JPH07166044A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To improve the flame retardancy of a resin compsn. comprising a polycarbonate-polyorganosiloxane copolymer and a polycarbonate resin by compounding the compsn. with a halogenated PS and an inorg. filler. CONSTITUTION:A polycarbonate oligomer and a polyorganosiloxane having reactive terminal groups are subjected to interfacial polycondensation in a solvent (e.g. methylene chloride) by adding an aq. NaOH soln. of bisphenol A and using a terminal stopper, a catalyst, etc., to give a polycarbonate- polyorganosiloxane (PC-PDMS) copolymer having a viscosity-average mol.wt. of 10,000-40,000. Then, 100 pts.wt. resin compsn. comprising 5-100wt.% PC-PDMS copolymer and 95-0wt.% polycarbonate resin is melt mixed with 0.5-10 pts.wt. halogenated PS (e.g. polychlorostyrene) having a wt.-average mol.wt. of 10,000-500,000 and 0-100 pts.wt. inorg. filler at about 250-300 deg.C on an extruder, etc., thus a flame-retardant polycarbonate resin compsn. is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame retardant polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition having excellent flame retardancy and process stability.

[0002]

2. Description of the Related Art Polycarbonate resin (hereinafter sometimes abbreviated as PC) is a polycarbonate resin.
It has excellent mechanical strength, electrical characteristics, transparency, etc., and is widely used as an engineering plastic in various fields such as electric and electronic devices and automobiles.
As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fiber is added as an inorganic filler is known in order to improve impact resistance (Izod impact strength) and dimensional stability. However, the polycarbonate resin has a drawback that the impact resistance is significantly lowered by adding glass fiber. Heretofore, various studies have been made on a method of improving the impact resistance which is lowered by adding the glass fiber to a polycarbonate resin. For example, JP-A-5
In Japanese Patent Application Laid-Open No. 5-160052 and Japanese Patent Application Laid-Open No. 2-173061, a polycarbonate resin and a polycarbonate-polyorganosiloxane copolymer (hereinafter referred to as PC-PDMS
Abbreviated as a copolymer. ) Is disclosed,
By introducing this PC-PDMS copolymer,
The impact resistance is improved. Furthermore, the PC-PDM
In order to expand the market of S copolymer and inorganic filler (particularly glass fiber) resin composition mainly in the office automation field, it is necessary to develop materials with excellent flame retardancy and process stability. There is a strong demand.

[0003]

Therefore, the present inventors have
In view of the above situation, the inventors have conducted intensive studies to solve the drawbacks of the conventional method and develop a polycarbonate resin composition having excellent flame retardancy and process stability. As a result, it was found that a polycarbonate-based resin composition containing a polycarbonate-polyorganosiloxane copolymer as an essential component and a halogenated polystyrene and, if necessary, an inorganic filler, has desired properties. . The present invention has been completed based on such findings.

That is, the present invention is based on 100 parts by weight of a polycarbonate resin comprising (A) a polycarbonate-polyorganosiloxane copolymer (5 to 100% by weight) and (B) a polycarbonate resin (95 to 0% by weight).
A flame-retardant polycarbonate resin composition comprising 0.5 to 10 parts by weight of (C) halogenated polystyrene and 0 to 100 parts by weight of (D) an inorganic filler.

First, the polycarbonate-polyorganosiloxane copolymer (PC-PDMS copolymer) as the component (A) which constitutes the polycarbonate resin composition of the present invention.
Are various, but are preferably the general formula (I)

[0006]

[Chemical 1]

[Wherein R ¹ and R ² are each a halogen atom (eg, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group,
Propyl group, n-butyl group, isobutyl group, amyl group,
Isoamyl group, hexyl group, etc.), which may be the same or different. m and n are
Each is an integer of 0 to 4, and when m is 2 to 4, R
^1's may be the same as or different from each other, and when n is 2 to 4, they may be the same or different. Z is an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms (for example,
Methylene group, ethylene group, propylene group, butylene group,
Pentylene group, hexylene group, ethylidene group, isopropylidene group, etc.), C5-C15 cycloalkylene group or C5-C15 cycloalkylidene group (for example, cyclopentylene group, cyclohexylene group, cyclopentylidene group) , Cyclohexylidene group), or —SO ₂ —, —SO—, —S—, —O—, —CO— bond or the general formula (II) or (II ′).

[0008]

[Chemical 2]

The bond represented by ] Polycarbonate part having a repeating unit represented by the general formula
(III)

[0010]

[Chemical 3]

[Wherein R ³ , R ⁴ and R ⁵ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, etc.) Or a phenyl group, which may be the same or different. Further, p and q are each an integer of 0 or 1 or more. ] It consists of a polyorganosiloxane part having a repeating unit represented by the following formula. Here, the degree of polymerization of the polycarbonate part is
3 to 100 is preferable, and the degree of polymerization of the polyorganosiloxane part is preferably 2 to 500. PC-P above
The DMS copolymer comprises a polycarbonate part having a repeating unit represented by the general formula (I) and a general formula (II
A block copolymer comprising a polyorganosiloxane moiety having a repeating unit represented by I), having a viscosity average molecular weight of 10,000 to 40,000, preferably 15,000.
It is from 0 to 35,000.

Such a PC-PDMS copolymer may be prepared, for example, by a polycarbonate oligomer (PC oligomer) which constitutes a pre-manufactured polycarbonate part and a polyorgano having a reactive group at a terminal which constitutes a polyorganosiloxane part. Siloxane (for example, polydialkylsiloxane such as polydimethylsiloxane (PDMS), polydiethylsiloxane or polymethylphenylsiloxane) is dissolved in a solvent such as methylene chloride, chlorobenzene and chloroform, and an aqueous sodium hydroxide solution of bisphenol is added. It can be produced by carrying out an interfacial polycondensation reaction using a monohydric phenol as a terminal stopper and triethylamine or trimethylbenzylammonium chloride as a catalyst. Further, a polycarbonate-polyorganosiloxane copolymer produced by the method described in JP-B-44-30105 or JP-B-45-20510 can also be used. Here, the PC oligomer having a repeating unit represented by the general formula (I) can be prepared by the solvent method, that is, in the presence of a known acid acceptor and a terminal terminator in a solvent such as methylene chloride, in the general formula (IV).

[0013]

[Chemical 4]

[In the formula, R ¹ , R ² , Z, m and n are the same as defined above. ] It can manufacture by the reaction of the dihydric phenol and carbonate precursor like phosgene represented by these, or the transesterification reaction of dihydric phenol and carbonic acid diester (For example, carbonate precursor like diphenyl carbonate). Here, there are various dihydric phenols represented by the general formula (IV). Specifically, as the bis (4-hydroxyphenyl) alkane, for example, bis (4-hydroxyphenyl) methane [bisphenol F]; 2,2-bis (4-hydroxyphenyl) phenylmethane; bis (4
-Hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,5-dichloro-4-hydroxyphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) ) Methane; 1,1-bis (4-hydroxyphenyl) ethane; 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4
-Hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A]; 2-methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (4- Hydroxyphenyl-1-methylphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2- Bis (3,5-dichloro-4-
Hydroxyphenyl) propane; 2,2-bis (3,5)
-Dibromo-4-hydroxyphenyl) propane; 2,
2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2 , 2-bis (4-hydroxyphenyl) butane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) butane [bisphenol B]; 1,4-bis (4- Hydroxyphenyl) butane; 2,2-bis (4
-Hydroxyphenyl) pentane; 3,3-bis (4-
Hydroxyphenyl) pentane; 4-methyl-2,2-
Bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 3,3-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane and the like.

Examples of the bis (4-hydroxyphenyl) cycloalkane include 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane. 1,1-bis (4-hydroxyphenyl) cyclodecane and the like can be mentioned. And bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-
4-hydroxyphenyl) sulfone; dihydroxydiarylsulfones such as bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-4-hydroxyphenyl) ether, etc. Dihydroxydiaryl ethers, 4,4′-dihydroxybenzophenone;
3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiarylketones such as dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide;
Bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide;
Dihydroxydiaryl sulfoxides such as bis (3-methyl-4-hydroxyphenyl) sulfoxide,
Examples thereof include dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl, bisphenolfluorene such as 9,9-bis (4-hydroxyphenyl) fluorene, thiobisphenol, bisphenol Z, and tetrabromobisphenol A. Further, examples of the tetrahalogenobisphenols include tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, tetraiodobisphenol A, tetrabromobisphenol F, tetrachlorobisphenol F, tetrachlorobisphenol B and the like. Among these, bisphenol A is particularly preferably used. And these dihydric phenol may be used individually, and may be used in combination of 2 or more type.

As the carbonic acid diester, a carbonic acid diaryl compound, a carbonic acid dialkyl compound or a carbonic acid alkylaryl compound can be used. Here, examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, and bisphenol A bisphenyl carbonate. Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate and the like. Further, as the alkyl aryl carbonate compound, for example,
Methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate, etc. are mentioned.

Various kinds of end terminators can be used. Usually, it is used for polymerization of polycarbonate, and monohydric phenol is used.
For example, phenol, p-cresol, p-tert-butylphenol, p-tert-amylphenol, p-tert
-Octylphenol, p-cumylphenol, p-bromophenol, tribromophenol, nonylphenol and the like.

In the present invention, the PC oligomer used for producing the PC-PDMS copolymer may be a homopolymer using one of the above-mentioned dihydric phenols.
It may be a copolymer of two or more species. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol. The polyorganosiloxane represented by the general formula (III) can be obtained, for example, by reacting dialkyldicyclosilane and / or diaryldichlorosilane with water. Examples of such a polyorganosiloxane monomer include dimethylsiloxane and methylphenylsiloxane.

Next, the polycarbonate resin (P) as the component (B) which constitutes the polycarbonate resin composition of the present invention.
C) can be easily produced by reacting a dihydric phenol with phosgene or a carbonic acid diester compound. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator,
It is produced by a reaction between a dihydric phenol and a carbonate precursor such as phosgene, or by a transesterification reaction between a dihydric phenol and a carbonic acid diester (a carbonate precursor such as diphenyl carbonate).
Here, the dihydric phenol may be the same as or different from the compound represented by the general formula (IV). Examples of the carbonic acid diester include the above-mentioned diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol.

Various flame retardants made of halogenated polystyrene as the component (C) can be used. Specifically, polymer type aromatic halogen flame retardants such as polychlorostyrene, polydibromostyrene and polytribromostyrene are preferably used. The weight average molecular weight of these is preferably from 10,000 to 50,000. And the content of halogen is 50-80%
Are preferred. Furthermore, the average particle size is 1 to 3.
It is 0 μm.

Further, there are various kinds of inorganic fillers as the component (D) which constitutes the resin composition of the present invention.
It is used for the purpose of increasing the mechanical strength, durability or amount of a polycarbonate resin composition. Specifically, for example, potassium titanate whiskers, mineral fibers (eg, rock wool), glass fibers, carbon fibers, metal fibers (eg, stainless fibers), aluminum borate whiskers, silicon nitride whiskers, boron fibers, tetrapot shapes Zinc oxide whiskers, talc, clay, mica, pearl mica,
Aluminum foil, alumina, glass flakes, glass beads,
Examples thereof include glass balloons, carbon black, graphite, calcium carbonate, calcium sulfate, calcium silicate, titanium oxide, zinc sulfide, zinc oxide, silica, asbestos, and quartz powder. These inorganic fillers may be surface-treated in advance or may be untreated.
Examples of the surface treatment agent include chemical treatments with various treatment agents such as silane coupling agent type, higher fatty acid type, fatty acid metal salt type, unsaturated organic acid type, organic titanate type, resin acid type and polyethylene glycol type. Alternatively, physical surface treatment may be mentioned.

Among these, as the glass fiber as the fibrous filler, any of alkali-containing glass, low-alkali glass, non-alkali glass and the like can be preferably used. The length of this glass fiber is preferably 0.01 to 2 mm in the pellet, more preferably,
It is in the range of 0.05 to 1 mm. Since these glass fibers may break during the kneading with the above-mentioned polycarbonate resin, the size when resisting the kneading is generally preferably in the range of 1 to 6 mm in length. Further, the diameter is usually sufficient to be 1 to 20 μm. The form of these glass fibers is not particularly limited, and includes, for example, roving, milled fiber,
Any form such as chopped strands can be used. These glass fibers may be used alone or in combination of two or more. further,
For the purpose of improving the adhesiveness to the polycarbonate resin, it is desirable to use those glass fibers which have been surface-treated with a surface-treating agent and then subjected to bundling treatment with an appropriate bundling agent. Examples of the surface treatment agent include silane-based agents such as aminosilane-based, epoxysilane-based, vinylsilane-based, acrylsilane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and boron-based coupling agents. . Among these, silane coupling agents and titanate coupling agents, particularly silane coupling agents are preferable. There is no particular limitation on the method of treating the glass fiber with the above-mentioned surface treatment agent, and there are conventionally used methods such as an aqueous solution method, an organic solvent method,
Any method such as a spray method can be used. Also,
Examples of the sizing agent include urethane type, acrylic type, acrylonitrile-styrene type copolymer, and epoxy type, and any of them can be used. Regarding the method for bundling the glass fiber using these sizing agents,
There is no particular limitation, and any conventionally used method such as dip coating, roller coating, spray coating, flow coating, or spray coating can be used.

The carbon fiber is generally manufactured by firing using cellulose fiber, acrylic fiber, lignin, petroleum or coal-based special pitch as a raw material, and various carbon fibers such as flame resistance, carbonaceous or graphite are used. There are types. The length of carbon fiber is usually in the range of 0.01 to 10 mm in the pellet, and the fiber diameter is 5 to 15 μm.
m. The form of the carbon fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, chopped strand, and strand. The surface of the carbon fiber may be surface-treated with an epoxy resin, a urethane resin or the like in order to enhance the affinity with the above copolymer.

The resin composition of the present invention comprises the above-mentioned respective components (A), (B), (C) and (D). First, these respective components are the polycarbonate-polyorgano of the (A) component. The siloxane copolymer is blended in an amount of 5 to 100% by weight, preferably 50 to 100% by weight, and 95 to 0% by weight, preferably 50 to 0% by weight of the component (B) polycarbonate resin to prepare a polycarbonate resin. To be done. Here, in the preparation of the above polycarbonate-based resin, the proportion of the polyorganosiloxane moiety in the polycarbonate-polyorganosiloxane copolymer of the component (A) preferably comprises the components (A) and (B). 0.5-40% by weight based on polycarbonate resin
Is desirable. Then, component (A) and (B)
(C) component halogenated polystyrene 0.5-10 with respect to 100 parts by weight of the polycarbonate resin composed of the components
1 part by weight, preferably 1-5 parts by weight, and 1-100 parts by weight, preferably 10-80 parts by weight of the inorganic filler of the component (D) are blended, and the flame-retardant polycarbonate resin composition of the present invention. Is obtained. Here, if the component (C) is less than 0.5 parts by weight, the flame retardant effect is small. On the other hand, if it exceeds 10 parts by weight, the impact strength is lowered and the retention heat stability is further deteriorated, which is not preferable. Furthermore, when the amount of the component (D) exceeds 100 parts by weight, the mechanical properties such as rigidity and strength have little effect of improving the mechanical properties such as rigidity and strength relative to the blending amount, and impact strength , Rather lower. And
The take-off property of the strand during kneading becomes unstable, which is not preferable.

In the resin composition of the present invention, in addition to the components (A), (B), (C) and (D), if necessary, within a range not impairing the object of the present invention ( As the component E), various additives or other synthetic resins, elastomers and the like can be blended. First, as the additive, for example, a hindered phenol-based, phosphite-based, phosphoric ester-based, amine-based antioxidant, for example, a benzotriazole-based, benzophenone-based ultraviolet absorber, for example, hindered amine -Based light stabilizers, for example, aliphatic carboxylic acid ester-based, paraffin-based, internal lubricants such as silicone oil and polyethylene wax, mold release agents, commonly used flame retardants, flame retardant aids, antistatic agents,
Colorants and the like can be mentioned.

Examples of the other synthetic resin include polyester (polyethylene terephthalate, folybutylene terephthalate, etc.), polyamide, polyarylate, polyethylene, polypropylene, polymethylmethacrylate, polystyrene, AS resin, ABS resin and the above (A). Examples of the resin include polycarbonates other than the component polycarbonate). And
Examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, polyester elastomer, holamide elastomer, and core-shell type MBS and MAS.

The resin composition of the present invention can be obtained by blending the above-mentioned respective components (A), (B), (C) and (D) and, if necessary, (E) and kneading. it can. Then, for the compounding and kneading, a method usually used, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. Can be done using. In addition,
The heating temperature for kneading is usually selected in the range of 250 to 300 ° C. The resin composition thus obtained can be subjected to various known molding methods, for example, injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding, etc., to produce various molded articles. Can be offered.

[0028]

The present invention will be further described in detail with reference to production examples, examples and comparative examples. Production Example 1-1 [Production of PC oligomer] 60 kg of bisphenol A was added to 400 liters of a 5 wt% sodium hydroxide aqueous solution.
Was dissolved and a sodium hydroxide aqueous solution of bisphenol A was prepared. Then, the aqueous sodium hydroxide solution of bisphenol A kept at room temperature was flown at a flow rate of 138 liters / hour, and methylene chloride was flown at a flow rate of 69 liters / hour through an orifice plate into a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. Introduce phosgene into this and co-flow 1
It was blown in at a flow rate of 0.7 kg / hour and continuously reacted for 3 hours. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the discharge temperature of the reaction solution at 25 ° C. The pH of the discharged liquid is 10 to 11
Was adjusted so that The aqueous phase was separated and removed by allowing the reaction solution thus obtained to stand, and a methylene chloride phase (220 liters) was collected. The degree of polymerization of the PC oligomer obtained here was 3 to 4.

Production Example 2-1 [Synthesis of Reactive PDMS] 1,483 g of octamethylcyclotetrasiloxane, 18.1 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed, and at room temperature. It was stirred for 17 hours. Then, the oil phase was separated, 25 g of sodium hydrogen carbonate was added, and the mixture was stirred for 1 hour. After filtration, vacuum distillation was performed at 150 ° C. and 3 torr to remove low-boiling substances to obtain an oil. 60 g of 2-allylphenol and 0.0014 g of platinum as a platinum chloride-alcoholate complex
294 g of the oil obtained above in a mixture with
Was added at the temperature of. The mixture was stirred for 3 hours while maintaining the temperature of 90 to 115 ° C. The product was extracted with methylene chloride and washed 3 times with 80% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulphate and evaporated in vacuo to a temperature of 115 ° C. The obtained terminal phenol PDMS is NM
By measurement of R, the number of repeating dimethylsilanooxy units was 150.

Production Example 2-2 [Synthesis of Reactive PDMS] In Production Example 2-1,
The same procedure as in Production Example 2-1 was repeated, except that the amount of 1,3,3-tetramethyldisiloxane was changed to 96 g. In the obtained terminal phenol PDMS, the number of repeating dimethylsilanooxy units was 30 as measured by NMR.

Production Example 2-3 [Synthesis of Reactive PDMS] A mixture of 100 g of water and 206 g of dioxane was added to 800 g of dimethyldichlorosilane over 2 hours. The resulting mixture was heated to gentle reflux with stirring until homogeneous. The mixture was stripped under vacuum to 202 ° C. at a pressure of 12 mm Hg. The stripped product was then filtered to give a clear oil. 225 g of this oily substance
It was dissolved in 0 g dry dichloromethane and added to a mixture of 114 g bisphenol A, 130 g dry pyridine, 1,300 g dichloromethane. The addition was done over 65 minutes with vigorous stirring. After that, wash with alkali with 1,000 g of sodium hydroxide aqueous solution (0.01 N),
Acid wash with 1,000g hydrochloric acid (0.01N), 1,000g
Washing with water was sequentially performed. Dichloromethane was removed by evaporation to obtain a reaction PDMS having a phenolic hydroxyl group at a target end. Obtained terminal phenol PDMS
Was 13, and the number of repeating dimethylsilanooxy units was 13 as measured by NMR.

Production Examples 3-1 to 4 [Production of PC-PDMS Copolymers A _{1 to} A ₄ ] Production Example 2
The PC oligomer 10 obtained in Production Example 1 was prepared by dissolving the reactive PDMSag obtained in Nos. 1-2 in 2 liters of methylene chloride.
Mixed with liters. 26 g of sodium hydroxide
Dissolved in 1 liter of water and triethylamine 5.
7 cc was added, and the mixture was stirred at 500 rpm for 1 hour at room temperature. Then, 600 g of bisphenol A was dissolved in 5 liters of a 5.2 wt% sodium hydroxide aqueous solution,
Methylene chloride (8 liters) and p-tert-butylphenol bg were added, and the mixture was stirred at 500 rpm at room temperature for 2 hours. Thereafter, 5 liters of methylene chloride was added, followed by washing with 5 liters of water, washing with 5 liters of 0.01N aqueous sodium hydroxide solution with alkali, washing with 5 liters of 0.1N hydrochloric acid and washing with 5 liters of water. Finally, methylene chloride was removed to obtain a chip-shaped PC-PDMS copolymer. The amount of a and b used in Production Examples 3-1 to 4 was first
Shown in the table.

[0033]

[Table 1]

The PCs obtained in Production Examples 3-1 to 4
Table 2 shows the PDMS chain length (n: dimethylsilanooxy units), PDMS content and Mv (viscosity average molecular weight) of the PDMS copolymer.

[0035]

[Table 2]

The PDMS chain length, PDMS content and viscosity average molecular weight were measured as follows. 1: PDMS chain length: the peak of the methyl group (n dimethylsilanoxy unit) dimethylsiloxane seen 0.2ppm in ¹ H-NMR, seen in 2.6 ppm PC-
It was calculated from the intensity ratio with the methylene group peak of the PDMS bond. 2: PDMS content Bisphenol A found at 1.7 ppm in ¹ H-NMR
Was calculated from the intensity ratio of the peak of the methyl group of isopropyl and the peak of the methyl group of dimethylsiloxane seen at 0.2 ppm. 3: Viscosity average molecular weight (Mv) The viscosity of the methylene chloride solution at 20 ° C. was measured with an Ubbelohde type viscosity tube, and the intrinsic viscosity [η] was calculated from this, and then calculated by the following formula. [Η] = 1.23 × 10 ⁻⁵ × Mv ^0.83

Production Example 3-5 [Production of PC-PDMS Copolymer A ₅ ] 160 g of the reactive PDMS obtained in Production Example 2-3 was dissolved in 2 liters of methylene chloride to prepare the PC oligomer obtained in Production Example 1. 10
L was mixed. 26 g of sodium hydroxide
Dissolved in 1 liter of water and triethylamine
Add 5.7 cc and stir at 500 rpm for 1 hour at room temperature.
It was made to react. Then, to the above reaction system, bisphenol A60 was added to 5 liters of a 5.2 wt% sodium hydroxide aqueous solution.
Dissolved 0 g, 8 liters of methylene chloride and p
Add 81 g of -tert-butylphenol, 500 rpm
The mixture was stirred and reacted at room temperature for 2 hours. After the reaction, add 5 liters of methylene chloride and wash with 5 liters of water.
Alkali washing with 5 liters of 01 normal sodium hydroxide aqueous solution, acid washing with 5 liters of 0.1 normal hydrochloric acid and water washing with 5 liters of water are carried out in order, and finally methylene chloride is removed to obtain a chip-like PC-PDMS copolymer. Obtained. The obtained PC-
The PDMS content of the PDMS copolymer was 3.5% by weight and the viscosity average molecular weight was 20,000.

Examples 1-8 and Comparative Examples 1-7 PC-PDMS copolymer A obtained in Production Examples 3-1-5
_{1 to} A ₅ , polycarbonate, a flame retardant and an inorganic filler were mixed in the proportions shown in Table 2, and a twin-screw extruder with a vent [TOSHIBA MACHINE CO., LTD., TEM-35] was added from the top,
Glass fibers were fed from the side, kneaded at a temperature of 300 ° C., and pelletized. The obtained pellets were mixed with an injection molding machine [TOSHIBA MACHINE CO., LTD. IS100EN]
A test piece was produced by injection molding in a mold cavity at a molding temperature of 00 ° C and a mold temperature of 80 ° C.

The flame retardancy and Izod impact strength of the test pieces obtained in Examples 1 to 8 and Comparative Examples 1 to 7 were measured as quality evaluation. Further, it was allowed to stay in the injection molding machine at a cylinder temperature of 300 ° C. for 20 minutes, and the difference in color tone (color difference: Δ * ab) from the molded product of a normal cycle (cylinder temperature of 300 ° C., 40 seconds retention) was measured. The results are shown in Table 3. The materials used in the examples and comparative examples are as follows. 1) Polycarbonate TAFRON A1500 [Idemitsu Petrochemical Co., Ltd., Mv = 1
5,000] 2) C ₁ : Brominated polystyrene Pyrocheck 68PB [Nissan Ferro Organic Chemical Co., Ltd.]
Made, polytribromostyrene, bromine content 68%, Mw
= 27,000] C _2: brominated epoxy Purasamu EP-100 [Dainippon Ink and Chemicals Co., Ltd.,
Epoxy brominated bisphenol A oligomers type, bromine content 52%] C _3: Brominated bisphenol A (brominated BPA) Gray tray box BC-52 [Great Lakes Corporation, a brominated bisphenol A oligomers type, bromine content 52
%] 3) D ₁ : glass fiber 03MA409C [manufactured by Asahi Fiber Glass Co., Ltd., length 3 mm, diameter 13 μm] D ₂ : carbon fiber HTA-C6-SR [manufactured by Toho Rayon Co., Ltd., length 6 m]
m, diameter 7 μm]

[0040]

[Table 3]

[0041]

[Table 4]

Each measurement was performed as follows. 1) Combustibility UL94 standard vertical combustion test (wall thickness 1/16 inch), V-0 target 2) Izod impact strength conforming to JIS K7110 1/8 inch thickness measurement 2
3 ° C. with notch 3) Color difference (ΔE * ab) Measured by a reflection method according to JIS K7105.

[0043]

INDUSTRIAL APPLICABILITY As described above, the polycarbonate resin composition of the present invention is excellent in flame resistance and process stability as well as impact resistance. Therefore, the flame-retardant polycarbonate-based resin composition of the present invention is used as a material for various molded products, for example, various molded products widely used in the fields of electric and electronic devices, the field of automobiles, etc., particularly in office automation fields. It is effectively used.

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Claims (3)

[Claims] 1. A halogenated polystyrene (C) based on 100 parts by weight of a polycarbonate-based resin composed of 5 to 100% by weight of a polycarbonate-polyorganosiloxane copolymer (A) and 95 to 0% by weight of a polycarbonate resin (B). 0.5-10 parts by weight and (D) inorganic filler 0-10
A flame-retardant polycarbonate resin composition comprising 0 parts by weight. 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the weight average molecular weight of the halogenated polystyrene (C) is from 10,000 to 50,000. 3. The proportion of the polyorganosiloxane moiety in the (A) polycarbonate-polyorganosiloxane copolymer is 0.5 to 40% by weight based on the polycarbonate resin composed of the (A) component and the (B) component. The flame-retardant polycarbonate resin composition according to claim 1, wherein