JP2003049061A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition having excellent flame- retardance and heat-resistance. SOLUTION: This polycarbonate resin composition is produced by compounding 100 pts.wt. of a polycarbonate produced by a melt-process with 0.01-30 pts.wt. of a flame-retardant. The composition satisfies the formula: 2500<=Tanδ/η*<-0.87> <=6000 wherein δand η* are the loss angle and the complex viscosity (Pa.s) of the polycarbonate measured at 250 deg.C and an angular velocity of 10 rad/s, respectively.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition excellent in flammability and heat resistance.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent mechanical properties, and are used in the fields of automobiles, office automation equipment, and
It is widely used industrially as a raw material for the electronic field and the like. On the other hand, there is a strong demand for flame-retardant synthetic resin materials used mainly for applications such as office automation equipment and home appliances, and many flame retardants have been developed and studied in order to meet these demands. For example, the UL94 horizontal flame test, which is one of the standards of flame retardancy, is not only 94HB in the vertical flame test, but is also specified in three stages of V-0 to V-2 in the vertical flame test from the one having good flame retardancy. It is required to meet the demand for higher grade products.

Usually, halogen compounds are mainly used for flame retarding polycarbonate resins. Although the halogen-based compound is effective for flame retardancy, it has poor thermal stability during molding, and a change in hue due to thermal history during molding.
It is easy to cause defects such as deterioration of the appearance of molded products. For the purpose of improving such problems of halogen compounds, recently, for the purpose of reducing the amount of halogen compounds, for example, JP-A-59-202240 discloses a composition using a phosphate compound. JP-A-8-81620
The publication discloses a composition using a polycarbonate-polyorganosiloxane copolymer. However, in order to obtain excellent flammability, it is necessary to add such a flame retardant in a relatively large amount, and therefore, there have been drawbacks such as impairing the excellent mechanical properties and thermal properties inherent in polycarbonate.

[0004]

SUMMARY OF THE INVENTION The present invention provides a polycarbonate resin composition having excellent flammability and heat resistance.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have surprisingly found that
Polycarbonates obtained by the melting method, which have a specific melt viscoelasticity, have high flame retardancy per se, and in comparison with conventional polycarbonates which are usually UL94HB, they exhibit UL94V-2. Further, they have found that the amount of flame retardant required for higher flame retardancy can be reduced, and as a result, deterioration of mechanical properties due to stagnation during molding can be significantly suppressed, and have completed the present invention. . That is, in the present invention, 100 parts by weight of the polycarbonate obtained by the melting method is added with 0.0% flame retardant.
In a polycarbonate resin composition containing 1 to 30 parts by weight, the loss angle δ and the complex viscosity η ^* (Pa · s) of the polycarbonate measured under the conditions of a temperature of 250 ° C. and an angular velocity of 10 rad / s have the following relational expression (1 The polycarbonate resin composition characterized by satisfy | filling these.

[0006]

## EQU00002 ## 2500 ≦ ^tan δ / η ^{* -0.87} ≦ 6000 (1)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. Polycarbonate The polycarbonate constituting the composition of the present invention is produced by a melting method using an aromatic dihydroxy compound and a carbonic acid diester as raw materials.

Aromatic Dihydroxy Compound : An aromatic dihydroxy compound, which is one of the raw materials for polycarbonate, is a compound represented by the following formula (1).

[0009]

[Chemical 1]

(In the formula (1), A is a single bond, an optionally substituted linear, branched or cyclic divalent hydrocarbon group, or -O-, -S-, -CO
- or -SO ₂ - is a divalent group represented by, X and Y is halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, p and q are an integer of 0 or 1. Note that X and Y and p and q may be the same or different from each other. )

Typical aromatic dihydroxy compounds include, for example, bis (4-hydroxydiphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3-methyl). Phenyl) propane, 2,2-bis (4-hydroxy-3-t)
-Butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2
-Bis (4-hydroxy-3,5-dibromophenyl)
Propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybiphenyl, 3,
3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4- Hydroxyphenyl) ketone etc. are mentioned. These aromatic dihydroxy compounds can be used alone or in combination of two or more. Among these, 2,2-
Bis (4-hydroxyphenyl) propane (hereinafter, also referred to as “bisphenol A” and may be abbreviated as “BPA”) is preferable.

Carbonic acid diester : Carbonic acid diester, which is another raw material, is a compound represented by the following formula (2).

[0013]

[Chemical 2]

(In the formula (2), A ′ is an optionally substituted linear, branched or cyclic monovalent hydrocarbon group, and two A ′ are They may be the same or different from each other.)

Representative carbonic acid diesters include, for example, substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate. . These carbonic acid diesters may be used alone or
A mixture of two or more species can be used. Among these, diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) and substituted diphenyl carbonate are preferable.

The carbonic acid diester may be replaced with a dicarboxylic acid or a dicarboxylic acid ester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

These carbonic acid diesters (including the above-mentioned substituted dicarboxylic acids or dicarboxylic acid esters; the same applies hereinafter) are usually used for aromatic dihydroxy compounds.
Used in excess. That is, 1.001 to 1.3, preferably 1.01 to the aromatic dihydroxy compound.
Used at a molar ratio within the range of 1.2. Molar ratio 1.0
When it is smaller than 01, the terminal OH group content of the produced polycarbonate is increased to deteriorate the thermal stability and hydrolysis resistance, and when the molar ratio is larger than 1.3, the polycarbonate contains the terminal OH group. Although the amount decreases, the rate of transesterification reaction decreases under the same conditions, and it tends to be difficult to produce a polycarbonate having a desired molecular weight. In the present invention, the terminal OH group content is 50 to 10
It is preferable to use polycarbonate adjusted to the range of 00 ppm. As a method of supplying the raw material to the raw material mixing tank,
Since it is easier to maintain a high measurement accuracy in the liquid state, it is preferable that one or both of the aromatic dihydroxy compound and the carbonic acid diester be melted and supplied in the liquid state. When the raw material is supplied in a liquid state, an oval flow meter, a micro motion type flow meter, or the like can be used as the measuring device. On the other hand, when the raw material is supplied in a solid state, it is preferable to use one that weighs weight, rather than one that measures capacity such as a screw type feeder, and a weight feeder such as a belt type or loss-in-weight type feeder. Can be used, but the loss-in-wait method is particularly preferable.

Transesterification catalyst : When a polycarbonate is produced by a melting method, a catalyst is usually used. In the polycarbonate production method of the present invention, there is no limitation on the catalyst species, but generally an alkali metal compound,
A basic compound such as an alkaline earth metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound is used. These may be used alone or in combination of two or more. The amount of the catalyst used is the aromatic dihydroxy compound 1
0.05 to 5 μmol, preferably 0.08 mol
It is used in the range of ˜4 μmol, more preferably 0.1 to 2 μmol. When the amount of the catalyst used is less than the above amount, the polymerization activity required for producing a polycarbonate having a desired molecular weight cannot be obtained. When the amount is more than this amount, the polymer hue is deteriorated and the polymer is branched. , The fluidity during molding tends to decrease.

As the alkali metal compound, lithium,
There are inorganic alkali metal compounds such as sodium, potassium, rubidium and cesium hydroxides, carbonates and hydrogen carbonate compounds, and organic alkali metal compounds such as alcoholates, phenolates and organic carboxylates. Among these alkali metal compounds, cesium compounds are preferable, and the most preferable cesium compounds are specifically cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide.

As the alkaline earth metal compound,
There are inorganic alkaline earth metal compounds such as beryllium, magnesium, calcium, strontium and barium hydroxides and carbonates, and organic alkaline earth metal compounds such as alcoholates, phenolates and organic carboxylates.

Examples of the basic boron compound include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron and triethylphenylboron. , Sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt, barium salt or strontium salt of tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. Is mentioned.

Examples of the basic phosphorus compound are trivalent phosphorus compounds such as triethylphosphine, tri-n-propylphosphine, tri-i-propylphosphine, tri-n-butylphosphine, triphenylphosphine and tributylphosphine. Alternatively, quaternary phosphonium salts derived from these compounds can be mentioned.

Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium. Hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide , Methyltriphenylphosphonium ammonium hydroxide, butyltriphenyl ammonium hydroxide, and the like.

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

Of these catalysts, alkali metal compounds are practically desirable. In the present invention, the transesterification catalyst is used in the form of a catalyst solution dissolved in a solvent. Examples of the solvent include water, acetone, alcohol, toluene, and phenol, as well as a solvent that dissolves the raw material aromatic dihydroxy compound and the raw material carbonic acid diester. Of these, water is preferable, and when an alkali metal compound is used as a catalyst, an aqueous solution is preferable.

In the polycarbonate of the present invention, the temperature
Loss measured at a temperature of 250 ° C and an angular velocity of 10 rad / s
Blind angle δ and complex viscosity η^*(Pa · s) is the following relational expression
It is necessary to satisfy (1), preferably the following relational expression
It is within the range of (2), and more preferably the following relational expression
The range is (3). In the present invention, the Tan δ / η
^{* -0. 87}The value of is a value indicating the melt viscoelasticity of polycarbonate.
Used as a parameter. Tanδ / η^{* -0.87}The value of
If it is less than 2,500, the heat resistance is lowered and exceeds 6000.
If so, the combustibility decreases.

[0027]

(3) 2500 ≦ ^Tanδ / η ^{* -0.87} ≦ 6000 (1) 2800 ≦ ^Tanδ / η ^{* -0.87} ≦ 5500 (2) 3000 ≦ ^Tanδ / η ^{* -0.87} ≦ 5000 (3)

The loss angle δ represents the delay of the phase of strain with respect to stress, which is obtained from the measurement of dynamic melt viscoelasticity, and is generally known as one of the indexes showing the dynamic viscoelastic behavior. δ (Tan δ) indicates that the viscoelastic viscous property is strong when the value is large and the elastic property is strong when the value is small. The factors that determine this value are complex, such as the type of monomer that contains the copolymerization,
The copolymer composition, the structure of the copolymer, the molecular structure including the branched structure such as the number of branch points and the length of the branched chain, the molecular weight, the molecular weight distribution and the like can be mentioned. If the value of δ (Tan δ) is too large,
Since the resistance of polycarbonate to dripping during combustion becomes small, it is necessary to add a large amount of flame retardant, while if the value of δ (Tan δ) is too small,
Polycarbonate has a large resistance to dripping during combustion, and a flame retardant may be added in a relatively small amount, but it is considered that unfavorable side reactions occur in the polycarbonate and the thermal stability tends to decrease.

Production Method of Polycarbonate : In the present invention, the production method of the polycarbonate is not particularly limited as long as it is a melting method and a polycarbonate having the above-mentioned specific physical properties can be obtained. Can be manufactured in. That is, usually, both raw materials are uniformly stirred in a raw material mixing tank or the like, and then a catalyst is added to carry out polymerization to produce a polymer. For example, it is preferable that both the above-mentioned raw materials of the aromatic dihydroxy compound and the carbonic acid diester are continuously supplied to the raw material mixing tank, and the obtained mixture and the transesterification catalyst are continuously supplied to the polymerization tank. At that time, in order to stably produce the polymer having the above-mentioned specific physical properties of the present invention, for example, a method which satisfies at least the following conditions (1) and (2) is adopted. (1) Target catalyst supply for maintaining a constant amount of catalyst per 1 mol of aromatic dihydroxy compound or carbonic acid diester supplied to the polymerization tank, per unit production time obtained by fractionating the total production time into one or more The "set catalyst amount", which is the amount, is selected from the range of 0.05 to 5 µmol per 1 mol of the aromatic dihydroxy compound. The "total manufacturing time" means
It corresponds to the raw material supply time for stable production of the polymer in the polymerization tank, and does not include the polymer production time at the time of start-up, grade change, or instability such as production end. (2) The amount of the actual transesterification catalyst (hereinafter, simply referred to as the “actual amount of catalyst”) supplied during at least 95% of each unit production time is the aromatic dihydroxy compound 1
The amount of each catalyst should be kept within a value of ± 0.1 μmol per mol.

In the above (1), the set catalyst amount does not necessarily have to be a constant value throughout the entire production time, but the total production time may be fractionated into one or more and set for each unit production time. It is possible.

This method will be described in detail below. When the total production time is a unit production time of a single fraction, at least 95% of the time is based on 1 mol of the aromatic dihydroxy compound, and the set catalyst amount is set. Maintain the actual amount of catalyst within ± 0.1 μmol. When the total production time is fractionated into a plurality of unit production times and the set catalyst amount is changed, at least 95% of each unit production time is within the set catalyst amount ± 0.1 μmol. Maintain the actual amount of catalyst in the value. In either case, set catalyst amount ± 0.0
It is preferable to maintain within 8 μmol, and the set catalyst amount ±
It is particularly preferable to maintain it within 0.06 μmol. Furthermore, the percentage of time that the actual amount of catalyst is maintained at a controlled value may be at least 95% of the total production time or each unit production time, but the closer it is to 100%, the more preferable. When the time is less than 95%, a polymer having a desired molecular weight and a terminal OH group content cannot be obtained. Especially, when the ratio of the time more than the set catalyst amount is large, the obtained polymer hue is deteriorated and the polymer As branching progresses, as a result, the one satisfying the relational expression defined in the present invention cannot be obtained, and the fluidity at the time of molding the polymer tends to decrease. The polycarbonate of the present invention can be produced even if the production conditions during the polymerization reaction such as the polymerization temperature, the polymerization time, and the degree of reduced pressure are changed, but it is not preferable because stable production becomes difficult. The actual amount of catalyst
It is possible to satisfy a specific relational expression defined by the present invention and to achieve a narrow range without requiring a complicated polymerization operation only by keeping the set amount of catalyst within an extremely small fluctuation range of ± 0.1 μmol and continuing the supply. It was found that a polymer having various physical properties such as molecular weight distribution, color tone, fluidity, heat resistance and mechanical properties can be stably produced.

The above-mentioned actual catalyst amount is set to the set catalyst amount ± 0.
In order to maintain the value within 1 μmol, the catalyst flow rate to be supplied to the polymerization tank is preferably measured and supplied using an oval flow meter, a micromotion type flow meter, or the like.

In order to automatically control the catalyst supply, for example, first, the actual measured value of the catalyst flow rate is continuously input to the computer, and the set catalyst amount and the raw material preparation tank for the aromatic dihydroxy compound or carbonic acid diester are continuously input. It is compared with the set catalyst flow rate calculated from the supply amount of. At that time, when the actual measured value of the catalyst flow rate is different from the set catalyst flow rate, this result is transmitted to the catalyst metering / supplying device, and the valve opening etc. are adjusted so that the actual catalyst flow rate and the set catalyst flow rate are Control to match.

Here, in the automatic control of the catalyst supply, even if the control based on the continuous intermittent measurement is performed in the same manner as the continuous measurement, if the actual measurement interval of the catalyst flow rate is adequately considered. However, continuous automatic measurement is preferable in order to obtain a product of stable quality. That is, if the catalyst flow rate can be continuously and automatically measured, it becomes possible to control the catalyst supply rate to the polymerization tank quickly and continuously, and as a result, a constant set catalyst flow rate can be maintained, and the viscosity average molecular weight of polycarbonate and The fluctuation of the terminal OH group content is small, the molecular weight distribution is narrow, and the color tone
It is preferable because a product having various physical properties such as fluidity, heat resistance, and mechanical properties can be obtained.

It can be easily determined from the measurement result by the above-mentioned measuring means how long the actual catalyst amount was within the set catalyst amount ± 0.1 μmol during the unit production time of a certain set catalyst amount. Can be determined. For continuous measurement,
From the curve showing the relationship between the actual catalyst amount and the measurement time, the cumulative time within the preset catalyst amount ± 0.1 μmol and ±
By determining the cumulative time deviated from 0.1 μmol, at least 95% of the unit production time at the set catalyst amount can be obtained.
Was determined to be maintained within ± 0.1 μmol. Even if it is not a continuous measurement, if it is a continuous measurement, it can be determined by a method such as statistical processing.

In the present invention, the polymerization reaction (transesterification reaction) of polycarbonate is generally carried out continuously in two or more polymerization tanks, that is, in two or more stages, usually in a multistage process of 3 to 7 stages. It is preferable. As specific reaction conditions, temperature: 150 to 320 ° C., pressure: normal pressure to
2.0 Pa, average residence time: 5 to 150 minutes,
In each polymerization tank, in order to make the discharge of phenol by-produced with the progress of the reaction more effective, the temperature is gradually set to a higher temperature and a higher vacuum within the above reaction conditions. In order to prevent deterioration of quality such as hue of the obtained polycarbonate, it is preferable to set the temperature as low as possible and the residence time as short as possible. In the case of using a plurality of polymerization tanks in a multi-stage process, it is preferable to automatically control the actual amount of the catalyst continuously, and in that case, 1 / of the residence time of the first polymerization tank It is necessary that measurement and control be completed within 3.

The apparatus used in the above transesterification reaction may be of vertical type, tubular type, tower type, or horizontal type. Usually turbine blades, paddle blades, anchor blades,
Full zone wing (Shinko Pantech Co., Ltd.), Sunmelar wing (Mitsubishi Heavy Industries, Ltd.), Maxblend wing (Sumitomo Heavy Industries, Ltd.), helical ribbon wing, twisted lattice wing (Hitachi, Ltd.) One or more vertical type polymerization tanks equipped with etc., followed by horizontal uniaxial type polymerization tanks such as disk type and basket type, HVR, SCR, N-SCR (manufactured by Mitsubishi Heavy Industries, Ltd.), Vivolac (Sumitomo Heavy Industries) Machine Industry Co., Ltd.
Manufactured by Hitachi, Ltd.), or a combination of eyeglass blades and blades with a polymer feeding function, such as blades with twist and twist and / or blades with inclination. It is possible to use a horizontal biaxial type polymerization tank equipped with a tray and the like.

In the polycarbonate produced by the above method, a low molecular weight compound such as a raw material monomer, a catalyst, an aromatic hydroxy compound by-produced by a transesterification reaction, and a polycarbonate oligomer is usually left. Above all,
Since the raw material monomer and the aromatic hydroxy compound have a large residual amount and adversely affect the physical properties such as heat aging resistance and hydrolysis resistance, they are preferably removed at the time of commercialization.

The method for removing them is not particularly limited and may be continuously devolatilized by a vent type extruder, for example. At that time, the basic transesterification catalyst remaining in the resin is preliminarily added with an acidic compound or a precursor thereof to deactivate it, thereby suppressing side reactions during devolatilization, and efficiently reacting raw material monomers and Aromatic hydroxy compounds can be removed.

The acidic compound or its precursor to be added is not particularly limited, and any compound can be used as long as it has the effect of neutralizing the basic transesterification catalyst used in the polycondensation reaction. Specifically, hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid, Formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid, picrin Acid, picolinic acid,
Bronsted acids such as phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid and maleic acid, and esters thereof can be mentioned. These may be used alone or in combination of two or more. Of these acidic compounds or precursors thereof, sulfonic acid compounds or ester compounds thereof, such as p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate, are particularly preferable.

The addition amount of these acidic compounds or their precursors is 0.1 to 50 times mol, preferably 0.1 to 50 times the neutralization amount of the basic transesterification catalyst used in the polycondensation reaction.
It is added in the range of 5 to 30 times by mole. The timing of adding the acidic compound or its precursor may be any time after the polycondensation reaction, and there is no particular limitation on the addition method, depending on the properties of the acidic compound or its precursor or desired conditions,
Any method such as a method of directly adding, a method of dissolving in a suitable solvent and a method of using a master batch in the form of pellets or flakes may be used.

The extruder used for devolatilization may be a single screw or a twin screw. Further, the twin-screw extruder is a meshing twin-screw extruder, and the rotation directions thereof may be the same direction rotation or different direction rotations. For the purpose of devolatilization, those having a vent part after the acidic compound addition part are preferable. The number of vents is not limited, but a multi-stage vent having 2 to 10 stages is usually used. Also,
In the extruder, if necessary, a stabilizer, an ultraviolet absorber,
It is also possible to add additives such as a release agent and a colorant and knead with the resin.

Flame Retardant The flame retardant constituting the composition of the present invention is preferably a group consisting of metal sulfonate flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants and silicon-containing compound flame retardants. At least one selected from the above is included. The amount of the flame retardant compounded is usually 0.01 to 30 parts by weight, preferably 0.02, relative to 100 parts by weight of the polycarbonate.
From about 25 parts by weight, an appropriate amount is used depending on the type of flame retardant and the desired degree of flame retardancy. By blending the flame retardant, a thermoplastic resin composition having excellent flame retardancy can be obtained.

Sulfonic Acid Metal Salt Flame Retardant : Examples of the sulfonic acid metal salt flame retardant in the present invention include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts.
The metal of these metal salts is preferably an alkali metal, an alkaline earth metal or the like, and the alkali metal and the alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and There is a barium. The sulfonic acid metal salt may be used alone or in combination of two or more kinds. As the sulfonic acid metal salt, aromatic sulfone sulfonic acid metal salt, perfluoroalkane-sulfonic acid metal salt and the like are preferably selected from the viewpoints of flame retardancy and thermal stability. The aromatic sulfone sulfonic acid metal salt preferably includes an aromatic sulfone sulfonic acid alkali metal salt, an aromatic sulfone sulfonic acid alkaline earth metal salt, and the like, and an aromatic sulfone sulfonic acid alkali metal salt, an aromatic sulfone sulfone The acid alkaline earth metal salt may be a polymer. Specific examples of the aromatic sulfone sulfonic acid metal salt include sodium salt of diphenyl sulfone-3-sulfonic acid, potassium salt of diphenyl sulfone-3-sulfonic acid, 4,4′-
Sodium salt of dibromodiphenyl-sulfone-3-sulfonic acid, 4,4'-dibromodiphenyl-sulfone-
Potassium salt of 3-sulfone, calcium salt of 4-chloro-4'-nitrodiphenylsulfone-3-sulfonic acid,
Examples thereof include a disodium salt of diphenylsulfone-3,3′-disulfonic acid and a dipotassium salt of diphenylsulfone-3,3′-disulfonic acid.

The perfluoroalkane-sulfonic acid metal salt is preferably an alkali metal salt of perfluoroalkane-sulfonic acid, an alkaline earth metal salt of perfluoroalkane-sulfonic acid, or the like, more preferably carbon. Examples thereof include alkali metal sulfonates having a perfluoroalkane group of 4 to 8 and alkaline earth metal sulfonates having a perfluoroalkane group of 4 to 8 carbon atoms. Specific examples of perfluoroalkane-sulfonic acid metal salts include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate,
Sodium perfluoromethylbutane-sulfonate, potassium perfluoromethylbutane-sulfonate, sodium perfluorooctane-sulfonate, potassium perfluorooctane-sulfonate, perfluorobutane-
Examples thereof include tetraethylammonium salt of sulfonic acid.

The amount of the metal sulfonate flame retardant blended is preferably 0.0 with respect to 100 parts by weight of the polycarbonate.
1 to 5 parts by weight. When the amount of the metal sulfonate flame retardant is less than 0.01 part by weight, sufficient flame retardancy cannot be obtained, and when it exceeds 5 parts by weight, the thermal stability tends to decrease.

Halogen-containing compound flame retardant : Examples of the halogen-containing compound flame retardant in the present invention include tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A epoxy polymer. , Decabromodiphenyl oxide, tribromoallyl ether, tetrabromobisphenol A carbonate oligomer, ethylenebistetrabromophthalimide, decabromodiphenylethane, brominated polystyrene, hexabromocyclododecane and the like.
These halogen-containing compound flame retardants may be used alone or in combination of two or more.

The compounding amount of the halogen-containing compound flame retardant is
0.1-2 with respect to 100 parts by weight of the polycarbonate resin
0 parts by weight. When the content of the halogen-containing compound flame retardant is less than 0.1 parts by weight, it is difficult to obtain sufficient flame retardancy, and when it exceeds 20 parts by weight, the mechanical strength decreases, and the cause of discoloration due to bleeding of the flame retardant. May be

Phosphorus-Containing Compound Flame Retardant : Examples of the phosphorus-containing compound flame retardant in the present invention include red phosphorus, coated red phosphorus, polyphosphate compounds, phosphoric acid ester compounds, phosphazene compounds and the like. Examples of the phosphoric acid ester compound include a phosphoric acid ester compound represented by the following formula (3). These may be used alone,
You may use it in combination of 2 or more type.

[0050]

[Chemical 3]

(In the formula (3), R ¹ , R ² , R ³ and R ⁴
Each independently represent a hydrogen atom or an organic group, R
Represents a divalent or higher valent organic group, a is 0 or 1, and
b is an integer of 1 or more, and c is an integer of 0 or more in the case of a single compound, but it may be a mixture of a plurality of compounds having different values of c, and in this case, it is represented by the average value of c. . However, when c is 0, at least one of R ¹ , R ² and R ³ represents an organic group, except when R ¹ , R ² , R ³ and R ⁴ are simultaneously hydrogen atoms. ) Examples of the organic group represented by R ¹ , R ² , R ³ and R ⁴ include an optionally substituted alkyl group, cycloalkyl group and aryl group. Examples of the substituent when it is substituted include an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, an aryl group, an aryloxy group, an arylthio group,
Examples thereof include halogenated aryl groups, and groups in which these substituents are combined (for example, arylalkoxyalkyl groups, etc.), or groups in which these substituents are combined by bonding with an oxygen atom, sulfur atom, nitrogen atom, or the like. (For example, an arylsulfonylaryl group etc.) may be a substituent. Examples of the divalent or higher valent organic group represented by R include an alkylene group, a cycloalkylene group and an arylene group, and examples of the arylene group include a phenylene group which may have a substituent, bisphenols and polynuclear groups. Examples include groups derived from phenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred as the divalent or higher organic group are hydroquinone,
Resorcinol, 2,2-bis (4-hydroxyphenyl) methane (= bisphenol F), 2,2-bis (4
Examples include arylene groups derived from -hydroxyphenyl) propane (= bisphenol A), dihydroxybiphenyl, p, p'-dihydroxydiphenylsulfone, dihydroxynaphthalene, and the like. b is preferably an integer of 1 to 30, and c is preferably an integer of 1 to 10 or an average value thereof (in the case of the mixture).

Specific examples of the phosphoric acid ester compound include:
When c = 0, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl phosphate ) Phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,
3-dichloropropyl phosphate, tris (2,3-
Dibromopropyl) phosphate and bis (chloropropyl) monooctyl phosphate, and when c = 1 or more, R ^{1 to} R ⁴ are alkyl groups such as methyl group, ethyl group, propyl group, or preferably, Bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, which is a phenyl group which may be substituted with an alkyl group,
Examples include polyphosphates such as trioxybenzene triphosphate or mixtures thereof. Among them, triphenyl phosphate and various bisphosphates or a mixture thereof are preferable. These may be used alone,
You may use it in combination of 2 or more type.

The compounding amount of the phosphorus-containing compound flame retardant is preferably 0.1 to 2 with respect to 100 parts by weight of the polycarbonate.
0 parts by weight. The amount of the phosphorus-containing compound flame retardant compounded is 0.
If it is less than 1 part by weight, it is difficult to obtain sufficient flame retardancy.
If it exceeds 0 parts by weight, the heat resistance tends to decrease.

Silicon-containing compound flame retardant : The silicon-containing compound flame retardant in the present invention includes a silicone varnish, an aromatic hydrocarbon group having a substituent bonded to a silicon atom and an aliphatic hydrocarbon group having 2 or more carbon atoms. A silicone resin consisting of, a silicone compound having a branched structure in the main chain and having an aromatic group in the contained organic functional group, and a polydiorganosiloxane polymer which may have a functional group on the surface of silica powder Examples thereof include silicone powder and organopolysiloxane-polycarbonate copolymer. Of these, silicone varnish is preferably used.

As the silicone varnish used in the present invention,
Is mainly a bifunctional unit [R⁰ ₂SiO] and trifunctional
Type unit [R⁰SiO_1.5], A monofunctional unit [R
⁰ ₃SiO_0.5] And / or tetrafunctional unit [SiO₂]
Relatively low molecular weight solution silicone that can be included
It is a resin. Where R⁰Is a hydrocarbon having 1 to 12 carbon atoms
1 to 12 carbon atoms substituted with a group or one or more substituents
Is a hydrocarbon group of the
Group, a hydroxyl group, a vinyl group and the like. R
⁰By changing the type of
It is possible to improve the solubility. With silicone varnish
Is a silicone varnish containing no solvent or a silicone containing solvent.
Silicone varnish that does not contain solvent.
Varnishes are preferred. Silicone varnish is Alkyl Alco
It can be produced by hydrolysis of xysilane.
For example, alkyl trialkoxysilane, dialkyl dial
Coxysilane, trialkylalkoxysilane, tetra
Manufactured by hydrolyzing alkoxysilane etc.
be able to. Molar ratio of these raw materials, hydrolysis rate, etc.
By adjusting the molecular structure (degree of crosslinking) and molecular weight
Can be controlled. Furthermore, depending on the manufacturing conditions
Alkoxysilane remains, but remains in the composition
As a result, the hydrolysis resistance of the polycarbonate resin decreases.
That there is little residual alkoxysilane.
It is desirable that there be no rui. Viscosity of silicone varnish
Is 300 centistokes or less. 300 cm
Exceeding Stokes may result in insufficient flame retardancy.
It The viscosity of the silicone varnish is more preferably 250
It is less than or equal to centistokes, more preferably 200.
It is less than centistokes.

The compounding amount of the silicon-containing compound flame retardant is preferably 0.1% with respect to 100 parts by weight of the polycarbonate resin.
It is 1 to 10 parts by weight. If the content of the silicon-containing compound flame retardant is less than 0.1 parts by weight, it is difficult to obtain sufficient flame retardancy, and if it exceeds 10 parts by weight, the heat resistance tends to decrease.

Polytetrafluoroethylene for dripping prevention :
In the present invention, it is preferable to use polytetrafluoroethylene for dripping prevention in combination in order to achieve higher flame retardancy. The polytetrafluoroethylene for preventing dripping has a tendency to be easily dispersed in a polymer and to bond the polymers to each other to form a fibrous material. Polytetrafluoroethylene for dripping prevention is classified into type 3 according to the ASTM standard. For preventing dripping, for example, Teflon 6J or Teflon 30J from Mitsui DuPont Fluorochemical Co., Ltd., or Daikin Chemical Industry Co., Ltd.
More commercially available as Polyflon F201L.

The amount of polytetrafluoroethylene for dripping prevention is 100 parts by weight of the polycarbonate resin.
It is preferably 0.01 to 2.0 parts by weight. If the blending amount of the polytetrafluoroethylene for dripping prevention is less than 0.01 parts by weight, the melt dripping prevention effect at the time of combustion is insufficient,
If it exceeds 2 parts by weight, the appearance of the molded product tends to deteriorate.

Thermoplastic Elastomer In the present invention, a thermoplastic elastomer can be used if necessary. The thermoplastic elastomer is not particularly limited as long as it can be generally blended in a polycarbonate resin composition to improve its mechanical properties, but specifically, styrene-called SBS and SEBS- A butadiene-based triblock polymer and its hydrogenated product,
Styrene-isoprene triblock polymers called SIS and SEPS and hydrogenated products thereof, olefin elastomers called TPO, polyester elastomers, silicone rubbers, acrylate rubbers, silicone rubber components and acrylates Examples thereof include a composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl-based monomer into a composite rubber including a base rubber component. The acrylic rubber further includes a core-shell type polymer having a crosslinked diene rubber as a core. Among these, the composite rubber-based graft copolymer and the core-shell type polymer are preferably used as the thermoplastic elastomer from the viewpoint of practical performance such as thermal stability, flammability, and impact strength improving effect.

More specifically, the composite rubber-based graft copolymer is 10 to 90% by weight of a polyorganosiloxane rubber component and 90 to 10% by weight of a polyalkyl (meth) acrylate rubber component (the total amount of both rubber components is 100% by weight). (Meth) acrylic acid ester compound and aromatic alkenyl compound in a composite rubber having a structure in which both rubber components are entangled with each other and cannot be practically separated, and the average diameter of which is 0.08 to 0.6 μm. , A composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl-based monomer such as a vinyl cyanide compound. In the production of this composite rubber-based graft copolymer, the method described in JP-A 1-230664 or the like can be used. Such a composite rubber-based graft copolymer is commercially available from, for example, Mitsubishi Rayon Co., Ltd.
It is commercially available as METABLEN S-2001, METABLEN SRK-200.

The blending amount of the thermoplastic elastomer is preferably 10 parts by weight or less, more preferably 0.1 to 6 parts by weight, based on 100 parts by weight of the polycarbonate. When the blending amount of the thermoplastic elastomer exceeds 10 parts by weight, the strength and heat resistance are likely to decrease.

Polycarbonate Resin Composition The polycarbonate resin composition of the present invention contains various additives, such as stabilizers, ultraviolet absorbers, and release agents, in such amounts that the effects of the present invention are manifested, within a range that does not impair the effects of the present invention. , A colorant and an antistatic agent may be contained. In addition, in order to obtain various uses and desired performance, thermoplastic resins such as styrene-based resins and polyester-based resins, thermoplastic elastomers may be blended, or glass fibers, glass flakes, glass beads, carbon fibers. Additives such as inorganic fillers such as, wollastonite, calcium silicate, aluminum borate whiskers and the like can also be added. There is no particular limitation on the mixing method of the polycarbonate described in the present invention and the above-mentioned additives and the like and the mixing timing. It can be added in a molten state, but it is also possible to blend it with solid-state polycarbonate such as pellets or powder and then knead it with an extruder or the like.

[0063]

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

Preparation of Polycarbonate Polycarbonate PC-1 used in Examples and Comparative Examples,
2 was prepared according to Production Examples 1 and 2 described below,
PC-3 was obtained and prepared as described below. In addition, these polycarbonates PC-1 to 3 have the following (1) to
Analysis and physical property evaluation were performed by the measuring method of (4).

(1) Viscosity average molecular weight (Mv) The intrinsic viscosity [η] at 20 ° C. in methylene chloride was measured using an Ubbelohde viscometer, and the viscosity average molecular weight (Mv) was calculated from the following formula.

[0066]

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

(2) Terminal OH group content titanium tetrachloride / acetic acid method (Makromol. Chem. 8)
No. 8 215 (1965)). The measured value represents the weight of the terminal OH group relative to the weight of the polycarbonate in ppm.

(3) Molecular weight distribution (Mw / Mn) It was measured by gel permeation chromatography (GPC). HLC-8020 (manufactured by Tosoh Corp.) was used as a measuring device, and tetrahydrofuran was used as an eluent, and it was calculated in terms of polystyrene to calculate Mw / Mn.

(4) Melt Viscoelasticity Melt viscoelasticity was measured as follows. The polycarbonate is dried at 120 ° C for 5 hours, and the diameter is 25m at 250 ° C.
m and a thickness of 1.5 mm were press-molded to obtain a measurement sample. Before measurement, the sample was dried under reduced pressure at 120 ° C. for 4 hours and then subjected to measurement. Viscoelasticity measuring instrument (RDA-7
00, manufactured by Rheometrics Co., Ltd., and has a diameter of 25
mm parallel plate type jig is attached, and the measurement temperature is 250 ° C in a nitrogen stream that satisfies the proper conditions of this equipment.
Set to. The measurement temperature was set by measuring the temperature in the oven. After that, a dried measurement sample was set, and the sample was allowed to stand so that the whole sample was sufficiently set temperature, and then the measurement was performed by rotating at an angular velocity of 10 rad / s and a strain of 10%. By this measurement, the loss tangent Tan δ and the complex viscosity η ^* (Pa · s) were obtained.

[0070]

[Manufacturing Example 1] PC-1 An embodiment of a method for manufacturing a polycarbonate will be described with reference to FIG. FIG. 1 is a flow sheet diagram showing an example of the manufacturing method of the present invention. In the figure, 1 is a DPC storage tank, 2 is a stirring blade, 3 is a BPA hopper, 4a and b are raw material mixing tanks, 5
Is a DPC flow control valve, 6 is a BPA flow control valve, 7 is a pump, 8 is a catalyst flow control valve, 9 is a program controller, 1
0 is a pump and 11 is a catalyst storage tank. In the figure, 12 is a by-product discharge pipe, 13a, b, and c are vertical polymerization tanks, 14 is a Maxblend blade, 15 is a horizontal polymerization tank, and 16 is a lattice blade.

A diphenyl carbonate melt prepared at 120 ° C. under a nitrogen gas atmosphere and a bisphenol A powder measured under a nitrogen gas atmosphere were respectively supplied from a DPC storage tank (1) at 205.0 mol / hour and a BPA hopper ( 3) to 197.1 mol / h (raw material molar ratio 1.04)
0) Weighing with a micro-motion type flow meter and a loss-in-weight type weight feeder,
Raw material mixing tank (4a) adjusted to 140 ° C under nitrogen atmosphere
Was continuously fed to. Then, the raw material mixed solution is put into the raw material mixing tank (4b) and further, through the pump (7), the capacity is 100 L.
Was continuously supplied to the first vertical stirring polymerization tank (15a).
On the other hand, simultaneously with the start of the supply of the above mixture, a 2 wt% cesium carbonate aqueous solution as a catalyst was introduced through a catalyst introduction pipe.
Continuous supply was started at a flow rate of 1.6 mL / h (set catalyst amount: 0.5 μmol to 1 mol of bisphenol A).

At this time, in actual control of the catalyst flow rate, the program control unit (9) calculates the set catalyst flow rate from the BPA flow rate detected by the BPA flow rate control valve (6) and the set catalyst amount, and sets this value. This was performed by controlling the opening of the catalyst flow rate control valve (8) so that the catalyst flow rate actually measured by the measuring device provided in the catalyst flow rate control valve (8) would match.

The first vertical stirring polymerization tank (13a) equipped with the Maxblend blade (14) was placed under normal pressure and a nitrogen atmosphere.
The liquid level was kept constant while controlling the temperature to 220 ° C. and controlling the opening degree of the valve provided in the polymer discharge line at the bottom of the tank so that the average residence time would be 60 minutes.

The polymerization liquid discharged from the bottom of the tank was
Capacity 100 with 2nd and 3rd Maxblend blades
L vertical stirring polymerization tank (13b, 13c), and horizontal polymerization tank (1) having a capacity of 150 L equipped with a fourth lattice blade (16).
5) were successively and successively supplied.

The reaction conditions in the second to fourth polymerization tanks are as follows, as the reaction progresses: high temperature, high vacuum,
The conditions were set so that the stirring speed was low. Temperature Pressure Stirring speed Second polymerization tank (13b) 220 ° C. 1.33 × 10 ⁴ Pa 110 rpm Third polymerization tank (13c) 240 ° C. 2.0 × 10 ³ Pa 75 rpm Fourth polymerization tank (15) 280 ° C. 6.67 During the 10 × 10 Pa 10 rpm reaction, the liquid level was controlled so that the average residence time in the second to fourth polymerization tanks was 60 minutes, and in each polymerization tank, the by-produced phenol was by-produced. Biological discharge pipe (1
It was removed from 2). It operated continuously for 1500 hours under the above conditions. The polycarbonate extracted from the polymer discharge port at the bottom of the fourth polymerization tank was introduced into a twin-screw extruder equipped with a three-stage vent port in a molten state, and p
-Butyl toluenesulfonate was added to the polycarbonate weight in an amount of 4.0 ppm (4.4 times mol with respect to the neutralization amount of the catalyst), hydrogenated and devolatilized, and then pelletized.

Viscosity average molecule of the obtained polycarbonate
The amount (Mv) and the content of terminal OH groups are 21,
It was 500 and 500 ppm. Also, catalyst flow rate control
Of the catalyst flow rate measured by the measuring device installed on the valve (8)
Continuous measurement data (hereinafter referred to as "catalyst flow control valve continuous measurement data
Data ". ) From aromatic dihydroxy compounds
With respect to 1 mol, the set catalyst amount is within ± 0.06 μmol and
When the time within ± 0.1 μmol was calculated,
The total manufacturing time was 96.7% and 99.1%. molecule
Quantity distribution (Mw / Mn) and Tan δ / η^{* -0. 87}The value of
They were 2.3 and 4,850, respectively. PC this
It is expressed as -1.

[0077]

[Manufacturing Example 2] (Comparative Manufacturing Example) In PC-2 Manufacturing Example 1, a program controller was not installed, and the catalyst flow rate was 1.6 mL / h (set catalyst amount: 0.5 μmol to 1 mol of bisphenol A). The same procedure as in Production Example 1 was carried out except that the above was fixed. The viscosity average molecular weight (Mv) and terminal OH group content of the obtained polycarbonate are
It was 22,400 and 500 ppm, respectively. Further, based on the continuous measurement data of the catalyst flow control valve, the set catalyst amount ± 0.06 per mol of the aromatic dihydroxy compound.
When the time within μmol and within ± 0.1 μmol was calculated, it was 89.9% and 91.7% of the total production time. Molecular weight distribution (Mw / Mn) and Tan δ / η ^{* -0.87}
The values of were 2.7 and 2,240, respectively. This is designated as PC-2.

PC-3 poly-4,4-isopropylidene diphenyl carbonate having a viscosity average molecular weight (Mv) of 22,100,
Terminal OH group content is 30ppm, molecular weight distribution (Mw / M
n) is 2.3 and the value of ^Tanδ / η ^{* -0.87} is 7,550 ( ^Upilon S-3000, Mitsubishi Engineering Plastics Co., Ltd.)

Polycarbonate Resin Composition The materials blended with the polycarbonate in the following Examples and Comparative Examples are as follows.

Flame retardant 1 Perfluorobutanesulfonic acid potassium salt (Megafuck F114, manufactured by Dainippon Ink and Chemicals) Flame retardant 2 Tetrabromobisphenol A carbonate oligomer (Upilon FR53, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) Flame retardant 3 Condensed phosphoric acid ester (in the formula (3), R
Is a resorcinol residue, R ¹ , R ² , R ³ and R ⁴ are 2,6-xylenol residues, a and b are 1 and c is 1.0.
1, ADK STAB FP500, manufactured by Asahi Denka Co., Ltd. Flame retardant 4 Condensed phosphate ester (in the formula (3), R
Is a bisphenol A residue, R ¹ , R ² , R ³ and R ⁴ are phenyl groups, a and b are 1, c is 1.08, ADEKA STAB FP700, manufactured by Asahi Denka Co., Ltd. Flame retardant 5 Silicone varnish (KR -219, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25 ° C. is 16.4 cSt) PTFE Drip prevention polytetrafluoroethylene (Teflon 6J, Mitsui DuPont Fluorochemical Co., Ltd.)
Made)

Elastomer 1 Polybutadiene core / polymethylmethacrylate shell copolymer (Paraloid EXL2603, manufactured by Kureha Chemical Industry Co., Ltd.) Elastomer 2 Composite rubber-based graft copolymer (Metablene SRK-200, manufactured by Mitsubishi Rayon Co., Ltd.)

The physical properties of the polycarbonate resin compositions obtained in the following Examples and Comparative Examples are evaluated in the following (5) to (7).
The measurement method of

(5) From an inflammable resin composition to an injection molding machine (SG75-Cycap MII, manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 280 ° C. and a molding cycle of 1 minute. The test piece was injection-molded and subjected to a UL standard 94 20 mm vertical combustion test.

(6) Deflection temperature under load (DTUL) Using a resin composition and an injection molding machine (SG75-Cycap MII, manufactured by Sumitomo Heavy Industries, Ltd.), a cylinder temperature of 280 ° C. and a molding cycle of 1 minute. Then, a predetermined test piece was injection-molded, and a thermal deformation test according to ASTM D-648 was performed.

(7) Heat resistance Izod: The resin composition was treated with an injection molding machine (SG75-Cycap MII, manufactured by Sumitomo Heavy Industries, Ltd.).
Injection molding was performed under the conditions of a cylinder temperature of 300 ° C. and a molding cycle of 5 minutes, and a predetermined test piece molded on the fifth shot under these conditions was subjected to a 1/8 inch thick notched Izod impact test according to ASTM D-256. . Appearance: Also, the appearance of the molded test piece was evaluated in four levels according to the following criteria. That is, ◎ indicates that no silver was generated, ○ indicates that silver was generated only in a small part of the molded product, and △
Indicates that about half of the molded product has silver, and x indicates that almost all of the molded product has silver.

[0086]

[Examples 1 to 4 and Comparative Examples 1 to 7] Using the components described above, the components were blended and blended according to the blending composition shown in Table 1 to obtain a twin-screw extruder (TE).
X30HSST (manufactured by Japan Steel Works, Ltd.) was kneaded at a barrel temperature of 280 ° C. to obtain a polycarbonate resin composition. The pellets thus obtained were dried at 120 ° C. for 5 hours, and then various test pieces were prepared according to the above-mentioned procedure.
TUL and heat resistance were evaluated. The results are shown in Table-1.

[0087]

[Table 1]

[0088]

The polycarbonate resin composition of the present invention is excellent in flammability and heat resistance.

[Brief description of drawings]

FIG. 1 is a flow sheet diagram showing an example of a manufacturing method of the present invention.

[Explanation of symbols] 1. DPC storage tank 2. Stirrer 3. BPA hopper 4
a, b. Raw material mixing tank 5. DPC flow control valve 6. BP
A flow control valve 7. Pump 8. Catalyst flow control valve 9. Program control device 10. Pump 11. Catalyst storage tank 1
2. By-product discharge pipe 13a, b, c. Vertical polymerization tank 1
4. Maxblend Tsubasa 15. Horizontal polymerization tank 16. Lattice wings

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tatsuya Masuki             5-6 Higashi-Hachiman 5-2, Hiratsuka City, Kanagawa Prefecture             Ryo Engineering Plastics Stock Association             Company Technology Center (72) Inventor Hiroshi Yoshioka             5-6 Higashi-Hachiman 5-2, Hiratsuka City, Kanagawa Prefecture             Ryo Engineering Plastics Stock Association             Company Technology Center F-term (reference) 4J002 BD153 CD122 CG001 CG011                       CG032 EB076 EJ056 EV236                       EW046 FD132 FD133 FD136

Claims (4)

[Claims] 1. A polycarbonate 10 obtained by a melting method.
In a polycarbonate resin composition in which 0 to 30 parts by weight of a flame retardant was mixed at 0.01 to 30 parts by weight, the loss angle δ and the complex viscosity η ^* (Pa · Pa) of the polycarbonate measured at a temperature of 250 ° C. and an angular velocity of 10 rad / s. The polycarbonate resin composition, wherein s) satisfies the following relational expression (1). [ ^Formula 1] 2500 ≦ ^Tanδ / η ^{* -0.87} ≦ 6000 (1) 2. The flame retardant is a sulfonic acid metal salt flame retardant,
The polycarbonate resin composition according to claim 1, which is at least one selected from the group consisting of a halogen-containing compound flame retardant, a phosphorus-containing compound flame retardant, and a silicon-containing compound flame retardant. 3. The polycarbonate resin composition according to claim 1, wherein 0.01 to 2.0 parts by weight of polytetrafluoroethylene for preventing dripping is blended. 4. The polycarbonate having a terminal OH group content of 50 to 1000 ppm.
The polycarbonate resin composition according to any one of items 1 to 3.