-
Octadecyl-3- (4-hydroxy-3 ', 5'-di-t-butylphenyl) propionate (Mark AO 50: manufactured by ADEKA ARGUS CORPORATION) 300 ppm, 3,4-epoxycyclohexylmethyl-3,'4'-epoxy Cyclohexylcarboxylate (Celoxide 2021P: manufactured by Daicel Chemical Industries) 300ppm
Was continuously kneaded, passed through a die in a water tank, and cut in a molten state with a cutter to obtain pellets.

A spherical pellet with a smooth surface is obtained,
No trouble occurred even after continuous operation for 24 hours, and the polycarbonate composition could be efficiently produced. When a molded injection-molded plate was observed with a polarizing plate at a cylinder temperature of 320 ° C., no distortion of light was observed.

[0106]

Comparative Example 1 In Example 1, after kneading the additives,
It was led to a die, the resin was drawn out in strands, cooled through a 5 m water tank, and cut with a cutter to obtain pellets. The pellet had a cylindrical shape and contained resin chips. There was a problem that strands were cut once every two hours.

When the injection-molded plate molded at a cylinder temperature of 320 ° C. was observed with a polarizing plate, some distortion of light was observed.

[0108]

Example 2 Bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) 0.44 kmole and diphenyl carbonate (manufactured by Any Co.) 0.44 kmole
Charge into a 50 liter tank type stirring tank, melt at 140 ° C,
While feeding each of bisphenol A and diphenyl carbonate at 0.16 kmol per hour so as to maintain this level, 0.16 kmol of this bisphenol A per hour was fed to the second 50-liter tank-type stirring tank. .. The temperature of this tank type stirring tank was maintained at 180 ° C.

Tetramethylammonium hydroxide was added as a catalyst in an amount of 0.04 mol / hour and sodium hydroxide was added in an amount of 0.00016 mol / hour (1 × 10 ⁻⁶ mol / mol-bisphenol A) so that the residence time was 30 minutes. The level was adjusted and stirred.

Next, this reaction solution was heated by 0.16 kilomoles per hour converted to bisphenol A by the following third temperature 210.
The solution was fed to a 50 liter tank type stirring tank at 200 ° C. and 200 mmHg. The level was adjusted so that the residence time was 30 minutes, and stirring was performed while distilling and removing phenol.

Next, this reaction solution was added in an amount of 0.16 kilomoles per hour converted to bisphenol A by the following fourth temperature 240.
The solution was transferred to a 50-liter tank-type stirring tank at a temperature of 15 ° C and a pressure of 15 mmHg. The level was adjusted so that the residence time was 30 minutes, and stirring was performed while distilling and removing phenol. The intrinsic viscosity [η] of the reaction product obtained when the reaction became steady was 0.15 dl / g
Met.

Next, the pressure of this reaction product was increased by a gear pump, and 0.16 kmoles per hour of bisphenol A conversion was fed into the centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. Gear pump from the bottom of the evaporator at 285 ℃, 0.2
Biaxial horizontal stirring polymerization tank controlled to mmHg (L /
D = 3, a stirring blade rotating diameter of 220 mm, and an internal volume of 80 liters were fed at a rate of 0.16 kmole (about 40 kg / hour) in terms of bisphenol A per hour to carry out polymerization for a residence time of 30 minutes. At this time, the intrinsic viscosity [IV] of the polymer was 0.49 dl / g, and the ratio of the phenol end group and the hydroxyl end group was 50/50.

Next, in the molten state, this polymer was added to a twin-screw extruder (L / D = 17.5, barrel temperature 265 ° C.) with a gear pump at an hourly rate of 0.16 in terms of bisphenol A.
Each of them was fed in kilomoles (about 40 kg / hour), and 40 parts by weight of polybutylene terephthalate (Valox 315, manufactured by Nippon GE Plastics Co., Ltd.) and 60 parts by weight of the polycarbonate and butyl p-toluenesulfonate were added to the polycarbonate. 8 ppm, tris (2,4-di-t-butylphenyl) phosphite (Mark 2112: manufactured by ADEKA ARGUS CORPORATION) 300 ppm, n-octadecyl-3- (4-hydroxy-3 ', 5'-di-t-butylphenyl) ) Propionate (Mark AO 50: ADEKA ARGUS) 300 ppm,
3,4-Epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate (Celoxide 2021P:
(Manufactured by Daicel Chemical Co., Ltd.) 300 ppm was continuously kneaded and passed through a die in a water tank to be cut in a molten state with a cutter to obtain pellets.

A spherical pellet with a smooth surface is obtained,
No trouble occurred even after continuous operation for 24 hours, and the polycarbonate resin composition could be efficiently produced. When the molded injection-molded plate was observed with a polarizing plate at a cylinder temperature of 340 ° C., no distortion of light was observed.

[0115]

Comparative Example 2 In Example 2, after polybutylene terephthalate and additives were kneaded, they were introduced into a die, the resin was drawn out in a strand form, cooled through a 5 m water tank, and cut with a cutter to obtain pellets. The pellet had a cylindrical shape and contained resin chips. There was a problem that the strands were cut once every hour.

When the injection-molded plate molded at a cylinder temperature of 340 ° C. was observed with a polarizing plate, distortion of light was observed.

[0117]

[Example 3] In Example 2, instead of polybutylene terephthalate, a glass fiber having an average length of 6 mm (manufactured by Nitto Boseki Co., Ltd., Chip Strand CS 6PE-231)
Was obtained in the same manner as in Example 2 except that 40 parts by weight of polycarbonate was added to 60 parts by weight of polycarbonate.

A spherical pellet with a smooth surface is obtained,
No trouble occurred even after continuous operation for 24 hours, and the polycarbonate composition could be efficiently produced.

[0119]

Comparative Example 3 In Example 3, glass fibers and additives were kneaded, then introduced into a die, the resin was drawn out in a strand form, cooled through a 5 m water tank, and cut with a cutter to obtain pellets. The pellet had a columnar shape and contained resin cutting powder and glass fiber powder. There was a problem that the pellet was damaged or the shape was not uniform.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C08K 5/13 KKJ 7167-4J 5/15 KKJ 7167-4J 5/41 KKL 7167-4J 5/521 KKM 7167-4J 5/524 KKM 7167-4J // C08L 69:00 (72) Inventor Kenichi Tominari 3 Chikusaigan, Chiba City, Chiba Prefecture Japan GE Plastics Co., Ltd. (72) Inventor Akira Kanazawa Ro, 3 Chikusaigan, Chiba City, Chiba Prefecture, Japan Japan Plastics Co., Ltd.

Claims (6)

[Claims] 1. An aromatic dihydroxy compound and a carbonic acid diester are subjected to melt polycondensation in the presence of a catalyst, and then, while the reaction product [A] polycarbonate is in a molten state,
[B] A resin other than polycarbonate and / or [C] an additive is added and kneaded, and then the polycarbonate resin composition is cut and granulated while in a molten state. A method for producing a resin composition. 2. The method for producing a polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition is granulated by cutting in a molten state in water. 3. The additive [C] is (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, (b) phosphorus compound, (c) epoxy compound and (D) The method for producing a polycarbonate resin composition according to claim 1 or 2, wherein the method is selected from the group consisting of phenolic stabilizers. 4. Use of (a) an alkali metal compound and / or an alkaline earth metal compound as a catalyst in an amount of 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol with respect to 1 mol of an aromatic dihydroxy compound. The method for producing a polycarbonate-based resin composition according to any one of claims 1 to 3, which is characterized in that. 5. The method for producing a polycarbonate resin composition according to claim 1, wherein the melt polycondensation is continuously carried out. 6. A molded article comprising a polycarbonate resin composition produced by the production method according to any one of claims 1 to 5.