JP2003096290A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant polycarbonate resin composition having excellent mechanical properties, weather resistance, flame retardance and mold depositing performance. SOLUTION: This flame-retardant polycarbonate resin composition comprises (a) a particular aromatic polycarbonate of 100 pts.wt., (b) a phosphoric ester of a particular structure of 0.5-40 pts.wt., (c) a poly(fluoroethylene) resin of 0.01-3 pts.wt., (d) an impact resistance improver of 0.5-30 pts.wt. and (e) a UV absorbent of 0.01-1 pts.wt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polycarbonate resin composition, and more particularly to a flame-retardant polycarbonate resin composition having excellent weather resistance.

[0002]

2. Description of the Related Art Polycarbonate resin compositions are used in various fields as excellent engineering plastics and also in applications requiring flame retardancy. The flame-retardant polycarbonate resin is disclosed in many resin compositions containing a phosphorus-based flame retardant represented by a phosphoric acid ester as a non-halogen material. Particularly, it is derived from resorcin, for example, from the problem of mold deposit during molding. An example of using a condensed phosphoric acid ester having a structure can be seen.

Further, JP-A-6-228426 and JP-A-7-53876 disclose resin compositions in which a condensed phosphoric acid ester having a structure derived from bisphenol is mixed with a thermoplastic resin such as a polycarbonate resin. And improves bleed or hydrolysis resistance. However, a polycarbonate resin composition containing such a condensed phosphoric acid ester is
The resin composition was not always satisfactory in terms of weather resistance.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant polycarbonate resin composition which is excellent in mechanical strength, weather resistance, flame retardancy and mold deposit property.

[0005]

As a result of intensive studies, the inventors of the present invention have found that (a) a polycarbonate obtained by a melting method and having a loss angle measured at a temperature of 250 ° C. and an angular velocity of 10 rad / s. δ and complex viscosity η * (Pa · s)
To 100 parts by weight of polycarbonate, which satisfies the following relational expression,

## EQU00002 ## ^{2500.ltoreq.Tan.delta./.eta.*-0.87.ltoreq.6000} (b) Phosphate ester represented by the following formula (1) 0.5 to 4
0 parts by weight,

[Chemical 2] (In the formula (1), R ₁ And R ₂ Each represent a methyl group, a hydrogen atom or a phenyl group, and n represents an integer of 1 to 5. ) (C) Polyfluoroethylene 0.01-3
It has been found that a resin composition obtained by blending parts by weight, (d) 0.5 to 30 parts by weight of an impact resistance improver and 0.01 to 2 parts by weight of an ultraviolet absorber (e) can solve the above problems, The present invention has been completed.

The present invention will be described in detail 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
It is a compound represented by the following formula (2).

[0008]

[Chemical 3]

(In the formula (2), A is a single bond, an optionally substituted linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms, 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 (3).

[0012]

[Chemical 4]

(In the formula (3), 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 materials to the raw material mixing tank, one or both of the aromatic dihydroxy compound and the carbonic acid diester are melted and supplied in the liquid state, because the liquid state is easier to maintain the high measurement accuracy. Is preferred. 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, the catalyst species is not limited, but generally, an alkali metal compound, an alkaline earth metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound, etc. The basic compounds of are used. These may be used alone or in combination of two or more. The amount of the catalyst used is 0.05 to 5 μmol, preferably 0.08 to 4 per 1 mol of the aromatic dihydroxy compound.
It is used in the range of 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, phenol, and a solvent that dissolves the raw material aromatic dihydroxy compound, carbonic acid diester, and the like. Of these solvents, water is preferable, and when an alkali metal compound is used as a catalyst, an aqueous solution is preferable.

[0025]Loss angle δ and complex viscosity η ^* : In the present invention
With polycarbonate, the temperature is 250 ° C and the angular velocity is 10
Loss angle δ and complex viscosity η measured under the condition of rad / s
^*(Pa · s) must satisfy the following relational expression
And preferably within the range of the following relational expression, and more preferably
Specifically, it is within the range of the following relational expression. In the present invention, the
Tanδ / η^{* -0.87}The value of is the melt viscosity of polycarbonate.
It was used as a parameter indicating elasticity. Tanδ / η
^{* -0.87}If the value of is less than 2500, the heat resistance decreases, and
If it exceeds 000, the flame retardancy decreases.

[0026]

## ^EQU00003 ## 2500 ≦ ^tan δ / η ^{* -0.87} ≦ 6000 2800 ≦ ^tan δ / η ^{* -0.87} ≦ 5500 3000 ≦ ^tan δ / η ^{* -0.87} ≦ 5000

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.

In the present invention, it is possible to add various stabilizers, ultraviolet absorbers, release agents, coloring agents, etc. to the polycarbonate, and these additives are added during the production of the polycarbonate or before the production of pellets. In some cases, these additives are added, and those containing these additives may be generally referred to as "polycarbonate", but the value of the above relational expression defined in the present invention is obtained for a polycarbonate containing no such additives at all. It is a thing.

The molecular weight of the polycarbonate used in the present invention is 2 at the temperature of methylene chloride as a solvent.
The viscosity average molecular weight converted from the solution viscosity measured at 5 ° C. is preferably 16,000 to 30,000, more preferably 18,000 to 26,000. If the viscosity average molecular weight is less than 16,000, the impact strength tends to be insufficient, and if it exceeds 30,000, the fluidity tends to decrease.

Polycarbonate production method : In the present invention, the polycarbonate production method 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. It can be manufactured by the method. 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.

In the following, this method will be described in detail. When the total production time is a unit production time of a single fraction, at least 95% of the total production 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.

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 raw material molar ratio and the measurement time, the cumulative time within the preset catalyst amount ± 0.1 μmol and the cumulative time deviating from ± 0.1 μmol were obtained, It is determined whether at least 95% of the unit manufacturing time at the set amount of catalyst was maintained at a value 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 polycarbonate polymerization reaction (transesterification reaction) 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, a polycarbonate oligomer and the like usually remains. 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 one can be used as long as it has an 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 amount of these acidic compounds or their precursors added 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 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.

Phosphoric Acid Ester (b) In the present invention, the phosphoric acid ester represented by the following formula (1) is a compound containing phosphorus in the molecule, does not contain a structure derived from resorcin and has a substituent on the benzene ring. It is a condensed phosphoric acid ester that does not have.

[0045]

[Chemical 5]

In the formula (1), R ₁ And R ₂ Each represents a methyl group, a hydrogen atom or a phenyl group, preferably a methyl group or a hydrogen atom, and most preferably a methyl group. n represents an integer of 1 to 5, preferably 1
Represents an integer of 3; However, when the phosphoric acid ester represented by the formula (1) is a mixture of condensed phosphoric acid esters in which n is different, n represents the average value of the mixture.

The amount of the phosphoric acid ester represented by the formula (1) is 0.
5 to 40 parts by weight. Phosphate ester content is 0.5
If it is less than 40 parts by weight, the flame retardance is insufficient, and if it exceeds 40 parts by weight, the mechanical properties tend to deteriorate. The amount of the phosphoric acid ester compounded is preferably 1 to 30 parts by weight, more preferably 2 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin.
-25 parts by weight.

[0048] As (c) polyfluoroethylene in polyfluoroethylene present invention,
For example, polytetrafluoroethylene having a fibril-forming ability is mentioned, and it has a tendency to be easily dispersed in a polymer and to bond the polymers to each other to form a fibrous material. Polytetrafluoroethylene having the ability to form fibrils is classified as type 3 according to the ASTM standard. Examples of the polytetrafluoroethylene having fibril forming ability include, for example, Mitsui DuPont Fluorochemical Co., Ltd.
It is commercially available as Teflon 6J or Teflon 30J or as Polyflon F-201L from Daikin Industries, Ltd.

The compounding amount of polyfluoroethylene is 0.01 to 3 parts by weight with respect to 100 parts by weight of aromatic polycarbonate. The blending amount of polyfluoroethylene is 0.0
If it is less than 1 part by weight, the effect of preventing molten dripping during combustion is insufficient, and if it exceeds 3 parts by weight, the appearance of the molded product tends to deteriorate. The blending amount of polyfluoroethylene is preferably 0. 0 with respect to 100 parts by weight of the aromatic polycarbonate resin.
02 to 2 parts by weight, more preferably 0.05 to
It is 1.5 parts by weight.

Impact modifiers (d) Impact modifiers used in the present invention include acrylic rubber, styrene / hydrogenated butadiene / styrene block copolymer, styrene / hydrogenated isoprene / styrene block copolymer. Examples thereof include polymer, AES resin, AAS resin, polybutadiene, butadiene / styrene copolymer, polyisoprene, and the like, preferably acrylic rubber, styrene / hydrogenated butadiene / styrene block copolymer, styrene / hydrogenated isoprene / styrene. Block copolymer, A
Examples include ES resins and AAS resins, and more preferably acrylic rubber. As acrylic rubber,
For example, a multilayer structure polymer including an alkyl (meth) acrylate (a generic name for alkyl acrylate and alkyl methacrylate, the same applies hereinafter) -based polymer can be mentioned. Specific examples thereof include a multilayer structure polymer having a core made of a saturated or unsaturated rubber component and a shell made of an alkyl (meth) acrylate polymer. By using an acrylic rubber, especially a polymer having a multi-layer structure, it is easy to obtain a resin composition excellent in impact strength and appearance of a molded product. Examples of the saturated or unsaturated rubber component forming the core include polyalkyl (meth) acrylate, polybutadiene, butadiene / styrene copolymer and the like. Examples of the alkyl (meth) acrylate-based polymer that forms the shell include alkyl (meth) acrylates having an alkyl group having about 1 to 8 carbon atoms, such as ethyl (meth) acrylate, butyl (meth) acrylate, and ethylhexyl (meth). Examples thereof include polymers or copolymers such as acrylate. A crosslinking agent such as an ethylenically unsaturated monomer may be used in the alkyl (meth) acrylate polymer, and examples of the crosslinking agent include alkylenediol di (meth) acrylate and polyester di (meth). Examples thereof include acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, and allyl (meth) acrylate.

The content of the impact resistance improver is 0.5 to 30 parts by weight based on 100 parts by weight of the aromatic polycarbonate. If the amount of the impact resistance improver is less than 0.5 parts by weight, the impact resistance is insufficient, and if it exceeds 30 parts by weight, the appearance of the molded product tends to be deteriorated. The compounding amount of the impact resistance improver is preferably 1 to 25 parts by weight, more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin.
Parts by weight.

Ultraviolet Absorber Examples of the ultraviolet absorber (e) in the present invention include benzophenone type, benzotriazole type, phenyl salicylate type and hindered amine type. As the benzophenone-based ultraviolet absorber, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-
Benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,
4'-dimethoxy-benzophenone, 2,2 ', 4
4'-tetrahydroxy-benzophenone and the like can be mentioned.

As the benzotriazole type ultraviolet absorber, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-
Ditertiarybutylphenyl) benzotriazole, 2
(2'-hydroxy-3'-tertiarybutyl, 5'-
Methylphenyl) benzotriazole and the like can be mentioned.

Examples of the phenyl salicylate type ultraviolet absorber include phenyl salicylate, 2,4-ditertiarybutylphenyl 3,5-ditertiarybutyl 4-hydroxybenzoate and the like. Examples of the hindered amine-based ultraviolet absorber include bis (2,2,6,6-tetramethylpipedinyl 4) sepacate.

In addition to the above, the ultraviolet absorber includes a compound having a function of converting energy held by ultraviolet rays into vibration energy in the molecule and releasing the vibration energy as heat energy or the like. Further, a compound which exhibits an effect when used in combination with an antioxidant or a coloring agent, or a light stabilizer which acts as a light energy converting agent, which is called a quencher, can also be used in combination.

The blending amount of the ultraviolet absorber is 0.01 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate. If the amount of the ultraviolet absorber is less than 0.01 parts by weight, the weather resistance is insufficient, and if it exceeds 2 parts by weight, yellowing is strong and the toning property is poor, and bleeding out tends to occur. The blending amount of the ultraviolet absorber is preferably 0.05 to 1.8 parts by weight, and more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the polycarbonate.

Titanium Oxide Titanium oxide, which is added as an optional component in the flame-retardant polycarbonate resin composition of the present invention, improves the whiteness, light-shielding property, light reflectance and the like of the molded product. Titanium oxide is produced by the sulfuric acid method or the chlorine method, but titanium oxide produced by the sulfuric acid method is inferior to titanium oxide produced by the chlorine method in terms of whiteness, so that the one produced by the chlorine method is It is suitable. The crystal forms of titanium oxide include rutile type and anatase type, and the rutile type is superior from the viewpoint of whiteness, light reflectance and light resistance, and the rutile type is preferable.

When the titanium oxide is not surface-treated, it is likely to cause a decrease in the molecular weight or discoloration of the polycarbonate when the resin composition is melt-kneaded at a high temperature. Therefore, the surface-treated titanium oxide is preferable. The surface treatment of titanium oxide is performed with at least one inorganic surface treatment agent selected from alumina hydrate and silicic acid hydrate. Further, an organic surface treatment agent, particularly titanium oxide treated with a silicone compound is preferable. As the silicone compound, polyorganosiloxane (Japanese Patent Publication No. 63-26140) is used.
Japanese Patent Publication), polyhydrocarbon siloxane (Japanese Patent Publication No. 63-
No. 31513), a silane coupling agent (see Japanese Patent Publication No. 3-2189), and the like.

The average particle size of titanium oxide is preferably 0.05 to 0.5 μm. Average particle size is 0.05μ
When it is less than m, the light-shielding property and light ray reflectance of the obtained molded product tend to be insufficient, and when it exceeds 0.5 μm, the light-shielding property and light ray reflectance of the molded product tend to be insufficient, and further, the surface appearance of the molded product is And the impact strength is likely to decrease. The average particle diameter is more preferably 0.08 to 0.45 μm, and most preferably 0.1 to 0.4 μm.

The content of titanium oxide is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of polycarbonate. By blending titanium oxide, the light-shielding property of the molded product is improved, but if it exceeds 20 parts by weight, the impact strength tends to decrease. The compounding amount of titanium oxide is polycarbonate 1
It is more preferably 1 to 15 parts by weight with respect to 00 parts by weight.

Flame-Retardant Polycarbonate Resin Composition The flame-retardant polycarbonate resin composition of the present invention contains, if necessary, stabilizers such as antioxidants, pigments, dyes, lubricants,
Other flame retardants, release agents, additives such as slidability improvers, fibrous reinforcing materials such as glass fibers and carbon fibers, mica, talc,
Plate-shaped reinforcing material such as glass flakes or potassium titanate,
Whiskers such as aluminum borate can be added and blended.

In the flame-retardant polycarbonate resin composition of the present invention, a thermoplastic resin such as a styrene resin, a polyester resin such as polybutylene terephthalate or polyethylene terephthalate, a polyamide resin, a polyolefin resin or the like, as long as the characteristics thereof are not impaired. Can be blended. The blending amount of such a thermoplastic resin is preferably 40% by weight or less, more preferably 30% by weight or less of the thermoplastic resin composition.

The flame-retardant polycarbonate resin composition of the present invention is a flame-retardant polycarbonate resin composition prepared by blending a non-halogen phosphate ester. The components blended in the resin composition of the present invention are chlorine-free. Since it is non-bromine, it is a preferable material for eliminating the corrosion problem of the molding machine and the mold.

The method for producing the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing components other than the polycarbonate during the polymerization reaction or the end of the weight reaction, and a resin during kneading. Examples thereof include a method of adding in a molten state, a method of blending components other than polycarbonate with solid-state polycarbonate such as pellets, and then kneading with an extruder or the like. For example, a method of melt-kneading a phosphate ester, polytetrafluoroethylene, an impact modifier, and an ultraviolet absorber all at once immediately after the completion of the polymerization reaction of polycarbonate, a method of kneading all components including polycarbonate after kneading with an extruder, and the like can be mentioned. To be

[0065]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof. The obtained polycarbonate was analyzed by the following measuring method.

(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.

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

(2) Terminal OH group content Titanium tetrachloride / acetic acid method (Makromol. Chem.
88 215 (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 sample polycarbonate resin is dried at 120 ° C. for 5 hours to give 250
A sample for measurement was obtained by press molding at a temperature of 25 ° C. into a shape having a diameter of 25 mm and a thickness of 1.5 mm. 120 samples before measurement
It was dried under reduced pressure at 4 ° C. for 4 hours and subjected to measurement. A viscoelasticity measuring device (RDA-700, manufactured by Rheometrics Co., Ltd.) was used, a parallel plate type jig having a diameter of 25 mm was attached, and the measurement temperature was 250 in a nitrogen stream satisfying the proper conditions of the device. It was set to ° C. The measurement temperature was set by measuring the temperature in the oven. After that, the dried measurement sample was set in the instrument, and the sample was allowed to stand so that the entire temperature was sufficiently set, and then the angular velocity was 10 rad /
s, strain was measured by rotating at 10%. By this measurement, the loss tangent Tan δ and the complex viscosity η * (Pa ·
s) was calculated.

[0070]

[Manufacturing Example 1] PC-1 An embodiment of a method for manufacturing the polycarbonate used in the Examples will be described with reference to FIG. FIG. 1 is a flow sheet diagram showing an example of a method for producing polycarbonate. In the figure, 1 is a DPC storage tank, 2 is a stirring blade, 3 is a BPA hopper, 4a and 4b are raw material mixing tanks, 5 is a DPC flow control valve, 6
Is a BPA flow rate control valve, 7 is a pump, 8 is a catalyst flow rate control valve, 9 is a program controller, 10 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 Maxblend blades, 15
Is a horizontal polymerization tank, and 16 is a lattice blade.

The diphenyl carbonate melt prepared at 120 ° C. in a nitrogen gas atmosphere and the bisphenol A powder weighed in a nitrogen gas atmosphere were supplied from a DPC storage tank (1) at 205.0 mol / h and a BPA hopper, respectively. From (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 (13a).
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. First with Maxblend wings (14)
The vertical stirring polymerization tank (13a) is kept under normal pressure and nitrogen atmosphere for 2
The liquid level was kept constant while controlling the temperature to 20 ° C. and controlling the valve opening provided in the polymer discharge line at the bottom of the tank so that the average residence time was 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 were set such that the temperature was high, the vacuum was high, and the stirring speed was low as the reaction proceeded, as described below. 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 × 10 Pa 10 rpm

During the reaction, the average residence of the second to fourth polymerization tanks
The liquid level is controlled so that the time is 60 minutes,
In each polymerization tank, the by-produced phenol is a by-product.
It was removed from the product discharge pipe (12). Under the above conditions,
It was operated continuously for 00 hours. The bottom of the 4th polymerization tank
Polycarbonate extracted from the rimer outlet is
Directed to a twin-screw extruder equipped with a three-stage vent port in the molten state
Butyl p-toluene sulfonate
4.0 ppm (based on the amount of neutralization of the catalyst)
Then, 4.4 times mol), hydrogenated and devolatilized, and
Turned into Viscosity average molecular weight of the obtained polycarbonate
(Mv) and terminal OH group content are 21 and 5, respectively.
It was 00 and 500 ppm. Also, the catalyst flow control valve
A series of catalyst flow rates actually measured by the measuring device provided in (8).
Continuous measurement data (hereinafter referred to as "catalyst flow control valve continuous measurement data
For short. ) From aromatic dihydroxy compound 1
Set catalyst amount within ± 0.06 μmol and ±
When the time within 0.1 μmol was calculated,
The manufacturing time was 96.7% and 99.1%. Molecular weight
Distribution (Mw / Mn) and Tan δ / η^{* -0. 87}The value of
They were 2.3 and 4,850 respectively. PC-
Represented as 1.

[0075]

[Comparative Production Example 1] In PC-2 Production Example 1, except that the program controller was not installed and the catalyst flow rate was fixed at 1.6 mL / h (set catalyst amount: 0.5 μmol to 1 mol of bisphenol A). Was carried out in the same manner as in Production Example 1. 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.

[0076]

[Comparative Production Example 2] PC-3 bisphenol A was polycondensed by an interfacial method, and the end was blocked with phenol. The viscosity average molecular weight (Mv) and terminal OH group content of the obtained polycarbonate are respectively
It was 22,100 and 30 ppm. Molecular weight distribution (M
The values of w / Mn) and Tan δ / η ^{* -0.87} are respectively
2.3 and 7,550. This is designated as PC-3.

Polycarbonate Resin Composition In the following Examples and Comparative Examples, the following were used as the materials blended with the polycarbonate. (1) Phosphoric acid ester-1: A condensed phosphoric acid ester represented by the following formula (4) (n = 1.1), CR-741, manufactured by Daihachi Chemical Co., Ltd.

[0078]

[Chemical 6]

(2) Phosphate ester-2: triphenyl phosphate, manufactured by Daihachi Chemical Co., Ltd. (3) Phosphoric acid ester-3: condensed phosphoric acid ester (n = 1.3) represented by the following formula (5), CR-733, manufactured by Daihachi Chemical Co., Ltd.

[0080]

[Chemical 7]

(4) Phosphate Ester-4: The following formula (6)
A condensed phosphoric acid ester represented by (n = 1.01), FP-
500, manufactured by Asahi Denka Co., Ltd.

[0082]

[Chemical 8]

(5) Phosphate ester-5: The following formula (7)
Condensed phosphoric acid ester (n = 1.1), CR-7
47, manufactured by Daihachi Chemical Co., Ltd.

[0084]

[Chemical 9]

(6) Polytetrafluoroethylene (hereinafter referred to as PTFE): Polyflon F-201L,
Daikin Corporation. (7) Impact resistance improver-1: Polyalkyl acrylate core / polymethyl methacrylate shell multilayer structure polymer, Paraloid EXL2315, manufactured by Kureha Chemical Industry Co., Ltd. (8) Impact resistance improver-2: Polybutadiene core / polymethylmethacrylate shell multilayer polymer, Paraloid EXL2603, manufactured by Kureha Chemical Industry Co., Ltd. (9) UV absorber: 2 (2'-hydroxy-5'-
t-octylphenyl) benzotriazole.

(10) Titanium oxide: Surface-treated titanium oxide (PC-3, manufactured by Ishihara Sangyo Co., Ltd.) manufactured by the chlorine method,
A rutile titanium oxide having an average particle diameter of 0.28 μm, which has been surface-treated with an inorganic surface treatment agent such as alumina hydrate and silicic acid hydrate, and then with an organic surface treatment agent, organohydrogensiloxane.

The physical properties of the polycarbonate resin compositions obtained in the following Examples and Comparative Examples are evaluated according to the following (11)-
The measurement method of (15) was performed. (11) Load deflection temperature (DTUL): From the resin composition,
An injection molding machine (SG75-Cycap MII, manufactured by Sumitomo Heavy Industries, Ltd.) was used to injection-mold a specified test piece under the conditions of a cylinder temperature of 280 ° C and a molding cycle of 1 minute, and heat it according to ASTM D-648. A deformation test was performed. (12) Izod impact strength: The resin composition was injection molded by an injection molding machine (SG75-Cycap MII, manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 300 ° C. and a molding cycle of 5 minutes, For a predetermined test piece molded on the fifth shot under these conditions, ASTM D-25
A 1/8 inch thick notched Izod impact test according to No. 6 was performed. (13) Hue (YI) and reflectance: 90 mm x 50 mm
A 3 mm plate was molded, and the hue was measured with a multi-light source spectrocolorimeter MSC-5N (manufactured by Suga Test Instruments), and the reflectance was
Wavelength 5 with spectrophotometer U-3400 (manufactured by Hitachi Ltd.)
The light reflectance at 50 nm was measured. (14) Mold deposit property: 500 shots continuous molding was carried out under the molding conditions of the following combustion test pieces, and after the completion, deposits on the surface of the mold were visually observed, and three-stage evaluation was performed based on the following criteria. ○: There is very little deposit on the mold. Δ: There are many deposits on the mold. X: There are very many deposits on the mold. (15) Flammability: From resin composition, injection molding machine (SG7
5-Cycap MII, manufactured by Sumitomo Heavy Industries, Ltd.
A vertical combustion test was performed on a 0.8 mm thick test piece injection-molded under the conditions of a cylinder temperature of 280 ° C. and a molding cycle of 1 minute, and evaluated according to the UL standard (UL-94).

Example 1 In 100 parts by weight of PC-1,
6 parts by weight of impact modifier-1, 0.25 parts by weight of PT
FE and 0.35 parts by weight of an ultraviolet absorber are mixed, mixed for 20 minutes with a tumbler, and then mainly supplied by a twin-screw extruder with a screw diameter of 30 mm (TEX30 manufactured by Japan Steel Works) set to a cylinder temperature of 270 ° C. A fixed amount of 106.6 parts by weight of the resin component mixed from the mouth was supplied, and 11
Part by weight of phosphoric acid ester-1 was supplied, melt-kneaded and pelletized. Pellets were pre-dried at 120 ° C for 5 hours and then 0.8 at cylinder temperature of 280 ° C with an injection molding machine.
mm mm thick fired test pieces were molded and evaluated according to the UL test method. Further, 500 shots continuous molding was carried out at a cylinder temperature of 280 ° C., and the deposits on the mold after the molding were visually judged. Further, the plate was molded at 280 ° C., and weather resistance evaluation (200 hours) was performed on the plate by sunshine fade to evaluate the hue before and after that. The test pieces used for evaluation of Izod impact strength and load deflection temperature were also used after being molded at 280 ° C. Table of evaluation results
Shown in 1.

[Comparative Examples 1 and 2] In Example 1, the PC
Example 1 except that -1 is changed to PC-2 and PC-3
Pelletization was carried out by the same method as above, and molding and evaluation were carried out in the same manner. The results are shown in Table-1. [Comparative Examples 3 and 5] The phosphoric acid ester-1 of Example 1 was changed to phosphoric acid ester-2 or phosphoric acid ester-4, and after all the components including the phosphoric acid ester were blended together, the cylinder temperature was 27.
It was melt-kneaded and pelletized by a twin-screw extruder (TEX30 manufactured by Japan Steel Works) having a screw diameter of 30 mm set to 0 ° C. After pre-drying the pellets at 120 ° C. for 5 hours, a test piece was molded and evaluated under the same conditions as in Example 1, and the results are shown in Table-
Shown in 1. Comparative Examples 4 and 6 In Example 1, the phosphoric acid ester-1
Was pelletized by the same method as in Example 1 except that phosphoric acid ester-3 or phosphoric acid ester-5 was changed, and molding and evaluation were performed in the same manner. The results are shown in Table-1.

[0090]

[Table 1]

Example 2 16 parts by weight of titanium oxide was further added to the composition of Example 1, pelletized by the same method as in Example 1, and molded and evaluated in the same manner. In the evaluation, the reflectance on the plate before and after the weather resistance evaluation was also measured. The results are shown in Table-2. [Example 3] Pelletization was performed in the same manner as in Example 2 except that the impact resistance improver-1 was changed to the impact resistance improver-2, and molding and evaluation were performed in the same manner. The results are shown in Table-2.

Comparative Examples 7 to 8 In Example 2, the PC
Pellets were formed in the same manner as in Example 2 except that -1 was changed to PC-2 and PC-3, and molding and evaluation were performed in the same manner. The results are shown in Table-2. [Comparative Examples 9 to 10] In Example 3, PC-1 was replaced with PC
-2 and PC-3, except that the pellets were formed in the same manner as in Example 2 and molded and evaluated in the same manner. The results are shown in Table-2.

[0093]

[Table 2]

[0094]

EFFECT OF THE INVENTION The flame-retardant polycarbonate resin composition of the present invention is excellent in impact strength and flame retardancy, and is also excellent in weather resistance, and further has a problem of corrosiveness of molds and screws during molding. Since it has no mold deposits and excellent moldability, it can be used not only in the electric and electronic fields, automobile fields, general industrial fields but also in fields where weather resistance is required, such as painting to compensate for the lack of weather resistance. It is possible to make products unpainted without the need for secondary processing and has great industrial value.

[Brief description of drawings]

FIG. 1 is a flow sheet diagram showing an example of a method for producing polycarbonate.

[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 12. By-product discharge pipe 13a, b, c. Vertical polymerization tank 14. Maxblend Tsubasa 15. Horizontal polymerization tank 1
6. Lattice wings

Continued front page    (72) Inventor Kazuhiko Ishii             5-6 Higashi-Hachiman 5-2, Hiratsuka City, Kanagawa Prefecture             Ryo Engineering Plastics Stock Association             Company Technology Center F-term (reference) 4J002 AC033 AC063 AC083 BD132                       BG043 BN073 BN133 BP013                       CG011 CG021 DE137 EE038                       EG068 EN028 EQ018 EU178                       EW046 FD017 FD058 FD136                       FD203

Claims (6)

[Claims] 1. (a) A polycarbonate obtained by a melting method, which has a loss angle δ and a complex viscosity η ^* (Pa · s) measured at a temperature of 250 ° C. and an angular velocity of 10 rad / s.
Of 100 parts by weight of a polycarbonate characterized by satisfying the following relational expression: 2500 ≦ ^Tanδ / η ^{* -0.87} ≦ 6000 (b) 0.5 to 4 of the phosphoric acid ester represented by the following formula (1)
0 parts by weight, (In the formula (1), R ₁ And R ₂ Each represent a methyl group, a hydrogen atom or a phenyl group, and n represents an integer of 1 to 5. ) (C) Polyfluoroethylene 0.01-3
A flame-retardant polycarbonate resin composition comprising 1 part by weight, (d) 0.5 to 30 parts by weight of an impact resistance improver, and (e) 0.01 to 2 parts by weight of an ultraviolet absorber. 2. The terminal OH group content of polycarbonate is
The flame-retardant polycarbonate resin composition according to claim 1, which is in the range of 50 to 1000 ppm. 3. The viscosity average molecular weight of polycarbonate is 1
The flame-retardant polycarbonate resin composition according to claim 1, which is in the range of 6,000 to 30,000. 4. The flame-retardant polycarbonate resin composition according to claim 1, wherein the impact resistance improver (d) is an acrylic rubber. 5. The flame-retardant polycarbonate resin composition according to claim 4, wherein the acrylic rubber is a multi-layer structure polymer containing an alkyl (meth) acrylate polymer. 6. The composition according to claim 1, further comprising 0.1 to 20 parts by weight of (f) surface-treated titanium oxide added to 100 parts by weight of (a) polycarbonate. A flame-retardant polycarbonate resin composition as described in.