JP2001329160A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material having improved flame retardance, color tone and heat resistance, suitable as a molding material for various kinds of moldings such as an optical disc, a sheet, an automobile-related part, an office automation instrument, parts of household electric appliances. SOLUTION: This aromatic polycarbonate resin composition is characterized by compounding 100 pts.wt. of an aromatic polycarbonate which is a polycarbonate produced by a reaction between an aromatic dihydroxy compound and a compound into which a carbonate bond can be introduced and having 12,000-40,000 viscosity-average molecular weight, which has <=1,000 ppm content of a specific cyclic oligomer of formula (1) in which the ratio of the specified cyclic oligomer content to the total oligomer content satisfies a specific relation and is incorporated with 0.01-30 pts.wt. of a flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin composition having improved color tone and heat resistance. These include optical discs, sheets, automotive parts, OA
An object of the present invention is to provide a material suitable for molding materials of various molded products such as devices and home electric parts.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent mechanical properties, and are used in the fields of automobiles, office automation equipment,
It is widely used industrially as a raw material for molded articles in the electronic field and the like. On the other hand, there is a strong demand for synthetic resin materials to be made flame-retardant, mainly for applications such as OA equipment and home electric appliances, and a large number of flame retardants have been developed and studied to meet these demands. Usually, a halogen compound or the like is mainly used for making the polycarbonate resin flame-retardant. Although the halogen compound is effective for flame retardancy, it is rather poor in terms of thermal stability at the time of molding and tends to cause problems such as a change in hue due to heat history at the time of molding. In order to improve the disadvantages of such halogen-based flame retardants, in recent years, for the purpose of reducing the amount of halogen-based compounds, for example, JP-A-59-202240 discloses a composition using a phosphate ester-based compound. And JP-A-8-81620
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a composition using a polycarbonate-polyorganosiloxane copolymer. However, even the polycarbonate resin composition thus obtained cannot be said to have sufficient thermal stability at the time of molding, and it has been desired to further improve the thermal stability of a polycarbonate resin composition containing a flame retardant. In order to solve these problems, polycarbonate produced by the interfacial method in which an aromatic dihydroxy compound and phosgene are reacted and polymerized is reduced by reducing the amount of methylene chloride used as a solvent and the amount of chlorine component derived from phosgene. Attempts have been made to improve the heat resistance, and in the transesterification method in which an aromatic dihydroxy compound and a carbonic acid diester compound are reacted under reduced pressure by heating, the content is reduced by reducing the amount of the raw material carbonic acid diester, etc., and the catalyst is deactivated. (JP-A-7-126374)
However, sufficient thermal stability has not been obtained. On the other hand, attempts have been made to add heat resistance to polycarbonate by adding a phosphoric acid antioxidant such as a phosphite or an antioxidant such as a hindered phenol to a polycarbonate. Could not be suppressed.

[0003]

SUMMARY OF THE INVENTION The present invention provides a polycarbonate resin composition having excellent color tone, heat resistance and flame retardancy.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have intensively studied the improvement of the color tone, heat resistance, flame retardancy and the like of the polycarbonate resin itself. Then, by combining the flame retardant with a polycarbonate resin in which the content of the generated cyclic oligomer is reduced to a specific amount and a specific ratio or less, it has been found that flame retardancy, color tone, and heat resistance can be significantly improved, and the present invention It was completed. That is, the present invention provides a compound having a viscosity average molecular weight of 12,000 produced by reacting an aromatic dihydroxy compound with a compound capable of introducing a carbonic acid bond.
４０40,000, wherein the content of the cyclic oligomer represented by the formula (I) is 1000 ppm or less, and the total amount of the oligomers represented by the formulas (I), (II) and (III) The present invention provides an aromatic polycarbonate resin composition characterized in that 0.01 to 30 parts by weight of a flame retardant is blended with 100 parts by weight of an aromatic polycarbonate whose ratio with respect to the above satisfies the relational expression (1).

[0005]

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(In the formula (I), B is a hydrocarbon group having 1 to 15 carbon atoms which may be substituted by halogen, O, S, C
It is a divalent group selected from O, SO and SO ₂ . X represents a halogen atom, an aliphatic group or a substituted aliphatic group having 1 to 14 carbon atoms, an aromatic group or a substituted aromatic group having 6 to 18 carbon atoms, an oxyalkyl group having 1 to 8 carbon atoms, and 6 carbon atoms.
And a monovalent group selected from oxyaryl groups of -18 to -18. m is an integer of 2 to 8, p is an integer of 0 to 4, and s is 0 or 1. X and p may be the same or different. )

[0007]

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(In the formula (II), A and A ′ are the same or different and each have an aliphatic group having 1 to 18 carbon atoms;
It represents a substituted aliphatic group, an aromatic group, or a substituted aromatic group. n
Is an integer of 1 to 7, and B, X, p and s have the same definition as in formula (I). )

[0009]

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(In the formula (III), A ″ represents an aliphatic group having 1 to 18 carbon atoms, a substituted aliphatic group, an aromatic group or a substituted aromatic group. N ′ represents an integer of 1 to 7, , X, p and s have the same definition as in formula (I).)

[0011]

(Equation 2)

(In the formula (1), [I], [II], [III]
Represents the content of the oligomer corresponding to each formula,
Mv represents the viscosity average molecular weight of the aromatic polycarbonate. )

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The aromatic polycarbonate according to the present invention can be produced by a known method such as an interfacial polycondensation method or a transesterification method using an aromatic dihydroxy compound and a compound capable of introducing a carbonic acid bond as raw materials. Among them, production by a transesterification method is preferred. Examples of the compound capable of introducing a carbonic acid bond include phosgene and carbonic acid diester. The carbonic acid diester is represented by the following formula (IV).

[0014]

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(In the formula (IV), A and A 'each have 1 to 1 carbon atoms.
18 aliphatic groups, substituted aliphatic groups, aromatic groups, or substituted aromatic groups, which may be the same or different. )
The carbonic acid diester represented by the above formula (IV) is, for example, dimethyl carbonate, diethyl carbonate, di-t-
Examples thereof include substituted diphenyl carbonates such as butyl carbonate, diphenyl carbonate, and ditolyl carbonate. Preferred are diphenyl carbonate and substituted diphenyl carbonate, with diphenyl carbonate being particularly preferred. These carbonic diesters may be used alone or in combination of two or more. A dicarboxylic acid or dicarboxylic acid ester may be used in an amount of preferably 50% or less, more preferably 30% by mole or less, together with the compound capable of introducing a carbonic acid bond as described above. As such a dicarboxylic acid or dicarboxylic acid ester, terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate and the like are used. When such a carboxylic acid or a carboxylic acid ester is used in combination with a carbonic acid diester, a polyester carbonate is obtained. The aromatic dihydroxy compound as another raw material is represented by the formula (V).

[0016]

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(In the formula (V), B is a hydrocarbon group having 1 to 15 carbon atoms which may be substituted by halogen, or
O, in which S, CO, selected from SO and SO _2. X is the same or different and each is a halogen atom, an aliphatic group or a substituted aliphatic group having 1 to 14 carbon atoms, an aromatic group or a substituted aromatic group having 6 to 18 carbon atoms, Oxyalkyl group and carbon number 6 to
And 18 represents an oxyaryl group. p is an integer of 0 to 4, and s is 0 or 1. The aromatic dihydroxy compound represented by the formula (V) is, for example, 2,2-bis (4
-Hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, , 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'-dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,
Examples thereof include 3′-dichlorodiphenyl ether and 4,4′-dihydroxy-2,5-diethoxydiphenyl ether. Among these, 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is preferable. In addition, these aromatic dihydroxy compounds can be used alone or in combination of two or more, and can also be used as a copolymer if necessary.

The mixing ratio between the carbonic acid diester 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 terminal hydroxyl groups depends on the thermal stability of the product polycarbonate,
In order to have a significant effect on hydrolysis stability, color tone, etc., and to have practical physical properties, it is preferable to use 1,000 pp.
m, more preferably 800 ppm or less, particularly preferably 700 ppm or less. In the case of a polycarbonate produced by a transesterification method, if the amount of terminal hydroxyl groups is too small, the molecular weight does not increase and the color tone deteriorates.
0 ppm or more is more preferable, and 300 ppm or more is particularly preferable. Therefore, it is common to use the carbonate diester in an equimolar amount or more with respect to 1 mole of the aromatic dihydroxy compound, and 1.01 to 1.30 mole, preferably 1.01 mole.
Preferably, it is used in an amount of １．２1.20 mol. When an aromatic polycarbonate is produced by the transesterification method, a transesterification catalyst is usually used. Although there is no particular limitation on the transesterification catalyst, an alkali metal compound and / or an alkaline earth metal compound are mainly used,
In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination. These catalysts may be used alone or in combination of two or more.

The catalyst is used in an amount of 1 × 10 ^-9 to 1 × 10 ^-3 mol per 1 mol of the aromatic dihydroxy compound. Particularly in the case of an alkali metal compound or an alkaline earth compound, usually 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol, preferably 1 × 10 ⁻⁴ mol per 1 mol of the aromatic dihydroxy compound.
It is used in a range of 10 ^-8 to 1 × 10 ^-5 mol. In a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound, the amount is 1 mol of the aromatic dihydroxy compound. 1 × 10 ^-9 to 1 × 1
It is used in an amount of 0 ^-3 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-4 mol. If the amount of catalyst is less than these amounts,
Polymerization activity required for producing a polycarbonate having a predetermined molecular weight and a terminal hydroxyl group content cannot be obtained. If the polymerization activity is larger than this amount, an increase in the amount of cyclic oligomers described later, deterioration of polymer color tone, decrease in heat resistance, resistance to heat Decrease in hydrolyzability,
It is not preferable because the amount of foreign substances increases due to the generation of gel. As the alkali metal compound, lithium, sodium, potassium, rubidium, cesium hydroxide, hydrogen carbonate, carbonate, acetate, hydrogen phosphate, phenyl phosphate and the like inorganic alkali metal compounds, stearic acid, Examples thereof include organic acids such as benzoic acid, alcohols such as methanol and ethanol, phenolic acid, and organic alkali metal compounds such as salts with phenols such as bisphenol A.
Examples of the alkaline earth metal compound include inorganic alkaline earth metal compounds such as beryllium, calcium, magnesium, strontium, barium hydroxide, hydrogen carbonate, carbonate, and acetate, and organic acids, alcohols, and phenols. And organic alkaline earth metal compounds such as salts thereof.

Specific examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl Sodium, potassium, lithium, calcium, magnesium, barium salts, such as boron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, or And strontium salts. Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine,
Examples include triphenylphosphine, tributylphosphine, and quaternary phosphonium salts. Examples of the basic ammonium compound include, for example, 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, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, such as butyl triphenyl ammonium hydroxide and the like.

Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine,
2-hydroxypyridine, 2-methoxypyridine, 4-
Methoxypyridine, 2-dimethylaminoimidazole,
Examples include 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like. Of these catalysts, practically, alkali metal compounds, basic ammonium compounds,
A basic phosphorus compound is desirable, and an alkali metal compound is particularly desirable. The polycarbonate of the present invention uses the compound capable of introducing a carbonic acid bond and an aromatic dihydroxy compound, and is usually produced using the above-mentioned transesterification catalyst, and has a viscosity average molecular weight of 12,000 to 40,000.
If the viscosity average molecular weight is less than 12,000, the mechanical strength decreases, and if it exceeds 40000, the moldability decreases, which is not preferable. In the aromatic polycarbonate in the present invention, the total content of the cyclic oligomer represented by the formula (I) needs to be 1000 ppm or less, preferably 700 ppm or less, more preferably 550 ppm or less. When the amount of the cyclic oligomer exceeds 1000 ppm,
It is colored and the heat resistance, hydrolysis resistance, etc. are reduced. Although the reason for this is not necessarily clear, it is assumed that the cyclic oligomer is rich in reactivity and easily generates a coloring component at high temperature or promotes hydrolysis. Furthermore, in the present invention, the amount of the cyclic oligomer (I) is determined by the amount of the above-mentioned formula (I)
The ratio to the total amount of the oligomers represented by I) and formula (III) must satisfy the following relational expression (1).

[0022]

(Equation 3)

(In the formula (1), [I], [II], [III]
Represents the content of the oligomer corresponding to each formula,
Mv represents the viscosity average molecular weight of the aromatic polycarbonate. Both the cyclic oligomers represented by the formula (I) and the linear oligomers represented by the formulas (II) and (III) are considered to be components formed during the production of polycarbonate, and The structure of the repeating unit in parentheses in the formula is derived from the aromatic dihydroxy compound used in the production of polycarbonate. The compounds represented by the terminal groups A, A 'and A "are derived from the terminal groups of the compound capable of introducing a carbonic acid bond represented by the formula (IV), and are obtained by interfacial polycondensation using phosgene. When the cyclic oligomer (I) is produced, it is derived from the terminal stopper used.
Above ppm, the properties are adversely affected. Further 1000
It has been found that even when the content of the cyclic oligomer (I) is less than ppm, if the proportion of the cyclic oligomer (I) exceeds the range of the above relational formula (1), physical properties are adversely affected. Reasons for worse physical properties are 100
Cyclic oligomer (I) as in the case of more than 0 ppm
This is probably because of high reactivity.

The mechanism of the formation of the cyclic oligomer (I) is not clear, but the heat history during the production of the polymer, the influence of the type and amount of the catalyst, the concentration of the monomer during the production of the polymer and the concentration of the aromatic hydroxy compound produced as a by-product, etc. The amount of generation changes due to the influence.
Generally, in order for a certain molecular chain to become a cyclic body, the terminal groups of the molecular chain need to react with each other. However, this is usually difficult to occur, and generally, in the early stage of polymerization, end groups between adjacent molecules react with each other, and the polymerization proceeds. However, when the polymerization proceeds and the ratio of terminal groups in the system changes, it is considered that the reaction between molecules is reduced and the reaction in the molecule is likely to occur. In particular, when a high temperature is maintained in a state where the number of terminal hydroxyl groups is small, a cyclic oligomer is easily formed. Therefore, it is preferable that the ratio of terminal hydroxyl groups is not extremely reduced during the production. For the purpose of merely reducing the content of the cyclic oligomer (I), the extraction treatment can be carried out with a solvent having a weak polycarbonate-dissolving power, such as hexane, heptane, methanol and acetone. However, in the extraction operation, the amount of the linear oligomer other than the cyclic oligomer is also reduced, and the ratio of the amount of the cyclic oligomer in the total amount of the oligomer does not change. There are many. Further, the heat resistance may not be improved due to the influence of the residual solvent due to the extraction operation, which is not preferable. The content of the oligomer represented by the formula (I), the formula (II) or the formula (III) is measured by, for example, gel permeation chromatography (GPC), high performance liquid chromatography (HPLC), mass spectrum, NM
It can be measured using R or the like. However, since it is generally necessary to separate a high molecular weight part and a low molecular weight part, MAL
DI-TOFMS (Matrix Assisted Lazer Desorption)
It is preferable to collectively measure from the high molecular weight part to the low molecular weight part using a measuring instrument such as Ionization Time of Flight Mass Spectrometory.

In the production of the polycarbonate of the present invention, the ester exchange reaction using the above-mentioned raw materials is carried out at 100 to 320 ° C.
At normal temperature or reduced pressure to carry out a melt polycondensation reaction while removing by-products such as aromatic hydroxy compounds. The melt polycondensation can be carried out batchwise or continuously, but in the present invention, it is preferably carried out continuously in view of product stability and the like. The reaction is usually carried out in two or more stages in which the temperature and pressure conditions are changed. The reaction temperature of each step is not particularly limited as long as the polymer is in a molten state within the above range, and the reaction time is also appropriately determined depending on the degree of progress of the reaction, but may be 0.1 to 10 hours. preferable. These conditions are determined in view of the molecular weight, hue and cyclic oligomer content of the polymer. Specifically, the first stage reaction is carried out at a temperature of 140 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours under normal pressure or reduced pressure. Then, the reaction temperature was raised while increasing the degree of pressure reduction of the reaction system, and finally 240 to 3 mm 2 under a reduced pressure of 2 mmHg or less.
The polycondensation reaction is performed at a temperature of 20 ° C. An effective method as a production method for reducing the content of the cyclic oligomer is
In particular, in the final polymerization step in which the molecular weight is increased by 5% or more, the reaction is carried out at 250 ° C. or more, particularly 260 ° C. or more, under such conditions that the proportion of terminal hydroxyl groups at the inlet of the polymerization apparatus used in the reaction becomes 100 ppm or more. The polymerization is preferably performed, and more preferably at 200 ppm or more. The activation energy for the formation of the cyclic oligomer is high, and the higher the temperature, the more rapidly it is generated. Therefore, the polymerization temperature in the final stage is preferably 310 ° C. or lower. If the amount of the catalyst is too large,
It is considered that the carbonate bond is easily activated, and a reaction between the carbonate terminals which usually does not occur easily occurs, so that a cyclic oligomer is also easily formed. Controlling the conditions of each of these reaction tanks so as not to fluctuate as much as possible can suppress the amount of the cyclic oligomer.

The apparatus to be used may be any of a tank type, a tube type, and a tower type, and includes a vertical polymerization tank equipped with various stirring blades, a horizontal single-axis or horizontal two-axis polymerization tank. Etc. can be used. The atmosphere in the apparatus is not particularly limited, but from the viewpoint of the quality of the polymer, the polymerization is preferably performed in an inert gas such as nitrogen gas at normal pressure or reduced pressure. One example of such a manufacturing method is schematically shown in FIG. After completion of the polymerization, the produced aromatic polycarbonate is usually recovered as pellets.In this case, in order to remove low molecular weight components such as monomers and by-products remaining in the resin, the aromatic polycarbonate may be passed through a vented extruder. It is possible. The extruder conditions at which the temperature is usually highest in the production process should be mild conditions in order to keep the generation of cyclic oligomers low. When the temperature is increased while the catalyst is active, a cyclic oligomer is formed. Therefore, it is preferable to deactivate the catalyst using a suitable deactivator. When a catalyst, particularly an alkali metal compound catalyst, is used, a compound that neutralizes the catalyst, for example, a sulfur-containing acidic compound or a derivative formed therefrom is used as a catalyst deactivator in the transesterification polycarbonate. The amount is preferably 0.5 to 10 equivalents, preferably 1 to the alkali metal of the catalyst.
5 to 5 equivalents, usually 1 to 100 ppm, preferably 1 to 20 ppm based on the produced polycarbonate.
Add within the range. Examples of sulfur-containing acidic compounds or derivatives formed therefrom are sulfonic acid, sulfinic acid, sulfuric acid or esters thereof, and specifically, dimethyl sulfate, diethyl sulfate, p-toluenesulfonic acid, its methyl, ethyl, Butyl, octyl and phenyl esters, benzenesulfonic acid, its methyl, ethyl, butyl, octyl, phenyl and dodecyl esters, benzenesulfinic acid, toluenesulfinic acid,
And naphthalenesulfonic acid. Of these compounds, esters of p-toluenesulfonic acid or esters of benzenesulfonic acid are preferred, and two or more of these compounds may be used.

The sulfur-containing acidic compound or a derivative formed therefrom can be added to the polycarbonate by any method. For example, a sulfur-containing acidic compound or a derivative formed therefrom can be added to a polycarbonate in a molten or solid state directly or diluted with a diluent, and dispersed. Specifically, it can be supplied and mixed in a polycondensation reactor, a transfer line from the reactor, or an extruder. Further, after mixing with polycarbonate pellets, flakes, powders and the like generated by a mixer or the like, the mixture can be supplied to an extruder and kneaded. In addition, when performing depressurization treatment by venting with an extruder, or when adding water, furthermore, oxidizing a weathering improver such as an ultraviolet absorber and a hindered amine compound used in the present invention, a hindered phenol compound and a phosphorus compound, and the like. When adding an inhibitor and other heat stabilizers, release agents, dyes, pigments, antistatic agents, antifogging agents, organic / inorganic fillers, etc., the addition and treatment of these various additives ,
Although it may be carried out simultaneously with the sulfur-containing acidic compound or the derivative formed therefrom, it is preferable to add the sulfur-containing acidic compound or the derivative formed therefrom and knead the compound before adding or treating them.

Examples of the flame retardant used in the present invention include a metal sulfonate flame retardant, a halogen-containing compound flame retardant, an antimony-containing compound flame retardant, a phosphorus-containing compound flame retardant, and a silicon-containing compound flame retardant. Can be Examples of the metal sulfonic acid-based flame retardant include metal salts of aliphatic sulfonic acids and metal salts of aromatic sulfonic acids. The metal of the metal salt preferably includes an alkali metal, an alkaline earth metal and the like. Examples of the alkali metal and the alkaline earth include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium. And the like. The sulfonic acid metal salts may be used alone or in combination of two or more. As the sulfonic acid metal salt,
From the viewpoints of flame retardancy and heat stability, preferably, metal salts of aromatic sulfonsulfonic acid, metal salt of perfluoroalkane-sulfonic acid and the like are used. As the aromatic sulfone sulfonic acid metal salt, preferably, an alkali metal salt of aromatic sulfone sulfonic acid, an alkaline earth metal salt of aromatic sulfone sulfonic acid, and the like, and an alkali metal salt of aromatic sulfone sulfonic acid, aromatic sulfone sulfone The acid alkaline earth metal salt may be a polymer. Specific examples of the aromatic sulfonesulfonic acid metal salt include diphenylsulfone-3.
Sodium salt of sulfonic acid, diphenyl sulfone-3
Potassium salt of sulfonic acid, sodium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid, 4,
Potassium salt of 4'-dibromodiphenyl-sulfone-3-sulfone, calcium salt of 4-chloro-4'-nitrodiphenylsulfon-3-sulfonic acid, disodium salt of diphenylsulfone-3,3'-disulfonic acid, diphenylsulfone And dipotassium salts of -3,3'-disulfonic acid.

Preferred examples of the perfluoroalkane-sulfonic acid metal salt include alkali metal salts of perfluoroalkane-sulfonic acid, and alkaline earth metal salts of perfluoroalkane-sulfonic acid. Examples thereof include alkali metal sulfonic acid salts having a perfluoroalkane group having 4 to 8 carbon atoms, and alkaline earth metal sulfonic acid salts having a perfluoroalkane group having 4 to 8 carbon atoms. Specific examples of perfluoroalkane-sulfonic acid metal salts include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate,
Examples thereof include sodium perfluorooctane-sulfonate, potassium perfluorooctane-sulfonate, and tetraethylammonium salt of perfluorobutane-sulfonic acid. The amount of the sulfonic acid metal salt is preferably 0.1 to 100 parts by weight of the aromatic polycarbonate resin.
It is 01 to 5 parts by weight. If the amount of the sulfonic acid metal salt is less than 0.01 part by weight, it is difficult to obtain sufficient flame retardancy, and if it exceeds 5 parts by weight, the thermal stability tends to decrease. Examples of the halogen-containing compound-based flame retardant in the present invention include tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, and tetrabromobisphenol A.
Epoxy oligomer, tetrabromobisphenol A epoxy polymer, decabromodiphenyl oxide, tribromoallyl ether, tetrabromobisphenol A carbonate oligomer, ethylenebistetrabromophthalimide, decabromodiphenylethane, brominated polystyrene, hexabromocyclododecane, etc. . These halogen-containing compound-based flame retardants may be used alone or in combination of two or more. The amount of the halogen-containing compound-based flame retardant is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polycarbonate-based resin composition. If the amount of the halogen-containing compound-based flame retardant is less than 0.1 part by weight, only insufficient flame retardancy can be obtained, while if it exceeds 20 parts by weight, the mechanical strength decreases,
Moreover, it may cause discoloration due to bleeding of the flame retardant.

In the present invention, the antimony-containing compound-based flame retardant is preferably blended as a flame-retardant auxiliary when the halogen-containing compound-based flame retardant is blended. Examples of the antimony-containing compound-based flame retardant compounded as a flame retardant aid include antimony trioxide, antimony pentoxide, sodium antimonate and the like. These antimony-containing compound-based flame retardants may be used alone or in combination of two or more. The amount of the antimony-containing compound-based flame retardant is 0.1 to 20 parts by weight based on 100 parts by weight of the polycarbonate-based resin composition. When the amount of the antimony-containing compound-based flame retardant is less than 0.1 part by weight, only insufficient flame retardancy can be obtained. On the other hand, when the amount exceeds 20 parts by weight, the mechanical strength is reduced, and discoloration due to bleeding of the flame retardant may be caused. Become. In addition, in the total amount with the halogen-containing compound-based flame retardant,
For 100 parts by weight of the polycarbonate resin composition,
The content is preferably in the range of 0.1 to 30 parts by weight. Examples of the phosphorus-containing compound-based flame retardant in the present invention include red phosphorus, coated red phosphorus, polyphosphate compounds, phosphate esters, cyanuric acid, melamine cyanurate, phosphazene and the like. As the phosphate compound in the present invention,
Examples include, but are not limited to, phosphate ester compounds represented by the following general formula (VI).

[0031]

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[0032] In the ^{formula, R 1, R 2, R} 3 and R ⁴ each independently represent a hydrogen atom or an organic group, R ^1,
Except when R ² , R ³ and R ⁴ are simultaneously a hydrogen atom. Examples of the organic group include an optionally substituted alkyl group, cycloalkyl group, and aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen,
Examples thereof include an aryl group, an aryloxy group, an arylthio group, and a halogenated aryl group. A group obtained by combining these substituents (for example, an arylalkoxyalkyl group), or these substituents are replaced with an oxygen atom, a sulfur atom,
A group bonded and combined by a nitrogen atom or the like (for example, an arylsulfonylaryl group) may be a substituent.

Y represents a divalent or higher valent organic group, and the divalent or higher valent organic group is a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group. Is mentioned. Examples of the divalent or higher valent organic group include an alkylene group, a phenylene group which may have a substituent, a group derived from polynuclear phenols and bisphenols, and the like. The position is arbitrary. Particularly preferable examples of the divalent or higher valent organic group include hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, and dihydroxynaphthalene. a is 0 or 1, b is an integer of 1 or more, preferably 1
C is an integer of 0 or more, preferably an integer of 1 to 10, provided that when c is 0,
^At least one of ¹ , R ³ and R ⁴ represents an organic group.

Specific examples of the phosphate compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, and the like. Diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3-dibromopropyl ) and bis (chloropropyl) monooctyl phosphate, R ¹ to R ⁴ is an alkoxy group such as methoxy, ethoxy, or flop And bisphenol A bisphosphate, which is preferably a (substituted) phenoxy group such as phenoxy or methyl (substituted) phenoxy, hydroquinone bisphosphate, resorcinol bisphosphate, trioxybenzene triphosphate, and the like. Phosphates and various bisphosphates. These may be used alone or in combination of two or more.

The compounding ratio of the phosphorus-containing compound flame retardant is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin. If the compounding ratio of the phosphorus-containing compound-based flame retardant is less than 0.1 part by weight, the flame retardancy is insufficient,
If it exceeds 20 parts by weight, heat resistance tends to decrease. Examples of the silicon-containing compound-based flame retardant used in the present invention include a silicone compound and a silicone varnish having a branched main chain and having an aromatic group in an organic functional group contained therein.
The compounding amount of the silicon-containing compound-based flame retardant is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin. If the amount is less than 0.1 part by weight, the flame retardancy is insufficient, and 1
If it exceeds 0 parts by weight, heat resistance tends to decrease. As the silicone compound having a main chain having a branched structure and having an aromatic group in the contained organic functional group, the following general formula (VII):
It is as shown in.

[0036]

Embedded image

(Where R ⁵ , R ⁶ and R ⁷ each represent an organic functional group in the main chain, Z represents a terminal functional group, d, e, and f each represent the amount of each repeating unit. The repeating units do not necessarily have to be continuous, and each unit may be mixed.) That is, the repeating unit is characterized by having a T unit and / or a Q unit as a branch unit. These are preferably at least 20 mol% of the total siloxane units. If the amount is less than 20 mol%, the heat resistance of the silicone compound is reduced and the flame retardant effect is reduced, and the viscosity of the silicone compound itself is too low, which may adversely affect the kneadability with the polycarbonate resin and the moldability. is there. More preferably, it is 30 mol% or more and 95 mol% or less. When the content is 30 mol% or more, the heat resistance of the silicone compound is further increased, and the flame retardancy of the polycarbonate resin containing the compound is greatly improved. However, when the content exceeds 95 mol%, the degree of freedom of the main chain of the silicone is reduced, so that condensation of aromatic groups during combustion may be difficult to occur, and it may be difficult to exhibit remarkable flame retardancy.

The silicone compound preferably contains at least 20 mol% of an aromatic group among organic functional groups contained therein. If it is less than this range, condensation of aromatic groups hardly occurs during combustion, and the flame retardant effect may be reduced. More preferably 40 mol% or more, 95 m
ol% or less. When the content is 40 mol% or more, the aromatic group at the time of combustion can be more efficiently condensed, and at the same time, the dispersibility of the silicone compound in the polycarbonate resin is significantly improved, and a very good flame retardant effect can be exhibited. However, when the content is 95 mol% or more, condensation may be difficult to occur due to steric hindrance between aromatic groups, and it may be difficult to exhibit a remarkable flame retardant effect.

The aromatic group to be contained is phenyl, biphenyl, naphthalene or a group derived therefrom. From the viewpoint of safety of the silicone compound, a phenyl group is particularly preferred. Among the organic functional groups in the silicone compound, among those attached to the main chain or the branched side chain, the organic group other than the aromatic group is preferably a methyl group, and the terminal group is a methyl group, a phenyl group, a hydroxyl group, It is preferable that one selected from an alkoxy group (especially a methoxy group) or a mixture thereof. In the case of these terminal groups, the gelling (cross-linking) of the silicone compound does not easily occur during kneading of the polycarbonate resin and the silicone compound due to low reactivity, so that the silicone compound can be uniformly dispersed in the polycarbonate resin. In addition, a better flame retardant effect can be obtained, and the moldability is further improved. Among these groups, a methyl group is particularly preferred. In this case, since the reactivity is extremely low, the dispersibility is extremely good, and the flame retardancy can be further improved.

The average molecular weight (weight average) of the silicone compound
Average) is preferably 5,000 or more and 500,000 or less.
If it is less than 5000, the heat resistance of the silicone compound itself decreases.
Reduced flame retardant effect and melt viscosity too low
During molding, the surface of the polycarbonate resin
Corn compounds may ooze out and reduce moldability.
If it exceeds 500,000, the melt viscosity increases and the
-Uniform dispersion in carbonate resin is impaired,
The effect and formability may be reduced. More particularly preferred
Or more than 10,000 and less than 270,000. In this range
Since the melt viscosity of the silicone compound is optimized,
-The silicone compound is very evenly distributed in the carbonate resin.
Better because it can be scattered and does not seep too much into the surface
High flame retardancy and moldability. The system used in the present invention
The silicone varnish mainly includes bifunctional units [R⁰ _Two
SiO] and trifunctional units [R⁰SiO_1.5]
Functional unit [R⁰ _ThreeSiO_{0 .Five}] And / or tetrafunctional single
[SiO_Two] Can contain a relatively low molecular weight solvent
It is a liquid silicone resin. Where R⁰Has 1 to 1 carbon atoms
Substituted with 12 hydrocarbon groups or one or more substituents
A hydrocarbon group having 1 to 12 carbon atoms;
Epoxy, amino, hydroxyl and vinyl groups
And the like. R⁰By changing the type of
It is possible to improve the compatibility with the Rix resin.
Solvent-free silicone varnish
And silicone varnish containing a solvent.
Preference is given to silicone varnishes which do not contain.

The silicone varnish can be produced by hydrolyzing an alkylalkoxysilane, for example, by hydrolyzing an alkyltrialkoxysilane, a dialkyldialkoxysilane, a trialkylalkoxysilane, a tetraalkoxysilane or the like. Can be manufactured. The molecular structure (degree of crosslinking) and molecular weight can be controlled by adjusting the molar ratio, hydrolysis rate, and the like of these raw materials. further,
Depending on the production conditions, the alkoxysilane remains, but if it remains in the composition, the hydrolysis resistance of the polycarbonate resin may decrease, and it is desirable that the residual alkoxysilane be small or not. The viscosity of the silicone varnish is preferably no greater than 300 centistokes. If it exceeds 300 centistokes, the flame retardancy may be insufficient. The viscosity of silicone varnish is
More preferably, it is 250 centistokes or less, and even more preferably, it is 200 centistokes or less. The polytetrafluoroethylene for preventing dripping according to the present invention has a tendency to be easily dispersed in a polymer and to form a fibrous material by combining the polymers. Polytetrafluoroethylene for dropping prevention is classified into type 3 according to the ASTM standard. For the purpose of preventing dripping, for example, it is commercially available as Teflon 6J or Teflon 30J from DuPont Fluorochemicals Co., Ltd., or as Polyflon F201L from Daikin Chemical Industries, Ltd.

The mixing ratio of the polytetrafluoroethylene for preventing dripping is 0.01 to 2.0 parts by weight, preferably 0.1 to 2.0 parts by weight, per 100 parts by weight of the polycarbonate resin.
To 1.0 part by weight. If the amount of the polytetrafluoroethylene for dropping prevention is less than 0.01 part by weight, the effect of preventing the molten dripping at the time of combustion is insufficient, and if it exceeds 2 parts by weight, the appearance tends to deteriorate. The polycarbonate resin composition of the present invention may contain various additives in such an amount that the effect of the present invention is exhibited, for example, a stabilizer, a release agent, an ultraviolet absorber, an antistatic agent, and a dye / pigment within a range that does not impair the effect of the present invention. Can be contained.
In addition, in order to obtain various uses and desired performance, a styrene-based resin, a polyester-based resin, a thermoplastic elastomer may be blended, or glass fiber, glass flake, glass beads, carbon fiber, wollastonite, Inorganic fillers such as calcium silicate and aluminum borate whiskers can also be blended. The mixing method of the polycarbonate and the thermoplastic resin described in the present invention, there is no particular limitation on the mixing timing, for example, as the mixing timing, when polycarbonate is produced by transesterification, during the polymerization reaction or at the end of the polymerization reaction, Furthermore, regardless of the polymerization method, the polycarbonate can be added in a molten state such as during kneading of the polycarbonate or the like, but it is also possible to knead with an extruder or the like after blending with the solid state polycarbonate such as pellets or powder. .

[0043]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following examples, the production of the aromatic polycarbonate was performed using the steps as shown in FIG. Also,
The analysis of the aromatic polycarbonate obtained by the present invention was performed by the following measurement method. (1) Viscosity average molecular weight (Mv) The intrinsic viscosity [η] at 20 ° C. in methylene chloride was measured using an Ubbelohde viscometer, and determined by the following equation.

[0044]

[Η] = 1.23 × 10 ⁻⁴ × (Mv) ^0.83

(2) Oligomer Content MALDI-TOFMS (manufactured by Finniganmat: VI
SION2000; laser (N ₂ laser = 337N
m) and the measured mass range (m / z = 0 to 35000)) were used for the measurement. 0.10 g of polycarbonate in 10 ml of dichloromethane and tris (3,5-di-t
-Butyl-4-hydroxybenzyl) isocyanurate (0.01 g) and a matrix solution of 2,4,6-trihydroxyacetophenone (80 mg) in tetrahydrofuran (THF) (1 ml) were prepared. The matrix solution was mixed at a volume ratio of 1:
The mixture was mixed at a ratio of 1 and used as a sample solution. (3) Combustibility After drying the resin composition at 120 ° C. for 4 hours, use a M150AII-SJ injection molding machine manufactured by Meiki Seisakusho Co., Ltd.
A 6 mm thick x 13 mm wide x 130 mm long molded product is
Molding was performed under the conditions of 0 ° C. and a molding cycle of 1 minute, and a combustion test was performed according to UL94 standard. (3) Initial color tone After drying the resin composition at 120 ° C. for 4 hours, 3 m was obtained using an M150AII-SJ injection molding machine manufactured by Meiki Seisakusho Co., Ltd.
An m-thick molded product is molded under the conditions of 300 ° C. and a molding cycle of 1 minute, and a spectral colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., S
E2000). The larger the YI value, the more colored.

(4) Retention stability (300 ° C. heat resistance test) After drying the resin composition at 120 ° C. for 4 hours, 3 m was measured using an M150AII-SJ injection molding machine manufactured by Meiki Seisakusho Co., Ltd.
An m-thick molded product is molded under the conditions of 300 ° C. and a molding cycle of 10 minutes.
YI was measured by the transmission method using SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. (5) Heat Aging Test The molded pieces whose initial color tone was measured were subjected to a heat aging test in a hot air dryer at 100 ° C. for 2000 hours, and the YI after the treatment was measured. (6) Amount of Terminal Hydroxyl Group Colorimetric determination was performed by the titanium tetrachloride / acetic acid method (method described in Macromol. Chem. 88 215 (1965)).

Production Example PC-1: Bisphenol A (BPA) and diphenyl carbonate (DPC) at 135 ° C. in a nitrogen gas atmosphere.
Are melt-mixed at a fixed molar ratio (DPC / BPA = 1.045), and are controlled at 205 ° C under a normal pressure and a nitrogen atmosphere through a raw material introduction pipe heated at 135 ° C under a first vertical stirring tank. The liquid level was kept constant while controlling the opening of a valve provided in the polymer discharge line at the bottom of the tank so that the average residence time was 70 minutes. Simultaneously with the start of the supply of the raw material mixture, cesium hydroxide as an aqueous solution was continuously supplied as a catalyst at a flow rate of 1 × 10 ⁻⁶ mol per 1 mol of bisphenol A. The polymerization liquid discharged from the tank bottom was successively and continuously supplied to the second, third, and fourth vertical polymerization tanks and the horizontal fifth polymerization tank. During the reaction, the liquid level was controlled so that the average residence time in each tank was a predetermined time as shown in Table 1 below, and at the same time, phenol produced as a by-product was distilled off. Table 1 below shows the polymerization conditions in each reaction tank, the monomer content, and the like, from the vertical second polymerization tank to the horizontal fifth polymerization tank. While a polycarbonate obtained continuously at a production rate of 50 kg / Hr is kept in a molten state, a thermometer for measuring an internal temperature is installed in a kneading section, and a twin screw extruder (Kobe Steel ( Co., Ltd., screw diameter 0.046m, L / D = 36)
-5 ppm of butyl toluenesulfonate was added, water was further added, the water and the monomer component were volatilized, and then pelletized. The operating condition of the extruder is discharge amount = 50 kg
/ Hr, number of rotations = 150 rpm, maximum resin temperature = 278
° C. The viscosity average molecular weight of the obtained polycarbonate was 22,000, and the amount of cyclic oligomer was 400 pp.
m, the ratio of the amount of the cyclic oligomer calculated by the formula (1) is 1
3.7%. Production Example 2 PC-2: A polycarbonate was obtained in the same manner as in Production Example 1, except that the catalyst was changed to sodium hydroxide, and the polymerization conditions and the like were changed as shown in Table 1.

Production Example 3 PC-3: In Production Example 1, the catalyst was changed to cesium carbonate, and the polymerization conditions were changed to those shown in Table 1 without using a horizontal polymerization tank. Obtained. Production Example 4 PC-4: A polycarbonate was obtained in substantially the same manner as in Production Example 2, except that the extruder conditions were changed as shown in Table 1.

Examples and Comparative Examples Using the polycarbonates obtained in the above production examples, Table 2
And kneading with a single screw extruder (trade name: VS-40, manufactured by Tanabe Plastics Co., Ltd.) at a barrel temperature of 280 ° C., followed by injection molding at 280 ° C. to obtain flammability, initial color tone, Evaluation of heat aging resistance and retention stability,
The results are shown in Table 2.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

The aromatic polycarbonate resin composition of the present invention is excellent in flame retardancy, hue and heat resistance.

[Brief description of the drawings]

FIG. 1 is a flow sheet showing one example of a production method for obtaining a polycarbonate of the present invention.

[Explanation of symbols]

1. Raw material mixing tank 2. 2. Vertical polymerization tank Stirrer blade 4. 4. By-product discharge pipe Horizontal polymerization tank 6. Stirring blade 7. Catalyst introduction pipe

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Nakano 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in the Technology Center of Mitsubishi Engineering-Plastics Corporation (reference) 4J002 BC112 BD153 CD122 CG001 CP032 DE126 DE186 EB096 EB136 ED056 EJ056 EU026 EV256 EW046 FD132 FD133 FD136 GN00 GQ00 GS02

Claims (5)

[Claims] 1. A polycarbonate having a viscosity average molecular weight of 12,000 to 40,000 produced by reacting an aromatic dihydroxy compound with a compound capable of introducing a carbonic acid bond, wherein the content of the cyclic oligomer represented by the formula (I) is as follows: Is 1
100 ppm or less, and the ratio of the aromatic polycarbonate 100 satisfying the relational expression (1) to the total amount of the oligomers represented by the formulas (I), (II) and (III).
An aromatic polycarbonate resin composition comprising 0.01 to 30 parts by weight of a flame retardant in parts by weight. Embedded image (In the formula (I), B is a hydrocarbon group having 1 to 15 carbon atoms which may be substituted with halogen, a divalent group selected from O, S, CO, SO and SO _2. X is a halogen. An atom, an aliphatic group having 1 to 14 carbon atoms or a substituted aliphatic group,
It represents a monovalent group selected from an aromatic group or a substituted aromatic group having 6 to 18 carbon atoms, an oxyalkyl group having 1 to 8 carbon atoms, and an oxyaryl group having 6 to 18 carbon atoms. m is 2
An integer of 8, p is an integer of 0 to 4, and s is 0 or 1. X and p may be the same or different. ) (In the formula (II), A and A ′ are the same or different and each represent an aliphatic group having 1 to 18 carbon atoms, a substituted aliphatic group, an aromatic group, or a substituted aromatic group. Integers of 1 to 7, B, X, p and s have the same definition as in formula (I). (In the formula (III), A ″ represents an aliphatic group having 1 to 18 carbon atoms, a substituted aliphatic group, an aromatic group, or a substituted aromatic group. N ′
Is an integer of 1 to 7, and B, X, p and s have the same definition as in formula (I). ) (Equation 1) (In the formula (1), [I], [II], and [III] each represent the content of the oligomer corresponding to each formula, and Mv represents the viscosity average molecular weight of the aromatic polycarbonate.) 2. The flame retardant is selected from the group consisting of metal sulfonate flame retardants, halogen-containing compound flame retardants, antimony-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. The aromatic polycarbonate resin composition according to claim 1, wherein the composition is at least one selected from the group consisting of: 3. The aromatic polycarbonate resin composition according to claim 1, further comprising 0.01 to 2.0 parts by weight of polytetrafluoroethylene for preventing dripping. 4. The aromatic polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate is produced by a transesterification reaction between an aromatic dihydroxy compound and a carbonic acid diester. 5. The aromatic polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate has a terminal hydroxyl group content of 100 to 1000 ppm.