TWI224611B - Method for producing a flame retardant polycarbonate resin composition - Google Patents

Abstract

Disclosed is a method for producing a flame retardant polycarbonate resin composition using a screw extruder comprising zones (a), (b) and (c), which are arranged in this order as viewed in an extrusion direction of the extruder, the method comprising (1) continuously feeding a resin component comprised mainly of a polycarbonate to zone (a), while continuously feeding an aqueous dispersion of a fluoropolymer to zone (a) separately from the resin component at a feeding rate which is 0.01 to 10 % of the feeding rate of the resin component, and continuously feeding an organic phosphorus compound to zone (b) at a feeding rate which is 1 to 30% of the feeding rate of the resin component, where the resin component, the aqueous dispersion and the organic phosphorus compound are extruded toward an extrusion outlet through zone (c), while kneading, wherein the resin components present in zone (a), (b) and (c) are maintained in non-molten state, partially molten state, and completely molten state, respectively, the extrusion being performed at a specific energy of from 0.13 to 0.20 kW.hr/kg, wherein the temperature of the resin component in the extruder is not higher than 300 DEC G, thereby producing a flame retardant polycarbonate resin composition; and (2) withdrawing the flame retardant polycarbonate resin composition through the extrusion outlet therefor.

Description

1224611 A7 ___B7 V. Description of the Invention (1) [Technical Field] (Please read the precautions on the back before filling out this page) The present invention relates to a method for manufacturing a flame retardant polycarbonate resin composition. In more detail, the present invention is printed using an employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which is provided with a screw extruder configured with sequential arrangement of sections (a), (b), and (C) in the extrusion direction, and includes ( 1) A resin component mainly composed of polycarbonate is continuously supplied to the section (a), and on the other hand, an aqueous dispersion of a fluoropolymer and the resin component are continuously and separately supplied at a specific rate. Outside the segment (a), an organic phosphorus compound is continuously supplied to the segment (b) at a specific rate, and the resin component 'the aqueous dispersion and the organic phosphorus compound are passed through the segment (c) during kneading. Extrude in the direction of the outlet directly communicating with the section (c). At this time, the resin components in the sections (a), (b), and (c) are maintained in an unfused state, a partially molten state, and a complete state, respectively. In the molten state, and the extrusion method is performed under the conditions that the resin temperature in the extruder is 300 t or less and the specific energy is 0.1 to 0.2 kw · hr / kg; (2) Steps such as pulling out the obtained resin composition from the above-mentioned discharge port The method of producing the flame-retardant polycarbonate resin composition. According to the method of the present invention, the manufacture of a flame-retardant polycarbonate resin composition can reduce the load on the extruder, prevent excessive heating of the molten resin, and can produce at a high speed, and can avoid the cause caused by fluoropolymer agglomerates. The resulting removal of foreign matter is blocked by a filter, or the extruded monofilament is troublesome in production, etc., and can be manufactured stably and continuously for a long time. In addition, according to the method of the present invention, if the dispersibility of the fluoropolymer in the composition is improved, a flame-retardant polycarbonate resin having excellent flame retardancy and mechanical properties, and a flame-retardant polycarbonate resin having excellent appearance and color tone can be obtained. Thing. i Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ~ -4-1224611 A7 B7 V. Description of the invention (2 [Previous technology] Polycarbonate (pc), doped with acrylonitrile butadiene Resin coins obtained from olefin-phenethyl fine resin (ABS) and organic phosphorus compound flame retardant (hereinafter, also referred to as "P s / AB s / phosphorus flame retardant composition") The resin composition using non-chlorine and bromine-based flame retardants has excellent melt fluidity, rigidity, impact resistance, heat resistance, and light discoloration resistance, so it is widely used in computer screens, notebook computers, Shell materials for office automation (〇A) machines such as printers, personal word processors, photocopiers, etc. pc / ABS / Phosphorous flame retardant composition, in general, PC and ABS with resin content, and Phosphorous Flame retardants, and even fluid polymers used as dripping preventives for combustibles, are prepared by melt-kneading using a kneading device such as an extruder. Fluid polymers, especially polysilicon with fibril formation ability Fluoroethylene (PTFE) The function of preventing the dripping of combustibles is the effect produced by the fibril structure of the fluoropolymer formed in the resin. In the past, the p C / ABS / phosphorus flame retardant composition, that is, the viscosity of the molten resin was low. Therefore, it has the property of dripping of the combustible solution. Therefore, in order to prevent dripping of the combustible PC / ABS / phosphorus-based flame retardant composition, if a chlorine 'bromine-based compound is used as a flame retardant in order to make it difficult When comparing the situation of flammable resin composition, it is relatively difficult to obtain satisfactory results if the amount of fluoropolymer is not increased. However, if the amount of fluoropolymer is increased, the melt flow of the resin composition will be caused Reduce the cost, and reduce the cost of resin composition Paper size Applies to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) Printed by the Bureau's Consumer Cooperatives -5- 1224611 A7 _____ B7 V. Impact strength of the molded product obtained according to the description of the invention (3). Moreover, often due to the poor dispersion of the fluoropolymer, it often fails to obtain the required The effect of preventing dripping. Therefore, how to add a small amount of fluoropolymer to the pc / ABS / phosphorus flame retardant composition to form a fibril structure is a problem that needs to be overcome in the current technology. The PC / ABS / phosphorus flame retardant composition is manufactured by first pre-mixing each resin component and the fluoropolymer in a mixing device such as a drum mixer, and then using a melt-kneading device such as an extruder. Melt-kneading. In addition, phosphorus-based flame retardants are usually liquid, so pumps in the middle of the extruder are often used, and they are often squeezed and added by nozzles for injection. However, in the manufacturing method described above, because the fluoropolymer is easy to aggregate due to its own friction, in the prepolymerization step, agglomerates of the fluoropolymer are often generated, and the agglomerates make the molded product The appearance is deteriorated. In addition, the fluoropolymer in the resin composition is not uniformly dispersed due to the generation of agglomerates, which makes it easy for dripping of combustible materials. Therefore, the expected flame retardance effect is often not achieved. In addition, in terms of production problems, in addition to a complicated pre-polymerization process, a filter for foreign matter removal installed in an extruder is required for industrially manufacturing a PC / ABS / phosphorus flame retardant composition. Obstacles caused by agglomerates of fluoropolymers often cause production obstacles such as increased resin pressure or filament breakage during extrusion. This problem is also a problem that cannot be completed without stopping the extruder, so it often causes continuous The lack of stability in production. Therefore, for the PC / ABS / phosphorus flame retardant composition, there have been various attempts to uniformly disperse the fluoropolymer drip prevention agent in the composition. This paper is applicable to the Chinese National Standard (CNS) A4 specification ( 210X297 mm) (Please read the precautions on the back before filling out this page) C. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -6-1224611 A7 ____ B7___ V. Description of the invention (4) (Please read the first Note that please fill out this page again). One of them is, for example, a method of mixing it with a small amount of a thermoplastic resin and using a fluoropolymer as a matrix batch. For example, Japanese Unexamined Patent Publication No. 6 0-2 5 8 2 6 3 describes that an aqueous fluoropolymer dispersion and an aqueous styrene-acrylonitrile resin or an aqueous acrylonitrile-butadiene styrene resin are described. A method of coagulating the emulsion mixture, and then washing and drying the obtained coagulum to obtain a powder obtained from a fluoropolymer and a thermoplastic resin. Thereafter, the powder is added to a carbonate resin and melt-kneaded. A method of preparing a resin composition in which the fluoropolymer is uniformly dispersed. However, in this method, it is necessary to have a production process for producing a powder formed by a fluoropolymer and a thermoplastic resin. Therefore, in addition to being extremely complicated, the entire production process is formed by the fluoropolymer and the thermoplastic resin produced by this method. Among the powders, because the proportion of the fluoropolymer is too large, the fluidity of the powder is extremely poor, and it may be difficult to quantitatively feed the powder into the extruder, or cause blockages near the feed inlet. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Japanese Patent Laid-Open No. 2-6 5 3 6 discloses that an aqueous dispersion of PTFE having fibril formation ability is continuously mixed so as not to be mixed with a thermoplastic resin. It is fed into the extruder for mixing and dispersing, so there is no need for special equipment or steps to continuously and simply prepare a thermoplastic resin containing dispersed PTFE. However, in this publication, the flame retardant is only exemplified by the use of bromine-based flame retardants, and the resin composition of the present invention is different from that of bromine-based flame retardants. There are no records on the manufacture of PC / ABS / phosphorus flame retardant compositions that cause problems such as dripping of combustibles. In addition, Japanese Unexamined Patent Publication No. 10—3 3 8 8 14 discloses that the scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) " 一 ---- -7- 1224611 A7 B7 V. Invention Note (5) (Please read the precautions on the back before filling out this page) A method for continuously adding a PTFE dispersion to a molten thermoplastic resin in order to obtain a composition with excellent combustible material drip prevention properties. However, in this method, when a PTFE dispersion is added to a high-temperature molten resin, the PTFE dispersion is easily scattered in the input port, and there is a disadvantage of generating a large amount of volatiles. Therefore, the stability of continuous productivity or From the perspective of operating environment, there are many problems to be solved. In addition, European Patent EP 9 0 0 641 discloses a method for continuously adding a PTFE emulsion to a press machine by peristaltic pump (perista 11 icpump) to produce a flame-retardant resin composition. The use of phosphorus-based flame retardants is not disclosed in the same patent. In addition, in the manufacture of the PC / ABS / phosphorus flame retardant composition, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, there is an urgent need for an addition to the requirement to improve the dispersion uniformity of the fluoropolymer in the composition. A method for reducing the load of the extruder and suppressing the heat generation of the molten resin as much as possible during melt-kneading, so that a resin composition having excellent color tone or mechanical properties can be efficiently produced at a high production speed. Among them, when melt-kneading, increasing the temperature of the molten resin can reduce the viscosity of the molten resin, reduce the load on the extruder, and increase the production speed of the resin composition. In the PC / ABS / phosphorus flame retardant composition, it is easier to react when the molecular weight of PC is lowered or the hue of the resin composition is lowered during the melt-kneading process, so the productivity can be improved without increasing the kneading temperature. limit. In order to maintain the mechanical properties or hue of the P c / ABS / phosphorous flame retardant composition, it should be better to melt-knead at a low temperature as much as possible, but when the kneading temperature of the PC resin is too low, its melt viscosity is significant. Due to the increased nature, there will be a problem of reduced production speed. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -8-1224611 A7 B7 V. Description of the invention (6) Especially the polycarbonate based on the flame retardant of organic phosphorus compound based flame retardant Resin compositions often suffer from reduced physical properties due to thermal decomposition or hydrolysis of organic phosphorus compounds. For example, when the resin composition is exposed to high temperature and high humidity for a long time, its mechanical properties such as impact resistance and breaking strength Physical properties will be significantly reduced, and problems such as a decrease in color tone will occur. This problem will cause great disadvantages such as loss of reliability for long-term use of the resin composition. Therefore, the same material also aims to improve its high temperature and humidity resistance. In response to this goal, Japanese Unexamined Patent Publication No. 1 1 3 1 0 6 95 discloses that the use of organic phosphorus compounds having an acid value of less than 1 mg K ◦ H / g as the polycarbonate resin is difficult to burn. The method of use. However, the use of an organic phosphorus compound having a low acid value as a flame retardant disclosed in the publication has not been able to easily produce a resin composition that can sufficiently improve high temperature and humidity resistance. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs --------- • Installation-(Please read the precautions on the back before filling this page) As mentioned above, it is difficult to manufacture PC / ABS / phosphorous In the fuel composition, there is an urgent need to develop a resin composition in which a fluoropolymer is uniformly dispersed, and at the same time, it has good flame retardancy and mechanical properties. In addition to flame retardancy, polycarbonate has excellent appearance and color tone. Ester resin composition, which has a small load on the extruder, can be produced at high speed, has better efficiency, and is an excellent method for stable and continuous production for long-term use. [Contents of the Invention] Based on the foregoing circumstances, the present inventors have conducted in-depth research on the development of a manufacturing method capable of producing a flame retardant polycarbonate resin composition having the excellent properties described above, and have proposed a method of using a configuration. Extrusion direction: This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) ~ ---- -9-1224611 A7 B7 V. Description of the invention (7) Configuration section (a), (b) And (c) a screw extruder, and (1) a resin component mainly composed of polycarbonate is continuously supplied in section (a), and on the other hand, an aqueous dispersion of a fluoropolymer and The resin component is supplied separately to the segment (a) at a specific rate, and the organic phosphorus compound is continuously supplied to the segment (b) at a specific rate to disperse the resin component and the water. The liquid and the organic phosphorus compound are extruded through the section (c) in the direction of the outlet directly connected to the section (c) during the kneading. At this time, the resin component is in the sections (a), (b), and ( c), are maintained in the unmelted state, part The molten state and the completely molten state, and the extrusion method is carried out under the conditions that the resin temperature in the extruder is 300 t: below, and the specific energy is 0.13 to 0.220 kW • hr / kg, and In this way, a flame-retardant polycarbonate resin composition is produced; (2) the steps including pulling out the resin composition from the above-mentioned ejection outlet, etc., are a kind of material which can be obtained with both good flame retardancy and mechanical properties.尙 The flame retardant polycarbonate resin composition has excellent appearance and color tone, and has a small load on the extruder, which can prevent the molten resin from generating excessive heat and can be produced at high speed. It has better efficiency and can be used for a long time. Excellent method for stable and continuous manufacturing. The present invention has been completed based on the foregoing research results. Therefore, a first main object of the present invention is to provide a flame retardant polycarbonate resin composition which has good flame retardance and mechanical properties and has excellent appearance and color tone, and The load on the extruder is small, which can prevent the molten resin from overheating and can be produced at high speed. It has better efficiency. It can also be manufactured stably and continuously for long-term use. The paper size is applicable to China National Standard (CNS) A4. (210X297mm) Shu 10-!: —— f — (Please read the notes on the back before filling this page)

1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1224611 A7 B7 V. Invention Description (8) Excellent method. The above and other objects, various features, and various effects of the present invention can be understood by referring to the drawings and cooperating with the following description and the scope of patent application. [Brief Description of the Drawings] FIG. 1 is a side cross-sectional view illustrating an internal schematic structure of an extruder used in the present invention. FIG. 2 is a side cross-sectional view illustrating an internal schematic structure of an extruder used in Examples and Comparative Examples. Figures 3 (a) to 10 (b) are examples of the extruder screw members used in the method according to the present invention. [Description of symbols] a Section where the resin component is maintained in an unfused state (a) b Section where the resin component is maintained in an unfused state (b) c Section where the resin component is maintained in an unfused state (c) I Prevent supply The organophosphorus compound in the section (b) flows back to the section (b-1) of the section (a). Π The resin component, the aqueous dispersion of the fluoropolymer and the organic phosphonium compound are prevented from melting. Bleed-out section (resin-blow-out valve for resin) B 1 to B 9 1st to 9th tube section 1 (a) Aqueous dispersion of resin component and fluoropolymer is suitable for this paper China National Standard (CNS) A4 specification (210X 297 mm)! |! -I — f 丨 (Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives-11-1211 A7 --- B7_____ V. Description of the invention (9) Supply port (a ') 2 Feed hopper (please read the notes on the back before filling this page) 3 a Polycarbonate 3 b, 3 c and 3 d Polycarbonate Supply of other resins or additives 4 Aqueous dispersion of fluoropolymer Nozzle 5 (b ') Supply port for organic phosphorus compound (b') 5 a Supply nozzle for supply of organic phosphorus compound 5 Aqueous dispersion of fluoropolymer or supply of organic phosphorus compound 0 (previous technique) 5 a Co-application nozzle for aqueous dispersion or organic phosphorus compound (previous technique) 6 Drain port 7 Screw 8 Die sleeve section 9 (c ') Outlet of flame retardant polycarbonate resin composition 10 Forward scraper screw Component 11 Forward kneading component Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 12 Reverse kneading component 13 Screw kneading component 14 Neutral kneading component 15 Reverse scraper screw component 16 Screw rotary shaft 17 Axis of the rotary shaft 18 The paper size of the rotation observed on the (c ') side of the spout is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 1224611 A7 B7 V. Description of the invention (10) Shaft rotation direction s 1 to S 5 Figure In 5 to 7, the kneading members are oval (please read the precautions on the back before filling this page). [Detailed description of the invention] The content of the present invention is mainly related to A resin composition composed of polycarbonate, an aqueous dispersion of a fluoropolymer, and a method of kneading with an organic phosphorus compound by a screw extruder to produce a flame-retardant polycarbonate resin composition; the screw extruder is used Segments (a), (b), and (c) are arranged in order in the extrusion direction, and the segment (a) is one or more of the resin component and the aqueous dispersion of the fluoropolymer. The supply port (a ') is in direct communication, and this section (b) is in direct communication with the supply port (b') of the organophosphorus compound, and this section (c) is connected to the outlet (c ') of the polycarbonate resin composition. ) A direct-connected extruder; and (1) the resin component is continuously supplied to the section (a) through a supply port (a '), and the aqueous dispersion of the fluoropolymer is separately from the resin component Continuously supply the segment (a) by the same supply port used by the resin component (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs) or by the different supply port (a ') used by the resin component. In the other hand, the organic phosphorus The compound continuously supplies the section (b) through the supply port (b '); for the supply rate of the resin component (kg / hr), the supply rate of the aqueous dispersion of the fluoropolymer is from 0.01 to 1 10%, in terms of the supply rate of the resin component (kg / hr), the supply rate of the organophosphorus (kg / hr) is 1 to 30%; this paper size applies the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) -13- 1224611 A7 B7 V. Description of the invention (11) The resin component, the aqueous dispersion of the fluoropolymer, and the organic phosphorus compound are extruded through the section (c) toward the ejection outlet during kneading. At this time, in the section (a), the resin component is maintained in an unmelted state, in the section (b), the resin component is maintained in a partially molten state, and in the section (c), the resin component is It is maintained in a completely molten state; and the extrusion method is based on the resin temperature in the extruder being below 300 ° C, and the flame retardant resin composition is manufactured at a speed of 1 kg / hr The output energy (k W) of the running motor of the screw extruder is defined as The specific energy is from 0. 13 to 0. 20kW, hr / kg; and a flame-retardant polycarbonate resin composition is formed in the foregoing manner; (2) the obtained flame-retardant polycarbonate resin composition is composed of The method of manufacturing the flame retardant polycarbonate resin composition is described in the above steps such as the ejection outlet (c ') being pulled out. Subsequently, in order to make the content of the present invention easier to understand, the basic features and preferred embodiments of the present invention will be listed first. 1. A method for producing a flame-retardant polycarbonate resin composition, which comprises kneading a resin component mainly composed of polycarbonate, an aqueous dispersion of a fluoropolymer, and an organic phosphorus compound with a screw extruder. In the method for manufacturing a flame-retardant polycarbonate resin composition, the screw extruder is characterized in that a segment (a), a segment (b), and a segment are sequentially arranged in an extrusion direction. (C), and the section (a) is in direct communication with one or more supply ports (a ') of the resin component and the aqueous dispersion of the fluoropolymer, and the section (b) is connected with an organophosphorus Compound supply port (This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) I ------- install-(Please read the precautions on the back before filling this page))

*, Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T-14-1211 611 A7 B7 5. The invention description (12) b ') is directly connected, and this section (c) is connected with the discharge of the polycarbonate resin composition □ ( (: ') An extruder directly connected; and (1) the resin component is continuously supplied to the section (a') through a supply port (a '), and the aqueous dispersion of the fluoropolymer and The resin component is continuously supplied in the section (a) by the same supply port (a ') used for supplying the resin component or different supply ports (a') used for supplying the resin component, respectively, on the other hand The organic phosphorus compound is continuously supplied to the section (b) through the supply port (b '); For the supply rate of the resin component (kg / hr), the supply rate of the aqueous dispersion of the fluoropolymer is 0 〇1 to 10%, in terms of the supply rate of the resin component (kg / hr), the supply rate of the organic phosphorus (kg / hr) is 1 to 30%; the water content of the resin component and the fluoropolymer Dispersion and organophosphorus compounds pass through section (c) during kneading Squeeze toward the discharge port. At this time, in the section (a), the resin component is maintained in an unmelted state, and in the section (b), the resin component is maintained in a partially molten state, and in the section (c) The resin component is maintained in a completely molten state; and the extrusion method is such that the resin temperature in the extruder is 300 t: or less, and the flame retardant resin composition is The output energy (k W) of the operating motor of the screw extruder consumed during manufacturing at a speed of kg / hr is defined as a specific energy of 0.13 to 0.20kW, hr / kg; and generated in the manner described above. Flame retardant polycarbonate resin composition; (2) The obtained flame retardant polycarbonate resin composition shall be printed from the above-mentioned paper. The paper shall be in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) —— — — — I — f, (Please read the precautions on the back before filling out this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives -15-1224611 A7 _______B7_ V. Description of the invention (13) Pull out the exit (c ') and other steps 2. The method as in item 1 above, wherein the The press is a 2-axis extruder (please read the precautions on the back before filling in this page) 0 3. The method as described in item 1 above, in which the screw revolution of the extruder is above 200 rpm. 4. If The method of the preceding paragraph 1, wherein a section for preventing the organic phosphorus compound supplied to the section (b) from flowing back to the section (a) is provided. In the section (b-1) provided on the upstream side of the supply position of the organic phosphorus compound, the resin filling ratio defined by the volume ratio of the resin component in the internal space of the extruder is increased, and the resin component, The kneading of the aqueous dispersion of the fluoropolymer with the organic phosphorus compound is mainly performed in a region on the downstream side of the organic phosphorus compound supply position in the extrusion direction of the extruder. 5. The method as described in the above item 1, wherein the resin component is composed of polycarbonate and modified styrene resin. 6. The method according to the preceding paragraph 1, wherein 70% by weight or more of the resin component supplied to the extruder is a pellet. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 7. The method as in the preceding paragraph 1, wherein the temperature of the aqueous dispersion of the fluoropolymer supplied to the section (a) of the extruder is 5 to 30 t. 8. The method according to the preceding paragraph 1, wherein the acid value of the organic phosphorus compound supplied to the section (b) of the extruder is 1 mg KOH / g or less. 9. The method according to the preceding paragraph 8, wherein: The acid value of the organophosphorus compound supplied to the section (b) of the extruder is 0.1 mg KOH / g. At this paper scale, the Chinese National Standard (CNS) A4 specification (210X 297 mm) -16 -1224611 A7

(In the formula, Ar is a divalent aromatic residue having 5 to 200 carbon atoms, such as, for example, phenylene, naphthyl, biphenyl, or diphenyl, or the following formula (3) Radicals, etc.) -Ar1——Y——Ar 2 · 3 (In the formula, each of A r 1 and A r 2 is a θ field squaring group, such as phenylene, naphthyl, or biphenyl 1, pyridyl Y is an alkylene group or a substituted alkylene group represented by formula (4);)

R — C — R 2

1 2 R —-C——R

3 1 4 R 丨 cIR and VX 0 4 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R1, R, R, and R4 are each independently a hydrogen atom, Lower alkyl with 1 to 6 carbons, cycloalkyl with 5 to 10 carbons' aryl with 6 to 3 carbons, aralkyl with 7 to 31 carbons, if necessary, halogen atoms, carbons Substituted by an alkoxy group of 1 to 10, k is an integer of 3 to i, R · 5 and R6 can be selected according to each X, and they can be independently hydrogen atoms or lower alkane of 1 to 6 carbon atoms And an aryl group having 6 to 30 carbon atoms may be substituted by a halogen atom and an alkoxy group having 1 to 10 carbon atoms if necessary, and X is a carbon atom;) and may contain the following formula (5) A divalent aromatic residue is shown as a copolymer component. ——Ar 1——Z——Ar 2—— (5) (In the formula, Ar1 and Ar2 have the same content as in formula (3); Z is the paper size and applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) 18-1224611 A7 B7 V. Description of the invention (16) Early bond, or 101, 1 C 0—, 1 S —, 1 S 02 —, 1 C 0 2 —, 1 CON (R1) — ( R1 has the same content as formula (4)) Equivalent divalent bases;) Specific examples of A r in the above formula (2) and divalent aromatic residues represented by formula (5), each of which is shown in the following formula, for example Content holder; (R7).

(P8) n CH

(R7) m (Ρ8) π CH, (R7) m ^ w (R8) n

(R?) M (p8) n

(Please read the notes on the back before filling out this page) · Equipment · ‘Order ^ 1. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

CH, CH 3 CH,

(R7) m (P8) n CH2-CH2

This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -19- 1224611 A7 B7 H: I ___ Description of Inventions printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (17) (R7) -〒8 ) n (R7) m (strict 8) n ~ Ό) ~, (R7). (R7) r

(R7) T (^ 8) n (R?) R (P8) r (P8) f (R7) r (R7) r (^ 8) r (P8), and (Please read the precautions on the back before filling (This page)

『修 〇

CH, (wherein R7 and R8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a ring group having 5 to 1.0 carbon atoms or carbon number An aryl group of 6 to 30; m and η are integers of 1 to 4, in the case where .m is 2 to 4, each R 7 may be the same or different in the case of 2 to 4, each R 8 may be the same Or different;) Among them, the base shown by the following formula (6) is a better example. ? H3

CH, (6 -------------- clothing ----'-- order ------ η This paper size is applicable to China National Standard (CNS) 8 4 size (210X297 (Mm) -20-1224611 A7 B7 V. Description of the invention (18) Among them, 85 mol% or more of the repeating unit of the formula (2) containing the base represented by the formula (6) above is represented by polycarbonate Polyesters based on all monomer units in esters are the best. Polycarbonates that can be used in the present invention may also have aromatic residues with trivalent or higher carbon numbers from 6 to 300 The branching structure of the branching point. There is no particular limitation on the molecular structure of the polymer terminal, and it can be used with one or more terminal groups selected from phenolic terminal groups, aryl carbonate groups, and alkyl carbonate groups. Bonded. Aryl carbonate terminal group, for example, the group represented by the following formula (7); 〇-C-0-Ar 3 f η \ (where, A r 3 is a monovalent carbon number 6 to 3 0 Aromatic residue, its aromatic ring can also be substituted) Specific examples of aryl polycarbonate end groups, such as the base shown in the following formula (please read the precautions on the back before filling this page) Order the Ministry of Economic Affairs wisdom Property bureau The paper size printed by the employee's consumer cooperative applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -21-1224611 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (20) A terminal group, a phenyl carbonate group, a P-t-butylphenyl carbonate group, a P-cumylphenyl carbonate group, etc. are more preferred. In the present invention, the ratio of a phenolic terminal group to other terminal groups There is no particular limitation, but from the viewpoint of obtaining excellent hue and mechanical properties, the proportion of phenolic terminal groups is preferably 20% or more of the total number of terminal groups, and 20 to 8 A range of 0% is more preferred. If the ratio of phenolic terminal groups exceeds 80% of the total number of terminal groups, the thermal stability during melting tends to decrease slightly. The method for measuring the amount of phenolic terminal groups is generally It is obtained by a method using NMR measurement (NMR method), a method using titanium measurement (titanium measurement method), or a method using UV or IR measurement (UV method or IR method). The weight average molecular weight (Mw) of the group polycarbonate is generally preferably 5,000 to 50,000, more preferably 10,000 to 40,000, and even more preferably 15,000 to 30,000. 10,000 is more preferable, and 18,000 to 25,000 is most preferable. When it is less than 5,000, the impact resistance of the flame-retardant polycarbonate resin composition tends to be insufficient, When it exceeds 50,000, the melt fluidity of the resin group removal product tends to be insufficient. The weight average molecular weight (Mw) can be measured by colloidal chromatographic analysis (G P C). The measurement conditions are as follows. That is, it is obtained by using a tetrahydrofuran as a solvent, using a polystyrene colloid, and calculating a conversion curve of molecular weight according to the following formula according to the calibration curve of a standard monodisperse polystyrene. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) 23 1224611 A7 B7 V. Description of the invention (22) (Please read the precautions on the back first Fill in this page again) Styrene (AS) resin, styrene resins such as methyl methacrylate-styrene (M s), acrylonitrile-butadiene-styrene (A bs) tree month purpose, acrylonitrile- 1 Rubber modified styrene resins such as butyl acrylate monostyrene (AAS) resin, methyl acrylate monobutadiene-styrene (M BS) resin, η IPS (high impact polystyrene) resin, polystyrene ether resin, Polyamide resins, polyester resins, polyolefin resins, polyoxymethylene resins, polymethyl methacrylate resins, polyvinyl chloride resins, and core-shell rubbers are typical examples of graft rubbers used as impact resistance improvers or Various elastomers, among which rubber modified styrene resin such as ABS resin is the best. The rubber modified styrene resin described above refers to rubbery polymers and rubber modified containing at least one ethylene polymer. Styrene resin. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Rubber polymers for rubber-modified styrene resins. For example, polymers with a glass transition temperature below 0 ° c. Specific examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, diene-based rubber, acrylic rubber such as butyl acrylate, polyisobutylene, poly Block copolymers such as chloroprene, ethylene-propylene rubber, ethylene-propylene-diene terpolymer rubber, styrene-butadiene block copolymer rubber, styrene-isobutylene block copolymer rubber, and their hydrogen Additives, etc. Among these polymers are polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polybutyl acrylate, and the like. The proportion of the rubbery polymer in the rubber-modified styrene resin is 1 to 95% by weight, and can be processed according to the necessary mechanical strength, rigidity, and molding. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) -25- 1224611 A7 _ B7 _ 5. The description of the invention (23) is determined by the properties, etc., preferably 5 to 45% by weight, and more preferably 10 to 40% by weight. (Please read the notes on the back before filling out this page) The vinyl compounds used in the printing of rubber modified styrene resins by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as styrene, α-methylstyrene, p-formaldehyde Aromatic vinyl compounds such as styrene, alkyl (meth) acrylates such as methyl methacrylate, methacrylate, butyl acrylate, and ethyl acrylate; (fluorenyl) acrylic acid such as acrylic acid and methacrylic acid Type, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, α, yS monounsaturated carboxylic acids such as anhydrous maleic acid, N-phenylmaleimide, N-methylmaleimide, Maleimide-based monomers such as N-cyclohexylmaleimide, glycidyl-containing monomers such as glycidyl methacrylate, and the like. Aromatic ethylene compounds, alkyl (meth) acrylates, vinyl cyanide monomers, and maleimide monomers are preferred, and styrene, acrylonitrile, and N-phenylmaleimide are more preferred. , Butyl acrylate. These ethylene compounds can be used alone or in combination of two or more. A combination of an aromatic vinyl compound and an ethylene compound other than aromatic is preferred. In this case, the aromatic vinyl compound and an ethylene compound other than the aromatic compound may be mixed in an arbitrary ratio. The preferred ratio of the ethylene compound other than the aromatic compound is 5 to 5 to the total amount of the aromatic vinyl compound and the other ethylene compound. 80% by weight. The method for producing the rubber-denatured styrene-based resin is not particularly limited. Generally, for example, there are generally known production methods such as block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. When polycarbonate is blended with rubber-modified styrene, the proportion can be determined according to the required mechanical strength, rigidity, molding processability, heat resistance, and the like. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -26-1224611 A7 B7 V. Description of the invention (24) (Please read the precautions on the back before filling this page) It is better for polycarbonate 50 to 9 5 parts by weight of 50 to 5 parts by weight of rubber-modified styrene resin, more preferably 60 to 90 parts by weight of polycarbonate to 40 to 10 parts by weight of rubber-modified styrene resin Resin. The organic phosphorus compound used in the method of the present invention is at least one organic phosphorus compound and a compound having one or more phosphorus atoms. Compounds having one phosphorus atom (hereinafter, also referred to as monoorganophosphorus compounds), such as triphenyl phosphate, tricresyl phosphate, tolyl phenyl phosphate, xylyl phenyl phosphate, and the like. However, when a single organic phosphorus compound is used to mold a flame-retardant polycarbonate resin composition, there is a disadvantage that mold fouling (MD) is easily generated on the surface of the mold. Therefore, the organic phosphorus compound used in the present invention has the following disadvantages: An organic phosphorus compound oligomer of a compound having two or more phosphorus atoms is preferred. The best example of the organic phosphorus compound oligomer used in the present invention is, for example, one selected from the group of compounds represented by the following formula (1).

ch3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Ra, Rb, R. Independent from 1 ^, the basic paper size of the aromatic paper with carbon number 6 to 20 is applicable to the Chinese National Standard (CNS) A4 specification (210X: 297 mm) -27-1224611 Α7 B7 5. It can be attached when the description of the invention (26) The amount of mold fouling on the mold surface is lower than that of oligomeric phosphate esters. (Please read the notes on the back before filling this page.) Generally, the oligomers of organic phosphorus compounds represented by formula (1) are η 値 (η is a natural number) that are different from those of formula (1). It is often the case that the oligomerization of the phosphorus compound is used by mistake in the form of a mixture. In this case, the weight-average degree of condensation (N) of the majority of different organic phosphorus compound oligomers is preferably between 1 and 1.2. Ν is the weight fraction (An) of components with different η, which is obtained by polymerizing with silicon penetrant chromatographic analysis or liquid chromatographic analysis, and then according to the formula N = Σ (η · Αη) / Σ (An) What is sought. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. When A η is obtained, the detector can be a U V detector, an I R detector, or an R I detector. Among them, in the calculation of N, the above-mentioned organic phosphorus compound is an organic phosphorus compound oligomer of the above formula (1) and a compound having a structure in which n is 0 in the above formula (1) (that is, the phosphorus atom in one molecule is only In the mixture of monoorganophosphorus compounds of 1), compounds with η of 0 need to be removed from the calculation of N. The weight average condensation degree N is generally preferably 1 or more and 5 or less, and more preferably 1 or more and 2 or less, more preferably 1 or more and 5 or less, and most preferably 1 or more and 1.2 or less. The smaller the N, the better the compatibility with the resin components, the better the melt flow, and the higher the flame retardancy. In particular, the compound having N = 1 has the best balance between flame retardancy and melt flowability in the resin composition. If the N of the compound of formula (1) of the organophosphorus compound is 5 or more, the viscosity of the compound will increase, especially the flowability in the high shear rate region will tend to decrease, and the flame resistance will also This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -29- 1224611 A7 B7 V. Description of invention (27) The tendency to decrease. (Please read the notes on the back before filling this page) In addition, the organic phosphorus compound used in the present invention has an acid value of preferably 1 mgKOH / g or less, more preferably 0.5 mgKOH / g or less, more preferably It is 0.2 mg K〇H / g or less, and most preferably 0-1 mg K 0 Η / g or less. When an organic phosphorus compound having a lower acid value is used, a flame-retardant polycarbonate resin product having higher temperature resistance and high humidity resistance can be obtained. Therefore, in the present invention, when using an organic phosphorus compound, the acid value is avoided. For the increase, it is necessary to prevent the mixing of water or prevent overheating, so it needs more care during storage and transportation. The amount of organic phosphorus compounds in the flame-retardant polycarbonate resin composition produced by the method of the present invention printed by the employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs shall be determined in accordance with the required degree of flame retardance. The component is generally in the range of about 1 to 30 parts by weight based on 100 parts by weight. Therefore, according to the method of the present invention, the organic phosphorus protective compound is continuously supplied to the extruder at a supply rate (kg / hr) of the resin component of 1 to 30% (kg / hr). . When the addition amount of the organic phosphorus compound is less than 1 part by weight, the necessary flame retardance effect cannot be exhibited, and when it exceeds 30 parts by weight, the addition of the organic phosphorus compound is difficult, which may cause resistance of the resin product. The impact resistance and heat resistance are reduced. The addition amount of the organic phosphorus compound is preferably in the range of 2 to 20 parts by weight, and more preferably in the range of 5 to 18 parts by weight. The fluoropolymer in the aqueous dispersion of the fluoropolymer used in the method for producing a flame-retardant polycarbonate resin composition of the present invention may be, for example, tetrafluoroethylene such as polytetrafluoroethylene, a tetrafluoroethylene-propylene copolymer, and the like. Ethylene polymer, perfluoroolefin polymer other than polytetrafluoroethylene, preferably tetrafluoroethylene polymer. The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -30-1224611 A7 B7 V. Invention Note (28), the best is polytetrafluoroethylene. An aqueous dispersion of the above-mentioned fluoropolymer is exemplified by a fluoropolymer obtained by using a suspension polymerization method or an emulsion polymerization method described in the "Fluoro Resin Handbook" (Japan, Nikkan Kogyo Shimbun, 1990). When the aqueous dispersion is concentrated to 40 to 70% by weight, it is stabilized with a surfactant to prepare a milky white aqueous dispersion. The concentration of the fluoropolymer in the aqueous dispersion of the fluoropolymer can be hydrolyzed with water in a state where the concentration of the fluoropolymer can be stabilized, and it is preferably 5 to 70% by weight, and 20 to 6 5 wt% is more preferred, and 30 to 60 wt% is more preferred. The average particle diameter of the fluoropolymer particles in the aqueous dispersion is preferably from 0.01 to 0.6 / m, more preferably from 0.05 to 0.4 // m, and from 0.18 to 0 · 3 // m is the best. In addition, as the surfactant that stabilizes the aqueous dispersion of the fluoropolymer, for example, an anionic surfactant such as an epoxidized alkylphenol, an epoxidized higher alcohol, or the like is preferred, and the added amount is generally 1 to 1 5 % By weight, preferably 2 to 10% by weight, and more preferably 3 to 7% by weight. In addition, the P Η 値 of the aqueous dispersion of the win polymer is generally preferably adjusted to a range of 9 to 10. When the concentration of the fluoropolymer in the aqueous dispersion is 60% by weight, the specific gravity of the liquid is about 1.5, and the viscosity (25 ° C) is in the range of 15 to 30 c p. Fluoropolymer aqueous dispersions that are preferably used in the present invention, for example, "Teflon 30 J" manufactured by Mitsui DuPont Chemical Co., Ltd., and "Polyfluoron D-1" and "Polyfluoro D" manufactured by Daikin Corporation of Japan. -2 "," PTFE D-2C "," PTFE D-2CE ", etc. In the method of the present invention, as shown below, if the fluoropolymer water-based ^ paper size is applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) " ~ " -31-(Please read the note on the back first Please fill in this page for further details.) Clothing and order Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1224611 A7 B7 V. Description of the invention (30) The dispersion liquid and organic phosphorus compound are mixed in a screw extruder to make it flame-resistant Polycarbonate resin composition. (Please read the precautions on the back before filling out this page) Section (a), section (b) and section (c) in the screw extruder are arranged in the order of the extrusion direction, and the section ( a) is in direct communication with one or more supply ports (a ') of the resin component and the aqueous dispersion of the fluoropolymer, and the section (b) is directly connected with the supply port (b') of the organic phosphorus compound The section (c) is an extruder in direct communication with the outlet (c ') of the polycarbonate resin composition; and the method of the present invention includes only polycarbonate, or Resin components other than polycarbonate are continuously supplied to the section (a) through the supply port (a '), and the aqueous dispersion of the fluoropolymer and the resin component are separately supplied by the resin component. The same supply port (a ') used or the different supply port (a') used to supply the resin component is continuously supplied in the section (a). On the other hand, the organic phosphorus compound is passed through the supply port (b '). Continuous supply sector (b); Intellectual Property Office, Ministry of Economic Affairs Industrial and consumer cooperatives are printed in the extruder. The resin component, the fluoropolymer aqueous dispersion and the organic phosphorus compound are extruded through the section (c) toward the discharge port (c ') during kneading. At this time, in the section (a), the resin component is maintained in an unmelted state, in the section (b), the resin component is maintained in a partially molten state, and in the section (c), the resin component is maintained In a completely molten state. Sections (a), (b), and (c) of the resins in the extruder are maintained in the state described above, and they can generally be synthesized by using the extruder in accordance with common methods. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) '' — — -33-1224611 A7 _ B7 V. Description of the invention (31) (Please read the precautions on the back before filling this page) Also, this In the invention, a section for preventing the organic phosphorus compound supplied to the section (b) from flowing back to the section (a) is provided, and the organic phosphorus compound in the section (b) is supplied according to the extrusion direction of the extruder. In the section (b-1) set on the upstream side of the position, the resin filling ratio defined by the volume ratio of the resin component in the internal space of the extruder is increased, and the resin component and the fluoropolymer The kneading of the aqueous dispersion and the organic phosphorus compound is mainly performed in a region on the downstream side of the organic phosphorus compound supply position according to the extrusion direction of the extruder (hereinafter, also referred to as the "main kneading section"). . In addition, the "resin filling rate" in the extruder is different depending on the measurement site inside the extruder. The resin filling rate in a specific area inside the extruder is based on the inside of the extruder barrel. The volume is obtained by subtracting the ratio of the total volume of the screw rotating shaft and the screw member to the volume of the resin component. When the resin component is completely filled in the specific field, the resin filling ratio is 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the method of the present invention, the extruder described above is preferably a two-axis extruder, and a co-rotating two-axis extruder is most preferably used. The two-axis extruder with co-rotating meshing can obtain self-cleaning effect through the way of the left and right screw shafts meshing with each other. It can make the resin raw material stay in the extruder for a short time, so it has excellent resin transportation. Performance, kneading performance and volatility, etc., it is very suitable as the preferred extruder of the present invention. Especially when using a two-shaft extruder with high torque and high revolutions, it can increase the production speed and reduce the temperature of the molten resin during kneading, so it is an excellent extruder. Furthermore, an extruder having a rotation number of 3 0 0 r p m or more, preferably 4 0 ◦ r p m or more, more preferably 5 0 r p m or more is more preferable. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -34-1224611 A7 B7 V. Description of the invention (32) (Please read the precautions on the back before filling this page) The squeeze used in the method of the present invention The best examples of presses are, for example, TE M — SS series manufactured by Toshiba Machinery Co. of Japan, ZSK-MC series manufactured by Werner & Pfleiderer of Germany, and TEX Super α-ΙΙ series manufactured by Japan Steel Wait. In addition, in the method of the present invention, the screw configuration content of the two-axis extruder (the entire screw) can be arbitrarily selected in accordance with the screw configuration requirements of the extrusion, and the temperature of the drum of each section of the extruder can be controlled. A two-axis extruder is even better. This extruder can appropriately select the whole screw or the internal temperature distribution of the extruder to adjust the length of the above-mentioned sections (a), (b), and (c), so that the above-mentioned sections can be formed in the extruder. (B-1) or the area where the mixing is performed. A specific example of an extruder suitable for use in the present invention is an extruder having an internal structure shown in FIG. Fig. 1 is a side cross-sectional view illustrating an outline internal structure of an extruder used in the present invention. An extruder having a screw configuration shown in Fig. 1 is an example of a screw configuration which is preferable for carrying out the method of the present invention. Before explaining the method of the present invention with reference to Fig. 1, the contents of the extruder screw used in the present invention will be described. In the method for printing the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the extruder screw member constituting the extruder screw may be a forward scraper screw member, a reverse scraper screw member, a forward kneading member, and a reverse kneading Members, neutral kneading members, forward screw mixing members, reverse screw mixing members, sealing members, and the like. After the combination, the content of the extruder screw suitable for the present invention can be prepared. Hereinafter, the screw members of each extruder and their effects will be described with reference to FIGS. 3 (a) to 10 (b). This paper size applies to China National Standard (CNS) A4 (210X297 mm) -35- 1224611 A7 B7 V. Description of the invention (33) Figure 3 (a) is an extruder with a forward scraper member with a rotating shaft , Observed from the direction of the outlet (C ') of the extruder. (Please read the precautions on the back before filling out this page) Figure 3 (b) is a schematic diagram of the screw member of the forward scraper. "Forward scraper screw member" refers to the structure of a screw that continuously rotates in the right-hand direction, and can be viewed from the direction of the outlet (C ') of the extruder when the screw rotates. Right rotation) Extruder screw member that extrudes the resin component in the extrusion direction. The two-shaft extruder preferably used in the present invention is arranged at two corresponding positions on the rotary shaft. The number of forward squeegee screw members (scraper number) is generally 1 to 3, and can be distinguished according to the purpose of use. Fig. 3 (a) and Fig. 3 (b) show the forward screw member of the 2-scraper which is used more frequently in the present invention. In Fig. 3 (a), the ratio 螺杆 / D i (hereinafter referred to as the meshing ratio) of the screw outer diameter (D.) to the screw inner diameter (D i) is generally in the range of 1.3 to 1.8, which is economical. The Ministry of Intellectual Property Bureau's employee consumer cooperative prints that the range of 1.4 to 1.7 is preferred, the range of 1.5 to 1.6 is more preferred, and the mesh ratio of the screw is 1.5 5 Its forward scraper screw member. In addition, the distance between the squeegees in the forward squeegee screw member is generally equal to the outer diameter D of the screw. The length is 0.5 to 2.0 times, and can be distinguished according to the purpose of use. Generally speaking, when the distance between the scrapers is too long, the amount of conveyance can be increased but the filling rate of the resin can be reduced. Conversely, when the distance is too short, the amount of resin can be reduced to increase the filling rate of the resin. The resin in the forward squeegee screw member proceeds from right to left as shown in Fig. 3 (b). Figure 4 (a) is a schematic diagram of a reverse scraper screw member with a rotating shaft, viewed from the direction of the outlet (C ') of the extruder, and Figure 4 (b) is a sketch of the reverse scraper screw described above. Side view. "The reverse scraper screw structure paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) -36- 1224611 A7 _B7 _ ^ __ V. Description of the invention (34) (Please read the precautions on the back before filling this page "Part" refers to an extruder screw member that has a structure of a screw that rotates continuously in the left-hand direction and can move the resin component in the direction opposite to the extrusion direction due to the rotation of the screw. The two-shaft extruder preferably used in the present invention is arranged at two corresponding positions on the rotary shaft. FIG. 4 shows the reverse screw member of the 2-scraper, which is preferably used in the present invention and is used most frequently. Reverse Scraper The number of scrapers of the screw member is generally two, and the meshing ratio is 値 D. / D, generally in the range of 1 _ 3 to 1.8, and the distance between the scrapers is generally the diameter D of the screw. It is 0.5 to 2.0 times in length. If the reverse blade screw member moves the resin in the direction opposite to the extrusion direction, it will have a better effect. The result of using this extruder blade member depends on the extrusion direction. During observation, the resin charge rate on the upstream side of the screw member of the extruder was substantially 1, that is, the state of complete charge was present. Therefore, when viewed from the extrusion direction, if a later-described forward kneading member, reverse kneading member, neutral kneading member, forward screw mixing member, reverse screw mixing member and the like are added to the upstream side of the reverse blade screw member, When the screw member of the extruder has a high kneading effect, the resin inside the extruder can be melt-kneaded in a fully charged state, so it can provide a strong melt-kneading effect to the resin. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Figure 5 (a) is an extruder with a forward kneading member with a rotating shaft, and a schematic view of the extruder viewed from the direction of the outlet (C ') of the extruder. Fig. 5 (b) is a schematic side view of the above-mentioned forward kneading member. "Forward kneading member" refers to the axis of rotation of the extruder, using most of the oval-shaped flat plate. When the direction of rotation according to the axis of rotation is "positive", the direction of The staggering angle greater than 0 degrees and less than 90 degrees overlaps with each other in the opposite direction to form a laminate. This paper size applies the Chinese National Standard (cns) A4 specification (210X297 mm) -37- 1224611 A7 ____B7 V. Description of the invention (35) (Please read the precautions on the back before filling this page) While turning the screw member of this press to move the resin in the extrusion direction, the resin can be extruded by extrusion. Machine screw member. In the forward kneading member, it is preferable that the number of the oval-shaped flat plates mentioned above is at least 3 pieces, and it is more preferable to form a laminated layer with 5 pieces or more. In addition, it is preferable that the oval-shaped flat plate has a thickness of 0 · 05 to 0 · 5 times with respect to the outside of the screw ili (D0). In addition, the above-mentioned flat plate has an ellipse shape such that the ratio of the major axis to the minor axis is from 1.1 to 2.0. The ratio of the maximum diameter of the oval-like shape to the inner diameter of the cylinder itself is preferably in the range of 0.95 to 0.995. Fig. 5 is a forward kneading member obtained by laminating 5 pieces of oval-shaped flat plates with a staggering angle of 45 degrees, which is most commonly used in the present invention. Fig. 6 (a) is a schematic view of an extruder with a reverse kneading member attached to a rotating shaft, which is observed from the direction of the discharge port (C ') of the extruder. Figure 6 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (b) is a schematic side view of the above-mentioned forward kneading component. "Reverse kneading member" refers to the axis of rotation of the extruder, using most of the oval-shaped flat plate. When the direction of rotation according to the axis of rotation is "positive" ，, The twist angle of 0 degrees and less than 90 degrees overlaps with each other in the direction opposite to the extrusion direction to form a laminate. While rotating the screw member of the press to move the resin in the extrusion direction, the resin can be mixed. Extruder screw member. The number of the oval-shaped flat plates mentioned above is preferably at least 3 pieces, and it is more preferable to form a laminated layer with 5 pieces or more. The thickness of the oval-shaped flat plate, the ratio of the major diameter to the minor diameter, and the maximum diameter of the oval-shaped plate are the same as those in the case of the forward kneading member. Fig. 6 is a reverse kneading member obtained by laminating 5 pieces of oval-shaped flat plates with a negative staggering angle of 45 degrees, which is most commonly used in the present invention. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -38- 1224611 A7 B7 V. Description of the invention (36) Figure 7 (a) is an extruder with a neutral kneading member with a rotating shaft. Observed from the direction of the outlet (C ') of the extruder. Figure 7 (Please read the precautions on the back before filling out this page) (b) is a schematic side view of the neutral kneading member described above. "Neutral kneading member" refers to the axis of rotation of the extruder as the axis, using most of the substantially oval-shaped flat plates, overlapping each other at a staggering angle of 90 degrees to form a laminate, Then, the screw member of the extruder is kneaded by rotating the screw member of the press. Since the oval flat plate in the neutral kneading member has a staggering angle of 90 degrees to each other, it does not have the function of moving the resin in the extrusion direction or the opposite direction. In addition, the thickness of the oval-shaped flat plate, the ratio of the major and minor diameters, and the maximum diameter of the oval-shaped plate are the same as those of the kneading member in the forward direction. The case of using the neutral kneading group has better kneading effect than the case of generally using a forward kneader or a reverse kneader. Fig. 7 is a neutral kneading member obtained by laminating 5 kinds of oval-shaped flat plates most commonly used in the present invention. Fig. 8 (a) is a schematic view of an extruder with a forward screw kneading member with a rotary shaft, which is observed from the direction of the discharge port (C ') of the extruder. Fig. 8 (b) is a schematic side view of the forward screw kneading member described above. "The printed screw mixing component printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs" means that a gap is provided on the twisting protrusion of the screw of the forward scraper screw, where the screw member is rotated to move the resin in the extrusion direction. At the same time, a part of the resin can be moved from the notched part to the opposite direction to promote the screw member of the extruder for kneading the resin. In the two-shaft extruder that is preferably used in the present invention, the aforementioned forward scraper screw member is arranged at two corresponding positions on the screw shaft in the same manner. Fig. 8 is a forward screw kneading member which is preferably used in the present invention. $ Paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -39- 1224611 A7 ________ B7 V. Description of the invention (37) Figure 9 (a) is the extrusion of a reverse screw kneading member with a rotating shaft Machine, viewed from the direction of the extruder's discharge port (C '). (Please read the precautions on the back before filling out this page) Figure 9 (b) is a schematic diagram of the side view of the reverse screw mixing component described above. "Reverse screw kneading member" means that a gap is provided on the twisting protrusion of the reverse scraper screw. While the screw member is rotated to move the resin in the extrusion direction, a part of the resin can be moved from the notch to the Extruder screw member moving in the opposite direction to promote resin kneading. The screw member of this extruder has a left-handed structure, so the resin's moving force in the direction opposite to the extrusion direction is strong due to the rotation of the screw. Therefore, it has a greater effect when compared with the use of a forward screw member. Strong resin mixing effect. In the two-shaft extruder preferably used in the present invention, the above-mentioned reverse scraper screw member is arranged at two corresponding positions on the screw shaft in the same manner. Fig. 9 is a forward screw kneading member which is preferably used in the present invention. Fig. 10 (a) is a schematic view of an extruder with a sealing member attached to a rotary shaft, which is viewed from the direction of the extruder outlet (C '). Figure 10 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (b) is a schematic side view of the seal member described above. The "sealing member" is basically composed of at least one circular flat plate, and has the effect of hindering the advancement of the resin and increasing the resin charge rate. When a sealing member is used, the resin in the gap between the cartridge body and the sealing member can be sufficiently removed. The two-axis extruder which is more suitable for use in the present invention uses a sealing member. One sealing plate can be arranged on each of the two screws, or two or more can be arranged as necessary. The thickness of the seal member in the screw axis direction is generally 0.5 to 0.5 times the length of the outer diameter in the screw axis direction. The ratio of the maximum diameter of the circular flat plate to the inner diameter of the cylinder itself is in the range of 0.950 to 0.995. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) -40-1224611 A7 ___ B7 5. The invention description (38) is better. FIG. 10 is a sealing member most commonly used in the present invention. (Please read the precautions on the back before filling this page) In the method of the present invention, the resin component in the above-mentioned section (a) of the extruder is maintained in an unmelted state, for example, in the above-mentioned section (a) The screw of the extruder is only set according to the screw member of the forward scraper, and the temperature of the barrel section is set in the range of 20 to 200 ° C, preferably in the range of 30 to 100 ° C, more When the temperature is set within the range of 40 to 70 ° C, it is possible to prevent the resin component containing polycarbonate from melting. The length of this section (a) is affected by the number of revolutions or processing speed of the extruder, in addition to the temperature of the screw configuration and the barrel section temperature. If the rotation speed or processing speed increases, the section can also grow To match. The resin component (granular and / or powdered resin) in this section (a) is in a state where no melting is observed. This confirms that it can pass through the opening of the barrel section of the extruder (extruder). The supply port (a ')) or the observation window of the barrel section of the extruder is visually identified. In the method of the present invention, whether the fluoropolymer aqueous dispersion is continuously supplied in the section (a) or the optimal position for continuously supplying the fluoropolymer aqueous dispersion in the section (a) is determined by the input of the resin component. The hopper used, in addition, the temperature of the drum section below the hopper is 40 to 70 ° C. It is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the method of the present invention, the section of the extruder (b ), The resin component described above is maintained in a molten state. For example, in the above section (b), the screw of the extruder is a forward-direction scraper screw member, or it can be a forward kneading member, a reverse kneading member, a neutral kneading member, a forward screw kneading member, and the like. Composed of extruder screw components. In addition, if the temperature of the drum section is set to 201 to 350 ° C, preferably 210 to 300 ° C, it is better. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -41- 1224611 Α7 Β7 V. Description of the invention (39) (Please read the precautions on the back before filling in this page) When the range is 2 2 0 to 2 0 0 ° C, the kneading function of the screw components of the extruder is supplied. As a result of the amount and the thermal energy of the drum section, the resin component can be partially melted. In this section (b), a method for confirming that a part of the resin component is in a molten state can be observed visually through a viewing window provided in the extruder section, or the extruder in operation can be stopped. Cool the drum section, and then take out the extruder screw member and observe the molten state of the resin inside the extruder. (Among them, the supply of the organic phosphorus compound of the flame retardant should be stopped during the observation). At this time, the unmelted portion of the resin can be visually confirmed, and the resin component in the segment (b) is from 0.01 to 90% by weight, preferably from 0.1 to 70% by weight, more preferably from 1 to 5 0% by weight is preferably in a molten state. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the organic phosphorus compound as the flame retardant in the present invention, which is continuously supplied to the section (b). For example, the organic phosphorus compound can be a gear pump or a plunger pump. After it is quantified, it will be supplied by the injection nozzle set in the extruder section. In addition, the extruder screw member of the organic phosphorus compound supply position, in order to reduce the resin pressure to facilitate the addition of the organic phosphorus compound, it is better to use a forward scraper screw member or a forward scraper kneading member, and its resin filling rate. It is preferably 1 or less, preferably 0.4 to 0.8. The above "main kneading area" refers to the screw structure of the extruder. It incorporates extrusion mechanism parts with excellent resin sealing properties, such as reverse scraper screw members or sealing members, and then extrudes the screw members of the extruder. On the upstream side when viewed from the direction, there are a plurality of extruder screw members that are excellent in melt kneading, such as forward kneading screw members, reverse kneading screw members, neutral kneading screw members, forward screw kneading members, and reverse screw kneading members. The size of the paper that makes up the insects applies the Chinese National Standard (CNS) A4 regulations ^ 210 × 297 mm ~ ~ -42- 1224611 A7 B7 V. Description of the invention (40) (Please read the precautions on the back before filling this page ) Machine screw member, and if the temperature of the drum section is set to 201 to 350 ° C, preferably 210 to 300 t :, more preferably 220 to 28. (: In the range of, after supplying the energy of the kneading machine of the screw member of the extruder and the thermal energy of the drum section, the resin component, the organic phosphorus compound and the fluoropolymer can be brought to a resin filling rate of 1 ( That is, the molten resin is in a fully charged state) to achieve sufficient melt kneading. In the method of the present invention, after passing through the main kneading section, it is necessary to select a composition of a kneading screw that can completely unobserve the particles of unmelted resin. Combination. After confirming the molten resin in the section (c) after the main kneading section, it can be observed visually through the viewing window installed in the extruder section, or the extruder in operation can be stopped. Cool the drum section, then take out the screw member of the extruder and observe the molten state of the resin inside the extruder. In addition, the main kneading zone can be set at one or more places in the extruder. Economy In the above section (b) printed by the Ministry of Intellectual Property Bureau's Consumer Cooperative, the screw structure of the extruder can use 1 to 3 members selected from forward kneading screw members, reverse kneading screw members, and neutral kneading. Screw members, extruder screw members with a narrower pitch and forward scraper screw members (the distance between the scrapers to the screw outer diameter D. is about 0.5 to 0.8 times), so that the resin filling rate reaches 〇. 7 to 1 · 0. And if the temperature of the drum section is set to 201 to 3 50 ° C, preferably 2 1 ◦ to 3 0 ° C, more preferably 2 2 0 to 2 8 0 ° In the range of C, the organic phosphorus compound in the supply section (b) can be prevented from flowing back into the section (a). The section (b -1) (hereinafter, also referred to as "resin charging zone for preventing the organic phosphorus compound from flowing backward" The length of the segment (b-1) ") and the resin filling rate are changed according to the supply speed (processing speed) of the resin component or the number of revolutions of the extruder screw. A paper size applies the Chinese National Standard (CNS) A4 specification (210 > < 297 mm) '-43- 1224611 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (42) Fluorine polymerization using an organic phosphorus compound for flame retardance and containing a dripping preventive for combustibles The flame retardant polycarbonate resin composition of the present invention is characterized by the following (1) to (4) in the method of the present invention which is produced using an extruder. (1) The first feature in the method of the present invention is that the aqueous dispersion of the fluoropolymer does not need to be pre-mixed with polycarbonate or a resin component composed of polycarbonate and other resins, and is independently The section (a) in which the resin component is maintained in an unmelted state is continuously supplied at a supply rate (kg / hr) of 0.01 to 10% of the resin supply rate (kg / hr). In this way, the fluoropolymer in the flame-retardant polycarbonate resin composition can be dispersed and uniform, and the fibril structure can be uniformly formed in the entire composition. As a result, it can be obtained Resin composition with excellent function of preventing dripping of combustibles. In addition, when an aqueous dispersion of a fluoropolymer is supplied to the section (a), the fluoropolymer and the molten resin can be kneaded without the function of a lubricant, and can have the function of lowering the kneading temperature of the molten resin, and It can reduce the load of the extruder during melt kneading. The installation position of the aqueous fluoropolymer dispersion must be supplied in section (a). Therefore, for the section (a), the optimal supply position of the aqueous dispersion of fluoropolymer is as described above. The temperature is preferably below the hopper for resin input. In addition, the temperature of the drum section below the hopper is preferably 30 to 100 t :, and more preferably 40 to 70 ° C. If the supply position of the aqueous dispersion of the fluoropolymer is set in the section (b) in which the resin component is partially molten and / or the section (c) in which the resin component is completely molten, the continuous supply squeezes The paper size of the fluorine of the press is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) -45- 1224611 A7 _B7 _ V. Description of the Invention (43) (Please (Please read the precautions on the reverse side before filling out this page) The polymer is very likely to agglomerate due to the heat generated by the high temperature molten resin. The condensed fluoropolymer is the reason for the clogging of the filter screen installed in the extruder for removing foreign matter, so the filter screen must be replaced frequently. In addition, if the condensed fluoropolymer blocks or causes the filter screen When the filter sieve is broken, the molten resin at the head of the extruder will cause turbulence, and the fiber bundles will break, and the granulation cannot be performed stably, which will hinder the stability of the production of the composition. In addition, it may cause problems such as insufficient burning prevention of dripping of a molded product obtained by molding a resin composition, or great differences in physical properties or performance. In addition, if an aqueous dispersion of a fluoropolymer is supplied to the molten resin component, an opening must be provided in the barrel section of the extruder as a supply position of the aqueous dispersion of the fluoropolymer, and the fluoropolymer is supplied. The aqueous dispersion is faithful to the molten resin, and the aqueous dispersion is extremely easy to scatter, and the scattered fluoropolymer accumulates on the wall surface of the opening portion of the barrel section of the extruder, making it difficult to supply the fluoropolymer quantitatively. In the extruder. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Generally speaking, the higher the number of screw revolutions of the extruder, the higher the dispersibility of the fluoropolymer in the resin component, and the excellent function of preventing dripping of combustible materials. The higher the tendency of the resin composition. In particular, when the resin component is particulate, the dispersion of the fluoropolymer in the obtained resin composition is greatly affected by the number of rotations of the screw. When the number of rotations of the screw is low, aggregation of the fluoropolymer is likely to occur, preventing combustion. The dropping function of the object is reduced. The number of screw revolutions of the extruder is preferably from 200 to 1,500 r p m, more preferably from 300 to 1,000 rpm, and most preferably from 400 to 800 r p m. However, on the other hand, the increase in the number of revolutions of the screw will also increase the heating of the molten resin during kneading, making the color of the resin composition or the size of the machine paper suitable for the Chinese National Standard (CNS) A4 specification (210X297 mm) '- 46- 1224611 A7 B7 5. Description of the invention (44) The mechanical properties are reduced, so the number of revolutions of the screw should be determined after considering the resin temperature in the extruder, the supply speed of each component, and the specific energy described below. (Please read the precautions on the back before filling in this page.) Also, if the aqueous dispersion of fluoropolymer is directly supplied to the extruder continuously, the aqueous dispersion of fluoropolymer will be at a temperature of 5 to 30 t, It is preferably supplied at 5 to 20 ° C, more preferably at 5 to 15 t. At the same time as the temperature of the aqueous dispersion of the fluoropolymer rises, the fluoropolymer is more likely to cause agglomeration. Therefore, if the temperature of the dispersion exceeds 30 ° C, it is often caused by Condensation of fluoropolymer causes blocking. If it is less than 5 t, the actual effect will not be obtained, and it will take more energy to cool it, which is also not good. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The supply pump for the aqueous dispersion of the fluoropolymer can be used as a diaphragm pump, a plunger pump, a cartridge-type pump, etc. Generally, the diaphragm type pump is the best for continuous quantitative supply, especially when using a pump with less mechanical contact, it can suppress the aggregation of fluoropolymer, so it is more stable from the viewpoint of supply stability. Jia Zhipu. Among them, the "mechanical contact part" refers to the part necessary for contact between parts when the pump is acting, that is, for example, when the diaphragm is pumped, it is the diaphragm part and the countercurrent prevention part, and when the plunger pump is used ， It is the piston part and the backflow prevention 弁 part. In the case of cylinder-sealed pump, it is the gap part (flywheel part) of the cylinder-sealed part. In addition, the aqueous dispersion of the fluoropolymer is supplied to the supply line of the extruder, and the injection nozzle for injection into the extruder has a dual structure. In addition, it can be cooled by using a cooling device such as a circulation type cooler. It is preferable to prevent the aggregation of the aqueous dispersion of the fluoropolymer, and to prevent the supply line and the injection nozzle portion from being blocked. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -47- 1224611 A7 _ B7 V. Description of the invention (45) (Please read the precautions on the back before filling this page) (2) The invention The second feature in the method is that the organic phosphorus compound of the flame retardant, for the section (b) in which the resin component maintains a partially molten state, is at a rate of 1 to 30% of the supply rate (kg / hr) of the resin component. The supply speed (kg / hr) is continuously supplied so that it is melt-kneaded. That is, in the method of the present invention, the organic phosphorus compound is supplied to the section (b), which can add an organic phosphorus compound after the resin starts to melt, and the organic phosphorus compound can act as a molten plasticizer for the resin component, so that The load of the resin component on the extruder is reduced, and the viscosity of the molten resin is reduced due to the addition of the organic phosphorus compound, so that excessive temperature rise caused by shear heating during kneading can be prevented, so that excellent color tone and mechanical properties can be obtained. Resin composition with excellent physical properties. The organophosphorus compound is heated in advance to 60 to 120 t, preferably 70 to 100 ° C to reduce the melt viscosity, and then passes through the injection nozzle installed in the barrel section of the extruder. It is better to squeeze and add the gear pump and plunger pump quantitatively. In the case where the organic phosphorus compound used in the present invention is in a powder form, it is preferable that the organic phosphorus compound is heated to 60 to 120 ° C in advance to be melted and then used. Organized by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as an organic phosphorus compound to be used as a flame retardant, at a specific position in section (b), when the above-mentioned speed is continuously supplied, with the amount of organic phosphorus compound added Increasingly, the organic phosphorus compound may cause a countercurrent flow to an upstream position where the organic phosphorus compound is added (hereinafter referred to as "countercurrent of the organic phosphorus compound"). The countercurrent of the organic phosphorus compound is extremely easy to be generated when the amount of the organic phosphorus compound is too large. When the resin component is in the form of particles, the particles in the section (b) are not completely melted. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -48- 1224611 A7 B7 V. Description of the invention (46) There are many voids between molten particles, so it is easy to cause backflow of organic phosphorus compounds. The countercurrent of the organophosphorus compound will extend below the hopper for supplying resin components, which will hinder the supply of resin components to the extruder. In order to avoid this, it is preferable to provide a resin-filled section (b-1) for preventing the backflow of the above-mentioned organophosphorus compound from flowing backward. However, the main purpose of the segment (b-1) and the melt-kneading of the present invention is so long as it is the minimum segment length necessary to prevent the organic phosphorus compound from flowing backward. In this section (b-1), a part of the resin component is melted by the shear force of the extruder screw, so that the inter-particle space mentioned above can be reduced. In addition, as a result of setting the segment (b-1), the amount of the organic phosphorus compound added can be about 15 to 30 parts by weight based on 100 parts by weight of the resin component, so that stability can be obtained even at high addition amounts. And continuous operation. (3) The third feature of the method of the present invention relates to the stable production of a nonflammable resin composition having excellent mechanical strength and color tone and having excellent anti-flammable drip prevention function during combustion. Controlled from 0 _ 13 to 0 _ 20 kW, preferably in the range of hr / kg. The specific energy mentioned above is defined by the energy consumption (k W) of the screw extruder motor that is required for the flame-retardant resin composition to be manufactured at a speed of 1 kg / hr, and is used as a measure of the degree of resin kneading. When the specific energy is less than 0 _ 1 3 k W · hr / kg, the kneading of the resin composition is not sufficient, and the performance of the intended resin composition cannot be obtained. In addition, because the kneading is insufficient, the extruded single The silk is prone to breakage and other problems, and problems such as the difficulty in producing pellets stably, reduce production stability. In addition, when the specific energy exceeds 0.20 k W · hr / kg or more, the size of the paper used during melt-kneading is applicable to China National Standard (CNS) A4 (210X297 mm) I --------- clothing -(Please read the precautions on the back before filling this page), printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -49- 1224611 A7 _B7_____ V. Description of the invention (47) The shear heat generated is extremely large, making the molten resin The temperature rises to a temperature higher than necessary, so in addition to the significant coloration of the resin composition, the impact resistance or characteristics of the resin composition are also reduced, and the function of preventing dripping of the combustible material is also reduced. In the method of the present invention, the preferred specific energy is 0.135 to 0 · 18kW.hr/kg, more preferably 0 · 14 to 0. 17kW * hr / kg, and most preferably 0 _ 145 to ◦. 1 6 k W · hr / kg range. The specific energy can be controlled by making appropriate choices according to the screw configuration, screw rotation number, supply speed of each component, set temperature of the drum, and the molecular weight and addition ratio of the resin. In the method of the present invention, the organophosphorus compound is supplied in the section (b) in which the resin component is partially melted to perform the melt-kneading result. Because the resin component is kneaded in the presence of the organophosphorus compound in the flame retardant, the The plasticity-promoting effect of the organic phosphorus compound enables the resin component to be efficiently plasticized even at a temperature lower than the set temperature of the extruder drum. Therefore, even if the set temperature of the drum of the extruder is low, the specific energy can be suppressed to perform melt kneading. In order to obtain a flame-retardant polycarbonate resin composition having excellent mechanical properties or flame retardancy or color tone, it is preferable to perform melt-kneading at a low resin temperature as much as possible. The organic phosphorus compound of the present invention is in the supply section ( In case of b), when the specific energy is controlled in the range of 0.13 to 0. 20 kW · hr / kg and then the melt-kneading is performed, the melt-kneading can be performed at a lower resin temperature. (4) In addition, the fourth feature of the method of the present invention is that the resin temperature in the extruder is maintained below 300 ° C. In the method of the present invention, in general, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 × 0 × 297 mm) (please read the precautions on the back before filling out this page) -50-1224611 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (48) Extrusion is performed under the condition that the temperature of the die part at the front end of the extruder is set to the highest. The temperature of the molten resin measured near the head is regarded as the highest temperature of the resin in the extruder. If the resin temperature in the extruder is higher than 300 ° C, the function of preventing dripping of combustible materials will be reduced, and the decomposition of the resin composition will be rapidly carried out, which will increase the melt flow and make it impact resistant. significantly reduce. When the mechanical properties of the flame-retardant polycarbonate resin composition are to be increased upwards and the coloration is suppressed, the temperature of the resin in the extruder is better at a lower temperature within the range that can be melt-kneaded. , Will increase the viscosity of the molten resin, and cause the load on the extruder to reduce the productivity of the resin composition. Therefore, the resin temperature, in terms of the balance between the performance and productivity of the resin composition, is preferably from 230 to 290 t, more preferably from 250 to 285 ° C, and from 260 to 2 80 ° C. optimal. Hereinafter, preferred manufacturing conditions other than those described above will be described. In the method of the present invention, the shorter the residence time of the resin component in the extruder, the better the high-temperature and high-humidity resistance of the flame-retardant polycarbonate resin composition or the degree of improvement in color tone will be. Therefore, in order to obtain a resin composition having the desired performance, each component must be sufficiently melt-kneaded, but the result of excessive melt-kneading will also cause the resin composition to have high temperature and humidity resistance or reduce color tone. Therefore, in the method for producing a flame-retardant polycarbonate resin composition of the present invention, the time during which the resin component stays in the extruder is preferably 1 to 40 seconds, more preferably 5 to 30 seconds, and most preferably From 8 to 20 seconds, a flame retardant polycarbonate resin composition having improved high temperature and high humidity resistance and color tone can be obtained in this way. In addition, in the present invention, the "residence time in the extruder" of the resin component is (please read the precautions on the back before filling this page).

1P% This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -51-1224611 A7 B7 __ V. Description of the invention (49) (Please read the precautions on the back before filling this page) The color component is charged at the resin component input position, and the time from when the colored particles are injected to when the colored resin is discharged from the die is defined. The residence time of the resin component in the extruder is determined by factors such as the supply speed of each component, the number of revolutions of the screw, the L / D (length / diameter ratio) of the extruder, and the space volume of the die portion of the extruder. influences. In the present invention, in order to shorten the time during which the resin component stays in the extruder, the L / D of the extruder can be set to a smaller number within a range where the components are sufficiently melt-kneaded. Therefore, the range of L / D is preferably in the range of 25 to 50, more preferably in the range of 30 to 45, and most preferably in the range of 35 to 40. In addition, the space volume of the die portion of the extruder is also limited as much as possible, so that the residence time of the resin can be prevented. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, in the method of the present invention, the residence time of the resin component in the extruder is affected by the supply speed of each component or the number of screw revolutions of the extruder. In the present invention, The residence time of the resin component in the extruder is 40 seconds or less, preferably 30 seconds or less, and more preferably 20 seconds or less. The speed at which each component is supplied to the extruder is limited by the processing capacity of the extruder. However, when the supply speed of each component is increased as much as possible in the above range, the temperature of the molten resin can be reduced. In addition, the resin in the extruder can be shortened. Ingredient retention time in the extruder. In general, as the number of screw revolutions of the extruder is higher, the time for which the resin component stays in the extruder will be shorter, but when the number of screw revolutions of the extruder is increased, the resin will also produce significant shear. Cut heat, and because the temperature of the molten resin rises excessively, it will adversely affect the physical properties or color tone of the resin composition. Therefore, when considering the temperature of the molten resin, the number of revolutions of the extruder should be selected. This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -52- 1224611 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 ___ V. Description of the invention (50) As mentioned above, in the present invention In the method, if the organic phosphorus compound is added, the plasticization of the molten resin will be easier, and the viscosity of the molten resin may be reduced. Therefore, the temperature rise caused by excessive shear heat generated by the melt-kneading can be suppressed. Therefore, In the manufacturing method of the present invention, it is possible to carry out the production of a flame-resistant polycarbonate resin composition with a higher number of rotations of the extruder screw. When the number of screw revolutions of the extruder is high, the residence time in the extruder can be shortened due to the improvement of the handling capacity of the molten resin. Therefore, the manufacturing method of the present invention can be made with high temperature and humidity resistance at high production speed. Special resin composition. In the method of the present invention, it is preferable to use a solid resin component in a form in which 70% by weight or more is in a granular form. When more than 70% by weight of the resin component is in the form of granules, when the resin component is supplied to the extruder, the meshing state between the extruder screw and the resin component can be made good, so that the resin component can be stably supplied at a high supply speed. Therefore, a flame-retardant polycarbonate resin composition can be produced at a high production speed. In the present invention, it is more preferable that 80% by weight or more of the resin component is granular, and it is more preferable that 90% by weight or more is granular. In addition, if 30% by weight or more of the resin component is in the form of a powder, if the resin component is supplied to the extruder, the state of the bite between the screw of the extruder and the resin component will be poor, and the resin component cannot be used in a sufficient amount. Supply speed supply, or agglomeration in the supply part of the resin component makes it impossible to stably supply the aqueous dispersion of the fluoropolymer. Hereinafter, the method of the present invention will be described with reference to FIG. 1. Fig. 1 is a schematic cross-sectional view of an internal structure exemplified by an extruder used in the method of the present invention. This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) ~ -53- (Please read the precautions on the back before filling this page) 1224611 A7 B7 V. Description of the invention (51) Extruder of Figure 1 It consists of 9 drum sections B 1 to B 9 (the most upstream drum section of the press (please read the precautions on the back before filling this page) is the first drum section and the downstream drum section The section is the ninth cylinder section) and an extruder of a co-rotating co-rotating two-axis extruder composed of a die sleeve 8. In the screw structure of the extruder shown in Fig. 1, the screw components of the extruder can be appropriately combined to obtain the required constituents. In addition, the temperature of each barrel section can be controlled independently. In FIG. 1, the areas shown by a, b, and c each indicate a section (a) in which the resin component is maintained in an unmelted state, a section (b) in which the resin component is maintained in a partially molten state, and the resin component is maintained completely Section (c) in the molten state. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the extruder shown in Figure 1. If viewed from the extrusion direction of the extruder, it is from the upstream to the downstream direction, and five forward scraper screw members are provided. 1. A forward kneading member obtained by laminating 5 pieces of oval flat plates 1 1. A reverse kneading member obtained by laminating 5 pieces of oval flat plates 1 2. Two forward screw kneading members 1 3 2 pieces of forward kneading members obtained by laminating 5 pieces of oval flat plates 1 2 pieces of neutral kneading members obtained by laminating 5 pieces of oval flat plates 1 4 1 layer of 7 pieces of oval flat plates The obtained reverse kneading members 1 2, 1 reverse scraper screw member 1, 5, 3 forward scraper screw members 1 0, 1 forward kneading member obtained by laminating 5 pieces of oval flat plates 1 1. One screw was obtained by laminating 5 pieces of oval-shaped flat plates, a reverse kneading member 1, 2, and a reverse scraper screw member 15 were combined with four forward scraper screw members 10. In addition, the set temperatures of the temperatures of the nine barrel sections B 1 to B 9 are as follows: The first paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -54- 1224611 A7 B7 V. Description of the invention (52) ( Please read the notes on the back before filling in this page) 1 cylinder section B 1 is 30 to 7 0 t :, the second cylinder section B 2 is 180 to 220 ° C, and the third cylinder section B 3 22 ° to 260 ° C, 4th cylinder section B 4 is 2 2 0 to 2 8 0 ° C, 5th to 9th cylinder section B5 to B9 is 220 to 2 7 0 ° C, die sleeve section 8 The temperature is 230 to 270t. In the method of the present invention, the resin component 3 a (only polycarbonate, or a resin other than polycarbonate and the polycarbonate described above) or the additive component 3 b can be used as a weight feed extruder or crawler feeder, respectively. The supply port 1 (a ') is supplied quantitatively independently via the hopper 2 of the extruder. The number of quantitative feeders for these components is not particularly limited. The aqueous dispersion of fluoropolymer does not need to be mixed with the resin component in advance, and it can use a diaphragm pump or a plunger pump to cool the injection nozzle 4 for cooling, so as to supply the resin component at a speed (] ^ 忌 / ] 11 ') is continuously supplied at a supply rate (kg / h I ·) of 0.01 to 10% in the first and second drum sections B1 and B2 corresponding to the section (a). The first drum section B 1 is preferably supplied to the lower part of the hopper 2. In Fig. 1, the temperature of the first drum section B 1 is preferably set at 30 to 70 ° C. Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs in the 3rd to 5th cylinder sections B3 to B5 in Figure 1 are the sections (b) corresponding to the resin maintaining a partially molten state. The resin components are mixed in the extruder section. The organophosphorus compound is heated in advance to 60 to 120 t, using a gear pump or a plunger pump through the injection nozzle 5 a of the device in the third cylinder section, and the resin component is supplied from the supply port 5 (b ') Continuously supplied into the extruder at a supply speed (kg / hr) of 1 to 30%. The size of the injection spray paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -55- 1224611 A7 B7 V. Description of the invention (53) (Please read the precautions on the back before filling this page) _ 5 a It is set in the middle part of the resin charging section I (b-1), which is the resin charging section that prevents the backflow of the organic phosphorus compound, and the supplied organic phosphorus compound is melted during the melting process as the resin component through this nozzle stomach. The function of tapeworm plasticizer reduces the load of the extruder and reduces the heat of shear, so that high-performance resin products can be produced at high speed. In FIG. 1, the resin charging section I (b-1) for preventing the backflow of the organic phosphorus compound is formed by combining a forward kneading member 11 and a reverse kneading member 12 through the screw of the extruder. The structure can make a part of the resin component be melted by being squeezed by the shearing force, and the resin has the effect of moving the upstream side of the reverse kneading member, so the filling rate of the resin can be reached from 7 to 1. The range of 0. In this way, the organic phosphorus compound supplied from the supply port 5 (b ') in FIG. 1 can be prevented from flowing backward toward the upstream side in the extrusion direction. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the main mixing section Π in Figure 1. The resin components, organic phosphorus compounds and fluoropolymers can be added, and even other components that need to be added are kneaded in the forward direction. 1 1 The neutral kneading member 1 4, the reverse kneading member 1 2, and the reverse scraper screw member 15 are combined and melt-kneaded to a state where the resin filling rate reaches 1. If the melt-kneading of the main kneading section Π is insufficient, the quality of the obtained resin composition is not stable, which may easily cause problems such as the stoppage of the extruder due to problems such as monofilament breakage and the continuous operation is lost. The meaning of stability. In addition, if the melt-kneading is excessive, the color tone, flame retardancy, or mechanical properties of the resin composition are lowered, which is also not preferable. In Fig. 1, the resin charging section m for preventing the overflow of the discharge port is to prevent the molten resin of the discharge port 6 from overflowing, so it is necessary to increase the filling rate of the resin. Figure ^ Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -56-1224611 A7 B7 V. Description of the invention (54) 1 In the system, there is a forward kneading member 11, a reverse kneading member 1 2 is combined with a reverse scraper screw member 15 to form a resin filling section II for preventing overflow. In this section, the kneading degree of the molten resin can be increased as necessary. The vent port 6 shown in Fig. 1 can be opened to allow it to be devoured, and it is preferable to perform a reduced pressure devour. If necessary, a filter screen 7 for removing foreign matter may be installed on the membrane head sleeve 8. After the monofilament was extruded from the outlet 9 (c ') of the resin composition, it was water-cooled and pelletized to obtain a flame-retardant polycarbonate resin composition. In the manufacturing method of the present invention, the resin temperature can be measured by a thermoelectric pair installed near the die. The resin temperature and specific energy are affected by the operating conditions such as the design of the screw, the supply speed of the raw materials, the number of revolutions of the screw, and the set temperature of the extruder. However, in the present invention, the resin temperature is below 300 ° C, and the specific energy is When the resin composition is appropriately selected in the range of 0.13 to 0.20 W, hr / kg, a resin composition can be produced. There are no particular restrictions on the method for forming various molded articles from the flame-retardant polycarbonate resin composition produced by the method of the present invention. For example, the method can be formed by extrusion molding, compression molding, injection molding, and gas injection molding. Among them, injection molding is the best. Products such as laptops, computer terminals, printers, photocopiers and other OA machine bodies, A machine frames, mobile phone cases, etc. [Best Mode for Implementing the Invention] Hereinafter, the present invention will be described in more detail with examples and comparative examples. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before reading) (Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-57- 1224611 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs limited. In the examples and comparative examples, the following components were used to produce a polycarbonate resin composition. 1. Polycarbonate (P C-1) Granular bisphenol A-based polycarbonate is prepared by melting bisphenol A and bisphenyl carbonate through a melt transesterification method. Weight-average molecular weight (Mw) = 2 1,000 The ratio of benzene-based terminal groups (the ratio of phenol-based terminal groups to all the terminal groups) 23 3% (PC-2) A granular bisphenol A-based polymer was prepared by the phosgene method For the carbonate, a granule mixture (S- 2000 / Η- 4000 = 65) manufactured by Japan and Mitsubishi Plastics Co., Ltd. with the trade name r Youbilong S-2000 is used and the trade name is Yubilong Η-4 0 0 0. / 35) 2. Rubber modified styrenic copolymer (ABS-1) Acrylonitrile-butadiene-styrene resin with a granular butadiene rubber content of 22% by weight. Republic of China, Chi Mei company ABS resin (commodity Name: PA7 0 9 N) (ABS-2) This paper size applies Chinese National Standard (CNS) μ specification (210X297 mm) (Please read the precautions on the back before filling out this page) Clothing · ， 11 thread ·-58 -12246li A7 -------- B7 ____:-5. Description of the invention (56) Powdered acrylonitrile-butadiene-styrene copolymer Japan, Mitsubishi Liyang Corporation AB S resin (trade name: R ( :) (SAN) Granular acrylonitrile-styrene composed of acrylonitrile units of 25. 0% by weight and styrene units of 7 $ _ 0% by weight. Mw = 130, 〇〇〇 (Μ BS-1) powdered methacrylate-butadiene-styrene copolymer, MB S resin (trade name: A ^ Powder C- 2 2 3 A) (M BS-2) powdered methyl methacrylate-butadiene-styrene copolymer MB S resin (trade name: M — 5 1) manufactured by Formosa Plastics Corporation, Republic of China 3. Organic phosphorus The compound (phosphate ester 1) is an oligomer of an organophosphorus compound represented by the aforementioned formula (1), its substituents R3, Rb, R. and Rd are all phenyl groups, and the weight average condensation degree (N) is 1 · 12. Polymer having an acid value of 0.45 mgKOH / g. 0 (phosphate ester 2)

It is an oligomer of an organophosphorus compound represented by the aforementioned formula (1), and its substituents are Ra, Rb, and R. Both 1 and 1 ^ are phenyl, and the average weight of condensation (N paper size applies Chinese National Standard (CNS) A4 specifications (mm) ~ 1-59- (Please read the precautions on the back before filling this page). '' Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1224611 A7 _____B7 __ V. The polymer of the invention description (57) is 1.08 and the acid value is 0.01 mgKOH / g. 0 (Please read the precautions on the back before Fill in this page) (Phosphate ester 3) Japan, Mitsui DuPont, Japan, water-based p TFE (polytetrafluoroethylene) aqueous dispersion (trade name: Teflon 3 0 J) Teflon content = 6 0w t% 5. Other ingredients (Additive 1) η — Eighteen courtyard bases 3 — (3,, 5 — 1 t — Butyl — 4′-hydroxyphenyl) propionate (Switzerland, Ciba Gaget) Manufactured by a chemical company, trade name: IRGAN0X 1076) (Additive 1 2) Tris (2,4 121-t-butylphenyl) phosphite (Switzerland, Ciba Gaget Chemical Company, trade name · IRGAF0S 168) Example 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, using 2 axes with the structure shown in Figure 2 Press (TEM -58SS, L / D = 37, East Japan Co., Ltd.), melt-kneaded, to prepare a flame retardant polycarbonate resin composition. The structure of the extruder screw shown in Fig. 2 is composed of 5 forward scraper screw members 10 and 1 from the upstream direction to the downstream direction of the extrusion direction. Component 1 1, 2 forward worm tired rod kneading components 1 3, 3 forward scraper screw components 1 0, 2 from 5 This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 29 < 7 males) (%) -60-1224611 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (58) Neutral kneading members obtained by laminating oval flat plates 1 to 4, 1 from 7 pieces Ellipse-like flat plate laminated reverse kneading member 1 2, 1 reverse scraper screw member 1 5, 4 forward scraper screw member 10, 1 forward direction obtained by laminating 5 pieces of oval-shaped flat plate The kneading members 1 and 1 are composed of a screw obtained by combining a reverse kneading member 12 obtained by laminating 7 pieces of elliptical flat plates and 4 forward-screw screw members 10. The set temperatures for the temperatures of the nine drum sections B 1 to B 9 are as follows: the first drum section B 1 is 50 ° C, the second drum section B 2 is 2 2 0 ° C, and the third drum section Segment B 3 is 2 5 0 ° C, 4th cylinder section 34 is 260 ° (:, 5th to 9th cylinder section 65 to: 69 is 2 5 0 t :, and the temperature of die sleeve section 8 is 2 5 0 ° C. Granular polycarbonate resin (PC — 1) 3 a at 5 60 kg / hr, granular acrylonitrile-cetadiene-styrene resin (ABS -1) 3 b at 1 2 0 kg / hr, powdered methacrylate-butadiene-styrene copolymer (MBS-1) 3c at 20 kg / hr, and additive 1 and additive 2 fat powder mixture 3 d (additive 1 1 ·· additive 1 2 = 1 0 ·· 1) is continuously supplied to the supply port 1 (a ') through the hopper 2 at a speed of 0.7 kg / hr. Furthermore, an aqueous dispersion of a fluoropolymer cooled to 10 ° C (D PTFE) The supply nozzle 1 (a ') is continuously supplied at a supply rate of 3.5 kg / hr using a diaphragm pump by means of an injection nozzle 4 cooled by a circulating refrigerant to 1 0 t. Fig. 2 , The section of the formula a In the section (a) in the present invention, it is known from the observation of the supply port 1 (a ') that the resin component does not melt. This paper size applies the Chinese National Standard (CNS) A4 specification (21 °). '〆297 public envy) (Please read the precautions on the back before filling out this page) -61- Consumption Cooperation by Employees of Intellectual Property Bureau, Ministry of Economic Affairs 1224611 A 7 —________ B7 _ V. Description of Invention (59) The organophosphorus compound (phosphate-1) is heated in advance to 80 ° C, and then a plunger-type pump is used to continuously supply the supply port 5 at the injection nozzle 5a at a supply rate of 100 kg / hr b '). Also, in FIG. 2, the section represented by the symbol b is equivalent to the section (b) in the present invention, and is provided by a viewing window (not shown in the figure) provided in the tube section b 4 (Middle) Observation by eye method shows that the resin component is partially melted. In section I in Fig. 2, in order to increase the resin filling rate, a resin for preventing the organic phosphorus compound from flowing backward can be provided on the forward kneading member 11 of the above note. "Charging section" to prevent the supply from supply port 5 (b ') Phosphorus compounds generate countercurrent. In section Π, there are 3 forward screw members 10, 2 neutral kneading members 14, 4, 1 reverse kneading member 12, and 1 reverse scraper screw member 15. "Main Mixing Section". In section m, a "kneading prevention opening" composed of one forward kneading member 1 1 and one reverse kneading member 12 is provided to increase the resin filling rate and prevent molten resin from flowing out from the vent 6. Spilled resin filling section. " The rotation speed of the extruder was set to 480 r pm, and the vent 6 was decompressed and degassed at 50 m m H g. In addition, a 1 2 0 mesh sieve 7 is installed on the die sleeve section 8, and the resin composition monofilament extruded from the discharge port 9 (c ') is water-cooled and pelletized to obtain flame-retardant polycarbonate. Particles of an ester resin composition. The operation results of Example 1 and the physical properties of the obtained resin composition were evaluated by the following methods. (1) The temperature of the molten resin on the die head This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) _ -62- I Ί.IT. (Please read the precautions on the back before filling this page) 1224611 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_____ V. Description of the Invention (60) The temperature of the molten resin near the die is measured using thermoelectricity. (2) Specific energy The result obtained by dividing the output (k W) of the screw motor of the extruder by the production speed (k g / h r) of the resin composition. (Unit: k W · hr / kg) (3) After the filter screen is blocked for 1 hour of continuous operation, visually observe the 1 2 0 mesh filter screen 7 set on the die casing section 8 of the extruder. Hole blocked situation. 〇: No clogging of the filter screen mesh was found. △: The mesh of the filter screen is slightly blocked. X: The filter mesh is severely blocked. In this case, the filter sieve may break during operation, the pressure of the molten resin may exceed the allowable pressure, and the operation may be stopped. (4) Fracture of the extruded monofilament The continuous drawing stability of the monofilament of the resin composition extruded using a die having a diameter of 4.5 mm and 25 holes was evaluated. ○: During continuous operation for 1 hour, no filament breakage was found at all. △: Monofilament breaks during continuous operation for 1 hour. X: Extruded monofilaments frequently undergo monofilament breakage, and continuous granulation production cannot be performed stably. (5) Flame resistance Dry the obtained granules and place them in a drum set to a temperature of 250 ° C. The size of the mold paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back first) (Fill in this page) -63- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1224611 A7 B7 _ V. Description of Invention (61) Injection molding machine with a degree of 6 ot (Oder 5 0D, Japan, Feynec & Division _) For molding, make a short-form shaped body for burning test (thickness i / lS inches), and then according to UL94 standard 20MM vertical burning test (classified as V-0, V-1, v-2, etc., (flammable) Degree: V ~ 0 > V-1 > V-2)) The degree of flame retardancy was evaluated. (6) Hue The yellow color (γ I) of the composition was measured using a color computer with a Suzuka testing machine and a color difference meter of model S M 5. (7) The melting coefficient (M F R) is measured under the conditions of 26CTC and a load of 2 -16 k g based on ASTM D1238. (Unit ·· g / 10 min) (8) rz〇d impact test Measured under the notch with a thickness of 1/8 inch, based on A S M M D 2 56. The test piece was formed by an injection molding machine at a cylinder temperature of 240 ° C and a mold temperature of 60 ° C. (Unit: kg f · cm / cm) The results are shown in Table 1. As shown in Table 1, Example 1 is a flame retardant polycarbonate resin composition obtained by adding an organic phosphorus compound to make it flame retardant. At a low melting resin temperature and low specific energy, no filtration occurs. When the sieve is blocked or the extruded monofilament is broken, a flame-retardant polycarbonate resin composition can be continuously and stably produced. In addition, the obtained resin composition also has excellent flame retardancy, hue, and mechanical properties. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — Ί J. Line (Please read the precautions on the back before filling out this page) -64-1224611 Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed A7 B7 V. Description of the invention (62) Comparative Examples 1 and 2 Comparative Example 1 is based on Example 1 except that the supply of the fluoropolymer aqueous dispersion is changed to the supply port 5 'shown in Figure 2. Do the same. Further, Comparative Example 2 was manufactured in the same manner as in Example 1 except that the supply port of the flame retardant was changed to the supply port 5 '. Also, in Comparative Example 1, an opening is provided on the cylinder section at the position 5 'in FIG. 2 for the fluoropolymer aqueous dispersion to be directly supplied from the opening. Further, in Comparative Example 2, a flame-injection injection nozzle 5'a is provided at a position 5 'in FIG. 2, and the flame-retardant is supplied through this nozzle. The position of 5 ′ in FIG. 2 is the downstream position of the main kneading section Π in the extrusion direction. The fact that there is no unmelted substance at the position of 5 ′ can be observed visually from the opening of the above ( That is, the supply port 5 'is directly connected to the section (c).) 0 The operating results of Comparative Examples 1 and 2 will be evaluated in the same manner as in Example 1 with respect to the physical properties of the obtained resin composition. The results are shown in Table 1. In Comparative Example 1, the molten resin and specific energy were larger than those in Example 1. In Comparative Example 1, the clogging of the filter sieve due to the fluoropolymer agglomerates occurred within a short period of time. In addition, the extruded monofilaments frequently broke during operation, which deteriorated the productivity. In addition, the hue (Υ · I) of the composition obtained in Comparative Example 1 was worse than that of Example 1, and the flame retardancy and Izod impact strength were also poor. Comparative Example 2 is an example in which the resin temperature exceeds the range of the present invention, and its specific energy is also higher than that in Example 1. As a result, there was no obstruction of the filter sieve. The size of the paper was applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). --------------- Xu ------- (Please (Please read the notes on the back before filling this page) -65- 1224611 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7 V. Description of the Invention (63) However, the extruded monofilaments often break. When the obtained resin composition was compared with Example 1, its color tone, flame retardancy, or impact resistance were also not good, and MFR also showed a higher number than that of Example 1, so it also showed the resin caused by kneading. Deterioration situation. Comparative Example 3 Using the same raw material components as in Example 1, a resin component, an additive mixture, and an aqueous dispersion of a fluoropolymer (D is · PTF Ε) were mixed in advance with a Dempro mixer for 10 minutes, and the mixture was continuously continued. Supply port 1 (a,) was supplied at a speed of 700 kg / hr. Among them, the composition of the blend is the same as that of Example 1. pc-1: ABS— 1: MBS — 1: additive mixture: Di s.PEFE = 8 0 ·· 1 7: 3: 0 · 1: 0 5 (weight ratio). The organic phosphorus compound is also continuously supplied to the supply port 5 (b ') at a rate of 1000 kg / hr. Otherwise, a flame-retardant polycarbonate resin composition was obtained in the same manner as in Example 1. The operating results of Comparative Example 3 were evaluated in the same manner as in Example 1 for the physical properties of the obtained resin composition. The results are shown in Table 1. Comparative Example 3 In the operation, the extruded monofilament repeatedly broke, and it was impossible to continuously and continuously produce pellets. In addition, the result of obstruction of the filter sieve after one hour of operation was observed, and the situation of obstruction was observed. In addition, the obtained resin composition is not sufficient to prevent dripping of combustible materials, and has extremely poor flame retardancy. I Ί J ^. Line (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -66- 1224611 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (65) Example 2 The screw revolution number is set to 400 rpm, and the production speed 5 of the resin composition is affected by 600 kg / hr (where each raw material component is supplied to the press) The speed ratio is the same as in Example 1), and a flame retardant polycarbonate resin composition was produced under the same conditions as in Example 1. The operation results of Example 2 were evaluated in the same manner as in Example 1 for the physical properties of the obtained resin composition. The results are shown in Table 2. Example 3 The number of screw revolutions was set to 7000 rpm, and the production speed of the resin composition was set to other than 1,000 kg / hr. The flame retardant polycarbonate resin composition was produced under the same conditions as in Example 1 Thing. The operation results of Example 3 were evaluated in the same manner as in Example 1 for the physical properties of the obtained resin composition. The results are shown in Table 2. Comparative Example 4 A flame-retardant polycarbonate resin composition was produced under the same conditions as in Example 2 except that the supply of the organophosphorus compound was supplied from the supply port 5 'in FIG. 2. The operating results of Comparative Example 4 were evaluated in the same manner as in Example 1 for the physical properties of the obtained resin composition. The results are shown in Table 2. Comparative Example 4 has the same number of screw revolutions and resin production speed as in Example 2, but it has a higher molten resin temperature and higher specific energy. For the operation of Comparative Example 4, the Chinese standard (CNS) A4 specification (21〇 > < 297 mm) was applied to the paper size for several minutes after the start of production. I ΊI4r. Line (Please read the back first Please note this page, please fill in this page again) -68- 1224611 A7 _ B7 V. Description of the Invention (66) The machine is overloaded and the production is stopped, which cannot be performed in the same way as in Example 2 _. The flame retardancy, impact resistance, and color tone of the obtained resin composition were also inferior when compared with Example 2. Example 4 A flame-resistant polycarbonate resin composition was produced under the same conditions as in Example 2 except that the number of screw revolutions was set to 200 r p m and the production rate of the resin composition was set to 400 k g / h r. The operating results of Example 4 were evaluated in the same manner as in Example 1 for the physical properties of the obtained resin composition. The results are shown in Table 2. I. I--I ί 1-111 Ξι ai ^ f 1 ^ 1 · ϋι (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper applies to Chinese countries Standard (CNS) A4 specification (210X297 mm) -69- 1224611 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (68) Example 5 Using the extruder shown in Figure 2, Resin (PC-1) 3 a at 5 60 kg / hr, granular acrylonitrile-styrene copolymer (SAN) 3 b at 7 Okg / hr, powdered acrylonitrile-butadiene-styrene resin (ABS — 2) Mixture with MB S-1 at a mixing ratio (weight ratio) of 7 0/3 0 3 c at 70 kg / hr, mixture of additive 1 and additive _ 2 3 d (additive — 1: additive 2 = 10: 1) A flame retardant polycarbonate resin composition was produced under the same conditions as in Example 1 except that the supply port 1 (a ') was continuously supplied at a rate of 0.7 kg / hr. The operation results of Example 5 were evaluated in the same manner as in Example 1 for the physical properties of the obtained resin composition. The results are shown in Table 3. Example 6 A flame retardant polycarbonate resin was produced under the same conditions as in Example 1 except that the flame retardant was changed to an organic phosphorus compound (phosphate ester 2) having an acid value of 0.1 mg / K H / g.组合 物。 Composition. The operating results of Example 6 were evaluated in the same manner as in Example 1 for the physical properties of the obtained resin composition. The results are shown in Table 3. In Example 6, it has a particularly excellent composition hue and I ζ 0 d impact strength. Comparative Example 5 Except that the number of screw revolutions was set to 900 rpm, the Chinese team's (CNS) A4 specification (210 > < 297 Gongchu 1) was applied according to the paper size. -------- ir --- ---- (Please read the precautions on the back before filling this page) -71-1224611 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (69) Example 5 Production of flame retardant under the same conditions The operation results of Comparative Example 5 of the polycarbonate resin composition were evaluated in the same manner as in Example 1 for the physical properties of the obtained resin composition, and the results are shown in Table 3. The molten resin temperature of Comparative Example 5 The specific energy is outside the scope of the present invention, and the resin composition obtained in Comparative Example 5 has poor flame retardancy, hue, and izod impact strength. Comparative Example 6 Except for the fourth and fifth cylinder sections B 4 and Except that the three forward kneading members 11 in B 5 were changed to three neutral kneaded dry pieces, the pellets of the flame retardant polycarbonate resin composition were produced under the same conditions as in Example 5. Operation results of Comparative Example 6 The physical properties of the obtained resin composition are the same as in Example 1. The results are shown in Table 3. The molten resin temperature of Comparative Example 6 is outside the range of the present invention. When the resin composition obtained in Comparative Example 6 is compared with Example 5, its flame retardancy, hue and Izod The impact strength is poor. Comparative Example 7 Except changing the forward kneading member 11 in the third cylinder section B 3 to a forward blade member, three forward directions in the fourth and fifth cylinder sections B 4 and B 5 Kneading member 1 1, 2 neutral kneading members 1 4, 1 reverse kneading member 1 2, and 1 reverse scraper member 15 changed to 3 forward scraper screw members and 1 neutral kneading member, and The paper dimensions of the 7th and 8th tube sections are applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) —-I-72- (Please read the precautions on the back before filling this page) 1224611 A7 B7 5 、 Explanation of the invention (70) One forward kneading member 11 and one reverse kneading member 12 in B 7, B 8 are replaced by one forward scraper screw member, and the others are produced under the same conditions as in Example 5. Particles of a flame-retardant polycarbonate resin composition. The results of the operation of Comparative Example 7 and the obtained resin composition. The properties are evaluated according to the method of Example 1 and the results are shown in Table 3. The specific energy of Comparative Example 7 is beyond the scope of the present invention. The resin composition obtained in Comparative Example 7 has flame retardancy and color tone. Both Izod and Izod have poor impact strength. In addition, due to poor melt-kneading, monofilament has a lot of breakage, and stable granulation production is not possible. Comparative Example 8 Except the aqueous dispersion of fluoropolymer (D is · PTFE) ) The temperature was set at a temperature other than 35 ° C, and the pellets of the flame-retardant polycarbonate resin composition were prepared under the same conditions as in Example 5. Comparative Example 8 During operation, agglomerates of PTFE are generated inside the transport pump of the fluoropolymer aqueous dispersion and in the liquid delivery pipeline, resulting in the continuous and stable supply of the fluoropolymer aqueous dispersion ° — Ί J Order. Line ^^ (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 1224611 Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of the Invention (72) Example 7 Using the extruder shown in Figure 2, the polycarbonate resin (pc-1) 3a was 56kg / hr, granular ABS — 1 Mixture with SAN 8 8/17 (weight ratio) 3 b at 120 kg / hr, powdered methacrylate-butadiene monostyrene copolymer (MB S-2) 3 c at 20 kg / hr 'Additive-1 and Additive-2 mixture for 3 d (Additive 1: Additive 2 = 1 〇: 1) Continuously supply the supply port 1 (a,) at a rate of 0.7 kg / hr, all others A flame-retardant polycarbonate resin group was produced under the same conditions as in Example 1. Particles. The molten resin temperature of the die head and the flame retardancy of the resin composition were evaluated in the same manner as in Example 1. In addition, the residence time of the resin in the extruder, a notched 1/8 "Izod impact strength change at 80 ° C, 9 5 R Η% environment, and 80 ° C, 9 5 R Η% environment The hue change is evaluated according to the following methods: (1) Retention time of the resin in the extruder After the supply of each raw material component in the extruder is stabilized, 2 to 3 resin resin supply ports 1 (a ') will be used. The colored matrix particles with black color are thrown into it, and the time from the drop to the appearance of the colored molten resin on the die part is measured with a horse watch. (2) 8 0 ° C, 9 5 R Η% Environment The attached notch 1/8 "Izod impact strength change uses a short 1 / 8-inch thickness test sheet. The paper size is set at the drum temperature. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm): j Order. Thread ^^ (Please read the precautions on the back before filling in this page) -75 1224611 Α7 Β7 V. Description of the invention (73) 2 4 0 ° c, mold temperature setting 60 ° C injection molding machine for molding. After exposing the test booklet to a high temperature and high humidity environment (80 t, (please read the precautions on the back before filling out this page) 9 5 R Η%), use a color computer "Model S Μ 5 color difference meter" to pair the composition The yellow-indicated (标示 I) of a substance is measured over time. The results are shown in Table 4. As shown in Table 4, when the resin composition prepared in Example 7 was exposed to a high temperature and high humidity environment, the change with time of its impact strength was extremely slow, and ΥI 値 also increased only slightly, indicating that The change in color tone is also very small. Example 8 A resin composition was produced under the same conditions as in Example 7 except that the organic phosphorus compound was changed to phosphate-1. The operation results of Example 8 were evaluated in the same manner as in Example 7 for the physical properties of the obtained resin composition. The results are shown in Table 4. Example 9 Printed by the Intellectual Property of the Ministry of Economic Affairs and the Consumer Cooperative, except that the organic phosphorus compound was changed to phosphate ester-3, and the resin composition was produced under the same conditions as in Example 7. The operating results of Example 9 were evaluated in the same manner as in Example 7 for the physical properties of the obtained resin composition. The results are shown in Table 4. Example 10 Using an extruder shown in FIG. 2, a polycarbonate resin (PC-2) 3 3 was formed in a size of 14.0 1 忌 /] 11 ′, granular 6: 6 8-1 and 8 6 1 1 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -76- 1224611 A7 B7 V. Description of the invention (74) 8 3/1 7 (weight ratio) Mixture 313 to 3〇1 ^ 2/111 ' , Powdered methacrylate-butadiene-styrene copolymer (M BS-2) 3 c at 5 kg / hr, mixture of additive 1 and additive 2 3 d (additive 1: additive 1 2 = 1 0: 1) Continuously supply the supply port 1 (a ') at a speed of 0.17 kg / hr, and the supply speed of Di s. PTFE is 25 kg / hr. In the same manner as in Example 7, pellets of a flame-resistant polycarbonate resin composition were prepared under the condition that the screw rotation number was 350 rpm. The operating results of Example 10 were evaluated in the same manner as in the physical properties of the obtained resin composition (see Example 7). The results are shown in Table 4. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

1224611 A7 _____ B7 V. Description of the invention (76) [Industrial applicability] When the flame retardant polycarbonate resin composition is manufactured according to the method of the present invention, the load of the extruder can be reduced to prevent excessive heat generation of the molten resin, and In addition to high-speed production, it can also prevent production defects such as clogging of filter screens for removing foreign objects caused by fluoropolymers, or breakage of extruded monofilaments, and can continuously and stably produce for a long time. . In addition, according to the method of the present invention, a flame retardant polycarbonate resin having excellent flame retardance and mechanical properties, and a flame retardant polycarbonate resin having excellent appearance and color tone can be obtained by improving the dispersibility of the fluoropolymer in the composition. Composition, so it is very conducive to industrial production 0 —— — — ——— #! (Please read the precautions on the back before filling out this page) Alignment-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs China National Standard (CNS) A4 Specification (210X297 mm) -79-

Claims (1)

1224611 A8 B8 C8 D8 7T, Patent Application No. 901151 No. 19 Patent Application Chinese Application Patent Range Amendment June 10, 1993 10 Amendment 1 · A method for manufacturing a flame retardant polycarbonate resin composition, its system A method for producing a flame-retardant polycarbonate resin composition by kneading a resin component mainly composed of polycarbonate, an aqueous dispersion of a fluoropolymer, and an organic phosphorus compound with a screw extruder, is characterized in that: The screw extruder is a segment (a), a segment (b) and a segment (c) which are sequentially arranged according to the extrusion direction, and the segment (a) is related to the resin component and the fluorine One or more supply ports (a ') of the aqueous polymer dispersion are directly connected, and the section (b) is directly connected to the supply port (b') of the organic phosphorus compound, and the section (c) is connected to The extruder that directly communicates the discharge port (c ') of the polycarbonate resin composition; and (1) the resin component is continuously supplied to the section (a) through the supply port (a'), and the Aqueous dispersion of fluoropolymer and The resin component is continuously supplied in the section (a) by the same supply port (a ') used for supplying the resin component or different supply ports (a') used for supplying the resin component, on the other hand The organic phosphorus compound is continuously supplied to the section (b) through the supply port (b '); in terms of the supply rate of the resin component (kg / hr), the supply rate of the aqueous dispersion of the fluoropolymer (kg / hr) Applicable Chinese National Standard (CNS) A4 size (210 X 297 mm) for this paper size (Please read the notes on the back before filling this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 1224611 A8 B8 C8 D8 6. Scope of patent application (please read the notes on the back before filling in this page) 〇 · 01 to 10%, in terms of the supply rate of the resin component (kg / hr), the supply of the organic phosphorus The speed (kg / hr) is 1 to 30%; the resin component, the aqueous dispersion of the fluoropolymer, and the organic phosphide Θ are squeezed through the section (c) toward the discharge port (c ') during the kneading. _, At this time, in the section In a), the resin component is maintained in an unmelted state. In the section (b), the resin component is maintained in a partially molten state. In ^ @ (c), the resin component is maintained in a completely molten state; In addition, the extrusion method is a screw extruder consumed when the resin temperature in the extruder is 300 ° C or lower and the flame-retardant resin composition is manufactured at a speed of 1 kg / hr. The output energy (k W) of the running motor is determined under the condition that the specific energy is 0 · 13 to 0 · 20 kW.hr/ kg; and a flame-retardant polycarbonate resin composition is generated in the aforementioned manner; (2) The obtained flame-retardant polycarbonate resin composition is drawn through the above-mentioned discharge port (c ') and the like. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2. If the method of the first scope of patent application is applied, the extruder is a 2-axis extruder. 3. The method according to item 1 of the scope of patent application, wherein the number of screw revolutions of the extruder is more than 200 r p m. 4. The method according to item 1 of the scope of patent application, wherein a section is provided to prevent the organic phosphorus compound supplied to the section (b) from flowing back to the section (a), and the extrusion in the section (b) is squeezed The organic phosphorus in the pressing direction of the press The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1224611 A8 B8 C8 D8 VI. Patent application scope (please read the precautions on the back before filling this page) Compound In the section (b-1) provided on the upstream side of the supply position, the internal space of the extruder is to increase the volume ratio of the resin component to be a defined resin charge ratio, and the resin component, the fluoropolymer The kneading of the aqueous dispersion and the organic phosphorus compound is mainly performed in a region on the downstream side of the organic phosphorus compound supply position according to the extrusion direction of the extruder. 5. The method according to item 1 of the patent application, wherein the resin component is composed of polycarbonate and rubber-modified styrene resin. 6. The method according to item 1 of the scope of patent application, wherein 70% by weight or more of the resin components supplied to the extruder are pellets. 7. The method according to item 1 of the scope of patent application, wherein the temperature of the aqueous dispersion of the fluoropolymer supplied to the section (a) of the extruder is 5 to 300 ° C. 8. The method of claim 1 in which the acid value of the organic phosphorus compound supplied to the section (b) of the extruder is 1 mgKOH / g or less. 9. The method according to item 8 of the scope of patent application, wherein the acid value of the organic phosphorus compound supplied to the section (b) of the extruder is less than or equal to 0.1 mgKOH / g. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 10. The method according to item 1 of the scope of patent application, wherein the organic phosphorus compound is at least one compound selected from the compound group shown by the following formula (1); Paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1224611 A8 B8 C8 D8 Ra- (0) —ΡΠ ~ ° ~~ ×-V (where X is Patent Application Range (〇) irR Ra, Rb, Re and R 'are each independently an aryl group having 6 to 20 carbon atoms; η is a positive integer of 1 to 5; j, k, 1 and m are each independently 0 or 1). (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -4- 1224611 ^^ 1 (Co® 8 鲥 1111 · 8L 1224611