TW201122087A - Flame retardant resin composition and formed article obtained from the same. - Google Patents

Abstract

An objective of the invention is to provide a flame retardant resin composition and a formed article obtained from the same, which adopts a raw material originated from plants and has high flame retardance and excellent physical property,. The flame retardant resin composition of the invention contains 100 parts by weight of a resin constituent (A constituent) containing at least 50 mass% of unit polycarbonate (A-1 constituent) represented by the following formula (A-1) and 1 to 100 parts by weight of an organophosphorus compound (B constituent) represented by the following formula (1). (In the formula, X.supra.1 and X.supra.2 are respectively independent, and each is an aromatic-substituted alkyl group represented by the following formula (2))(In the formula, AL is a branched or linear chain aliphatic hydrocarbyl having 1 to 5 carbon atoms, and Ar is an optionally substituted phenyl group, optionally substituted naphthyl group or optionally substituted anthryl group. n is an integer of 1 to 3, and Ar can be bonded to any carbon atoms in AL.)

Description

201122087 VI. INSTRUCTIONS: [^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ A molded article derived therefrom. More specifically, it relates to a flame retardant resin composition containing a predetermined organic phosphorus compound and having substantially no pixels, and a molded article therefrom. BACKGROUND OF THE INVENTION In order to obtain a raw material for a resin molded article, polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), polyamine (PA6, PA66), polyester (PET, PBT) are generally used. Polycarbonate (such as ρ〇). However, these resins are manufactured using raw materials obtained from petroleum resources. In recent years, problems such as depletion of petroleum resources or the global environment have been a concern, using biologically derived substances such as plants. The production of the raw material resin is required. Especially when considering the global environmental problem, it is inferred that the resin derived from the plant material is used, even if it is burned after use, considering the amount of carbon dioxide absorbed by the plant when it is grown, the carbon revenue is reduced. Neutral's idea of carbon neutrality is also a resin that has a low load on the global environment. On the other hand, the use of resins derived from plant materials such as § Xuan is used in industrial materials, especially for electric/electronic related components. When A-related parts or automobile parts are used, it is necessary to impart flame retardancy in view of safety. At present, it is difficult to use resins derived from plant materials, especially about polylactic acid resins. Various attempts have been made to achieve a certain degree of hard-to-burn 201122087. However, such incombustible prescriptions use a large amount of flame retardant, which impairs the original physical properties of the resin. In addition to the polylactic acid resin, a polycarbonate resin which can be obtained from a raw material of an ether diol residue which can be produced from a saccharide is studied. For example, the following formula (a)

The diol which is not detected is easily produced from, for example, saccharides and starches, and three kinds of stereoisomers are known. The stereoisomers include 1,4:3,6-dianhydro-D-sorbitol (hereinafter referred to as "isosorbide" in the present specification) represented by the following formula (b).

Further, 1,4:3,6-dianhydro-D-mannitol (hereinafter referred to as "isomannitol") is shown in the following formula (4).

201122087

Isosorbide, isomannide, and isoidide are prepared from D_glucose, D_mannose, and L-idulose, respectively. For example, in the case of isosorbide, D_glucose can be hydrogenated and then dehydrated using an acid catalyst. Among the above-mentioned ether diols, it has been particularly studied to use the isosorbide of the polymer at the center and to combine them into the polycarbonate. Among them, in particular, homo-polycarbonate of isosorbide is described in Patent Documents 1 and 2. Among them, Patent Document 1 discloses a homopolycarbonate resin having a 2〇3 C melting point using a melt transesterification method. However, the polymer has only insufficient mechanical properties. As an example of high heat resistance, Patent Document 2 reports that a polycarbonate having a glass transition temperature of 17 (rc or more) measured by differential calorimetry at a temperature increase rate of i〇°c /min is considered as a molding material having a high contrast viscosity. On the other hand, in Patent Document 3, a copolymerized polycarbonate of isosorbide and a linear aliphatic diol is described. Regarding these polycarbonates formed of isosorbide, There is no research on the flame retardancy in each of the documents. (Patent Document 1) British Patent Application Publication No. 079686 (Patent Document 2) International Publication No. 2/7/3463 ( Patent Document 3) International Publication No. 2/1111〇6, 201122087 I: SUMMARY OF THE INVENTION The first object of the present invention is to provide a plant material derived from plants having high flame retardancy and good physical properties. A flame retardant resin composition and a molded article therefrom. A second object of the present invention is to provide a flame retardant resin composition containing a predetermined organic phosphorus compound and substantially free of li According to the study of the inventors of the present invention, it is an object of the present invention to use at least 50% by mass of a polycarbonate containing 100% by weight of the early form of the polycarbonate represented by the following formula (A-1). The resin component (component A) of the -1 component) and the flame retardant resin composition containing the organophosphorus compound (B) component represented by the following formula (1) in an amount of 1 to 100 parts by weight.

η η_ru ru _η η

(2) 201122087 (wherein 'AL is a branched or linear aliphatic hydrocarbon group having a carbon number of 1 to 5. Ar is a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Ar may be bonded. η is an integer of 1 to 3. η According to the present invention, a flame retardant resin composition derived from a plant material is obtained without impairing the original characteristics of the resin and achieving flame retardancy. . C. Embodiments j: Best Mode for Carrying Out the Invention Hereinafter, the flame retardant resin composition of the present invention will be described in more detail. (Resin component: bismuth component) The resin component in the present invention mainly contains polycarbonate (component A_i). The content of the polycarbonate (component A-1) in the resin component is preferably at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight. /. Most preferably at least 80% by weight, particularly preferably at least 90% by weight. The resin component (component A) also contains other resin (component A-2). The content of the other resin (component A-2) is preferably 50% by weight or less, preferably 4% by weight or more. Hereinafter, it is more preferably 30% by weight. /. The following 'best is 2% by weight or less, and particularly preferably 10% by weight. /. the following. A detailed description of other resins (component A_2) will be given later. (Polycarbonate: component A-1) The polycarbonate (A-component) in the present invention contains a carbonate unit represented by the following formula. In the percarbonate unit, the ratio of the unit represented by the following formula (A-1) is preferably 5 〇 mol% or more, more preferably 6 〇 mol% or more, and more preferably 7 〇 mol% or more, 8 G mol%. The above is especially suitable, 9 () Mo Er. The above 201122087 is the best. • 〇η /V II 0 oc- (Α-1) Polycarbonate (component A-1), the content of the biological origin of matter determined according to ASTM D6866 05 is preferably 25% or more, preferably 5% More preferably, it is 70% or more. In terms of the nature of the present invention, the higher the content of the biologically derived substance, the better, and when it is less than 25%, it is difficult to refer to the biomass material. The lower limit of the specific viscosity at 20 ° C of the solution of the polycarbonate (A) component in 100 ml of methane methane is preferably 14. 14 or more, more preferably 〇. 2 〇 or more, more preferably 0. · 22 or more. Further, the upper limit is preferably 〇45 or less, preferably 0.37 or less, more preferably 0.34 or less. When the specific viscosity is less than 0.14, it is difficult to impart sufficient mechanical strength to the molded article obtained from the resin composition of the present invention. Further, if the specific viscosity is higher than 0.45, the melt fluidity is too high, and the melting temperature which is required for fluidity at the time of molding is higher than the decomposition temperature. In addition, 'polycarbonate (Α-1 component), 250. (: The viscosity under the capillary rheometer is measured, and the range of 〇.〇8χι〇3~2'4xl〇3pa·s is better at the shear rate of GOOsec·1' O.lxlO3~2.0 The range of xl 〇 3Pa. s is preferably 0. 1 χ 1 〇 3 〜 1 5 x l 〇 3 Pa. The range of s is better. If the viscous melt viscosity is in the range of 哕, the mechanical strength is excellent, and when the resin composition of the present invention is used for forming The formation of silver at the time of molding is not good. The lower limit of the glass transition temperature (Tg) of the polycarbonate (component A-1) is preferably 1 〇〇C or more, preferably 120 (more than 3) The upper limit is preferably 165 ° C or less. If the Tg is less than 1 Torr, the heat resistance (especially the heat resistance due to moisture absorption) 9 201122087 is poor, and when the right exceeds 165 C, the resin composition of the present invention is used for molding. Melting "IL mobility is poor. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments. In addition, 'polycarbonate (component A-1), the lower limit of 5% weight loss temperature is 3 〇〇C or more Preferably, it is 32 〇. (: Above, the upper limit is 400. (: The following is better, preferably 39 〇t or less, more preferably 380. (The following: 5% weight loss temperature is within the above range, and it is suitable to use the resin composition of the present invention for molding, and there is almost no decomposition of the resin. The 5% weight reduction temperature is TGA manufactured by TA Instruments ( Model TGA2950) was measured. Polycarbonate (component A-1), glass transition temperature (Tg) at 1 〇〇 〇 165 ° C ' and 5% weight loss temperature (Td) at 300 ° C ~ 400. (: It is better. Polycarbonate (component A-1) can be obtained by the following formula (a)

The diol and the carbonic acid diester are produced by a melt polymerization method. Specific examples of the stilbene include isosorbide, isomannide, and isoidide represented by the following formulas (b), (c), and (d).

10 201122087

These saccharide-derived ether diols are also made from natural biomass and are known as renewable resources. Isosorbide is obtained by hydrogenating D-glucose prepared from starch and then dehydrating it. Other ether diols are obtained by the same reaction in addition to the starting materials. In particular, the carbonate unit is preferably a polycarbonate formed of a unit derived from isosorbide (1,4:3,6-dide-D-sorbitol). Isosorbide is an ether diol which can be easily produced from starch or the like, and is abundantly obtained as a resource. In addition, compared with isomannide or isoidide, the ease of production, the nature, and the breadth of use are all excellent. The polycarbonate (component A-1) may be copolymerized with an aliphatic diol or an aromatic bisphenol within a range not impairing the properties. As the aliphatic diol, a linear aliphatic diol having 3 to 12 carbon atoms and an alicyclic diol having 6 to 20 carbon atoms are suitably used. Specific examples thereof include a linear diol such as 1,3-propane diol, 1,4-butane diol or 1,6-hexane diol, or an alicyclic ring such as cyclohexanediol or cyclohexanedimethanol. Alkane and the like. Among them, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and cyclohexaneditol are preferred. Further, since the resin composition of the present invention has the above formula (a) as a raw material obtained from a renewable resource such as a plant, the plant-derived glycol is also suitably used. Specific examples include glycols containing a terpene component. The aromatic bisphenols are exemplified by 2,2-bis(4-hydroxyphenyl)propane (commonly known as "bisphenol A"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1- Bis(4-hydroxyphenyl 201122087)-3,3,5-trimethylcyclohexane, 4,4'-(p-phenyldiisopropylidene)diphenol (4,4,-(m-Phenylenediisopropyridene) Diphenol), 9,9-bis(4-carbyl-3-methylphenyl)anthracene, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-dual (4) -Hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, 1,3_bis{2-(4-hydroxyphenyl)propyl}benzene, and the like. These aliphatic diols and aromatic bisphenols may be used singly or in combination. Further, in the polycarbonate (component A-1), the terminal group can be introduced in a range which does not impair the properties. Such a terminal group can be introduced by adding a corresponding hydroxyl compound at the time of polymerization. The terminal group is preferably an end group represented by the following formula (1) or (ii).

In the above formula (i) (ii), R4 is an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula ( Iii). Conveniently, it is an alkyl group having 4 to 2 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the following formula (out). In particular, an alkyl group having 8 to 20 carbon atoms or the following formula (iii) is preferred. Y is preferably at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amine bond, and a guanamine bond. The comparative value is at least one bond selected from the group consisting of a single bond, an ether bond, and an ester bond. Among them, a single bond and an ester bond are preferred. & is an integer of 丨~5, and an integer of 1 to 3 is suitable, especially 1 is preferable. 12 201122087 —(CH2)b- R5 —Si—O· R6 R7 —Si—R8 R9 (ill) Further, in the above formula (iii), R 5 , R 6 , R 7 , R 8 and R 9 are each independently selected from carbon atoms. a calcination group of 1 to 10 Å, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a group of at least one of the constituent ethnic groups. It is preferable that each is independently a group selected from at least one of a group consisting of a group having 1 to 10 carbon atoms and an aryl group having 6 to 1 carbon atoms. In particular, it is preferred that the groups are independently selected from at least one of a group consisting of a methyl group and a stupid group. b is an integer of 〇~3, preferably an integer of 1 to 3, and particularly preferably an integer of 2 to 3. c is an integer of 4 to 100, preferably an integer of 4 to 5 inches, particularly preferably an integer of 8 to 5 inches. Since the polycarbonate S| (A_1 component) has a carbonated singapore S which uses a raw material obtained from a renewable lean source such as a plant, the main chain structure towel is a renewable resource such as a plant or a plant. The raw materials obtained are preferred. The & base compound obtained from plants is exemplified by long-chain alcohols (transol, hard alcohol, behenyl alcohol) having a carbon number of 14 or more, which are obtained from vegetable oil. Further, a bishydroxy compound and a carbonic acid diester containing the ether diol represented by the above formula (4) are mixed, and _ a is removed under a reduced pressure in the south tempering temperature to remove the oleic acid produced by the transesterification reaction, which is called (four) «carbon _ ( A_1 ingredient).

'*In order to suppress the decomposition of the diol, it is preferable to obtain a high-density resin with less coloration, and it is preferable to use a condition that the A-paste is low, but in order to appropriately promote the polymerization reaction, the polymerization, the electricity, and the electricity are 180. (: ~28 (the range of rc is better, preferably 13 201122087 is in the range of 180 ° C to 270 ° C. In addition, the ether diol and the carbonic acid diester are heated at normal pressure in the initial stage of the reaction, so that after the pre-reaction occurs, The pressure is gradually reduced and the system is depressurized to L3 xl (T3 to 1.3xl (T5 MPa or so, and it is preferable to remove the produced alcohol or phenol) at a later stage of the reaction. The reaction time is usually about 1 to 4 hours. A polymerization catalyst can be used for the polymerization rate. The polymerization catalyst may, for example, be an alkali metal compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or a sodium or potassium salt of a dihydric phenol. Further, an alkaline earth metal compound such as calcium hydroxide, barium hydroxide or magnesium hydroxide is exemplified, and tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutyl hydroxide chain, diammonium amine, and the like are also exemplified. Nitrogen-containing test compound, etc., may be used singly or in combination of two or more kinds thereof, and it is preferred to use a nitrogen-containing test compound and a metal test compound for use. , respectively, relative to the acid diester component 1 Mo's It is selected in the range of 1χ1〇_9 to 1X10-3 equivalents, preferably in the range of lxl〇_8~5Χι〇·4 equivalents. The reaction system is kept inactive gas with respect to raw materials such as nitrogen, reaction mixture, and reaction product. The atmosphere may be argon or the like as an inert gas other than nitrogen. Further, an additive such as an antioxidant may be added as needed. The carbonic acid diester used in the production of the polycarbonate (component A-1) is also listed. An ester such as an aryl group, an aralkyl group or an alkyl group having 1 to 18 carbon atoms which may be substituted with 6 to 20 carbon atoms, and specific examples thereof include diphenyl carbonate, bis(oxyphenyl) carbonate, and m-phenyl phenyl carbonate. , dinaphthyl carbonate, bis(p-butylphenyl) carbonate, dinonyl carbonate, diethylene carbonate, dibutyl carbonate, etc., wherein diphenyl carbonate is preferred. 14 201122087 Mixing carbonic acid diester into The molar ratio of the total ether diol compound is preferably from 1.02 to 0.98, more preferably from 1.01 to 0.98, still more preferably from 1.01 to 0.99. The molar ratio of the carbonic acid diester to more than 1.02 is a carbonate residue. It is not suitable as a terminal blocking function to obtain a sufficient degree of polymerization. When the molar ratio of the diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, and it is not preferable to add a catalyst deactivator to the polycarbonate (component A-1) obtained by the above production method. The catalyst deactivating agent acts as a catalyst deactivating agent, but among them, an ammonium salt or a sulphate salt of a sulfonic acid is preferred, and a dodecyl benzene sulfonic acid such as tetrabutyl sulfonate of tetradecylbenzenesulfonate is used. The above salts of p-toluenesulfonic acid such as the above salts or tetrabutylammonium p-toluenesulfonate are preferred. Further, methyl benzenesulfonate, ethyl benzenesulfonate and butyl benzenesulfonate of the sulfonate are suitably used. And octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate and the like. Among them, tetrabutylphosphonium dodecylbenzenesulfonate is preferably used. The amount of the catalyst deactivator to be used may be 0.5 to 50 moles per mole of the polymerization catalyst 1 molar selected from the alkali metal compound and/or the alkaline earth metal compound, and is preferably 0.5 to 10 moles. The ratio of ears is better to use in a ratio of 0.8 to 5 moles. (Other thermoplastic resin: component A-2) The resin component (component A) may contain other thermoplastic resin (component A-2) in addition to the polycarbonate (component A-1). The content of the other resin (component A-2) in the above component A is preferably 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, and most preferably 20% by weight to 15% by weight. Under 201122087, it is particularly good to be ίο% by weight or less. The component A-2 is exemplified by polyester resin (PEst), polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO), and styrene. A thermoplastic resin of at least one of a group consisting of a resin, a polyphenylene sulfide resin (PPS), and a polyether sulfimide resin (PEI). Among these A-2 components, polyester resin (PEst) 'polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (p〇), and benzene are preferable. Vinyl resin. Next, the thermoplastic resin of the component A-2 will be specifically described. The polyester resin (PEst) of the component A-2 is exemplified by an aromatic polyester resin or an aliphatic polyester resin, or a mixture of two or more thereof. It is desirable that the aromatic poly-lipids are formed by a two-component aromatic-based test and a diol component mainly composed of a carbon number 2 to a lipid (tetra)diol (IV). More preferably, it is 80 mol% or more, preferably 9 () mol% or more of aryl. The composition of the incense and the second base. On the other hand, the diol component is preferably 8 Å or more, and the sew is 90 mol% or more, and is formed of a carbon number 2 to an aliphatic component. An example of a call to acid, M^ 午 & week is a pair of 婪 曱 曱 间 间 曱 一 一 一 一 一 一 一 一 一 一 一 一 一 一 从 从 从 从 从 从 从 从 从 从 从 从 从 从 从 从 从 从 从.. Hai can use one or more than one. Fang Xiangzu, a carboxylic acid S text, the secondary appearance of the sip of the second acid, azelaic acid, twelve, for example, 'adipic acid, azelaic acid, Aliphatic acid or alicyclic second _ etc. "Citonic acid, cyclohexyl dicarboxylic acid, etc. aliphatic diol butanediol, 1,6-hexanediol, new, B- Yeast, propylene glycol, aliphatic diol. Further, an alicyclic diol such as 16 201122087 1,4-cyclohexanedimethanol can be cited. Examples of the diol other than the aliphatic diol having 2 to 10 carbon atoms include p,p'-dihydroxyethoxybisphenol A and polyoxyethylene glycol. A suitable example of the aromatic polyester resin is that the main dicarboxylic acid component is at least one dicarboxylic acid selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid, and the main diol component is A polyester of an ester unit formed from a diol of at least one selected from the group consisting of ethylene glycol, propylene glycol and butylene glycol. Specific aromatic polyester resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyp-naphthalene At least one of a group consisting of a butylene phthalate resin, a poly(trimethylene terephthalate) resin, a polytrimethylene terephthalate resin, and a poly(p-phenylene naphthalate) resin is preferred. Most preferably, at least one selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin. In particular, polybutylene terephthalate resin is preferred. Further, as the aromatic polyester resin of the present invention, a polyester elastomer in which the above repeating unit is a main repeating unit of a hard segment can also be used. a soft segment of a polyester elastomer having a main repeating unit of a hard segment of butylene terephthalate or 2,6-naphthalenedicarboxylate butane, for example, a dicarboxylic acid selected from Forming at least one dicarboxylic acid of terephthalic acid, isophthalic acid, sebacic acid and adipic acid, the diol component is selected from long-chain diols selected from carbon 5 to 10 and H(OCH2CH2)i〇 At least one type of diol of the group of H (i = 2 to 5) is formed, and a polyester or polycaprolactone having a melting point of 10 ° C or less or amorphous may be used. 17 201122087 Furthermore, the main compound is more than 80 mol% of the total tickotropic component or the total diol component, suitably 90 mol% or more, and the main repeating unit is 80 mol% of the total repeating unit. Above, it is appropriate to repeat more than 9% of Mo〇» early 兀. The molecular weight of the aromatic polyester resin may be an intrinsic viscosity which can be used as a normal molded article, and the intrinsic viscosity determined in the phenol of 35 〇c is suitably 0.5 to 1.6 dl/g, more preferably 0.6. ~i.5dl/g. Further, in the aromatic polyester resin, it is advantageous that the terminal carboxyl group (_c〇〇H) is in an amount of from 1 to 6 Å/T (1T polymer). The amount of the terminal carboxyl group can be calculated by, for example, potentiometric titration to determine the solution between the solution titration. For the Α-2 ingredient, the resin is called, and the commonly known pentoscene resin can be used. Specific examples of such an anthracene resin include (2,6-dimethyl·1,4-propenyl)ether, (2,6-diethyl-1,4-phenylene)ether, (2) , 6-dipropyl-1,4-extension, ether, (2-methylethyl-I,4-phenylene)ether, (2. fluorenyl-6-propyl-indole) Monomers and/or copolymers such as phenyl)ether and (2,3,6-trimethyl-l,4-extended)ether. Particularly preferred are (2,6-dimercapto), 4-phenylene) ethers. Further, a copolymer of a styrene compound is graft-polymerized on the crucibles. The method of producing the PPE is not particularly limited, and the method of the first copper salt and the amine may be used as a catalyst, for example, in the method described in U.S. Patent No. 3,306,874, and 2,6-diphenylbenzene may be added. Oxidative polymerization is easily produced. The reduced viscosity %p/C of the molecular weight scale of the PPE resin (0.5 g/cU, as determined by a solution of 30 ° C) is 0.2 to 0.7 dl/g, and preferably 〇.3 to 〇6 dl / & S. The PPE resin is more suitable for the flatness of the PPE resin in the dry circumference, and the flatness of the mechanical properties is improved. By adjusting the amount of the catalyst during the production of the PPE, the degree of reduction of the 201122087 can be easily adjusted. The polycarbonate resin (PC) of the component A-2 is obtained by an interfacial polymerization reaction of various dihydroxyaryl compounds and dicarbonized carbon using a solvent such as dioxane. Further, an ester exchange reaction of an aryl compound and diphenyl carbonate is also exemplified. Representative of a polycarbonate obtained by the reaction of 2,2'-bis(4-hydroxyphenyl)propane with dicarbonated carbon. The diaryl compound forming the polycarbonate starting material is bis(4-phenylphenyl)decane, 1, fluorene-bis(4-hydroxyphenyl)ethane, 2,2'-bis(4-hydroxyl Stupid) propane, 2,2'-bis(4-hydroxyphenyl)butane, 2,2'-bis(4-hydroxyphenyl)octane, 2,2'-bis (4_base) _Methylphenyl)propane, 2,2'-bis(4_trans)-3-tert-butyl-based propane, 2,2-bis(3,5-indolyl-4-phenylbenzene) Base), 2,2'-bis(4.hydroxy-3-cyclohexylphenyl)propane, 2,2'-bis(4-hydroxy-3-methoxyphenyl)propane, 1,1' _bis(4.hydroxyphenyl)cyclopentane, l,i'-bis(4-hydroxyphenyl)cyclohexane, 1, fluorene-bis(4-hydroxyphenyl)cyclododecane, 4,4 ·-Dihydroxyphenyl ether, 4,4,-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4,-dihydroxy-3 ,3·-dimethyldiphenyl sulfide, 4,4′-di-diphenyldiphenyl]; 5 wind '4,4′-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl) ketone Wait. These dihydroxyaryl compounds may be used alone or in combination of two or more. Suitable dihydroxyaryl compounds include bisphenols which form aromatic polycarbonates having high heat resistance, bis(hydroxyphenyl)alkanes such as 2,2,-bis(4-hydroxyphenyl)propane, and bis (4). Bis(hydroxyphenyl)cycloalkane such as -hydroxyphenyl)cyclohexane, dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfone, dihydroxydiphenyl ketone or the like. The most preferred dihydroxyaryl compound is 2,2,-bis(4-hydroxyphenyl)propane which forms a bisphenolphthalein type aromatic polycarbonate. 19 201122087 In addition, if a double-shot scented polycarbonate (4) is produced in a range that does not impair heat resistance, mechanical strength, etc., it is expected that a part of the bisphenol A is substituted by a di-aryl group. The molecular weight of the carbonic acid 6 is not particularly limited, but because the too low strength will be insufficient, the overwhelming melting degree will become high and it is difficult to form, so the average molecular weight in terms of dryness is usually 10,000 to 50, which is suitable for coffee. It is 15, 〇〇〇~ 30, 〇〇〇. Here, the viscosity average molecular weight (M) is obtained by taking the specific viscosity (%p) calculated by dissolving 0.7 g of the polycarbonate solution in 2 (rCTi〇〇mi dichloromethane) into the following formula. ^ sP /C= [;7]+〇·45χ[^]2 C ["]=1.23x10-4M083 (But '[^] is the ultimate dryness 'C is based on the polymer concentration 〇·7) The basic method of dissolving acid vinegar. The interfacial polymerization method (solution polymerization method) using a carbonate precursor material, two gasified carbon, is usually carried out in the presence of an acid binder and an organic solvent. For example, sodium hydroxide or potassium hydroxide is used. An amine compound such as an alkali metal hydroxide or a pyrimidine is used as an acid-binding sword. For example, a dichloromethane or a milk-only halogenated hydrocarbon is used as an organic solvent. Further, for the purpose of promoting the reaction, for example, a tertiary amine or a fourth-order ammonium may be used. For the catalyst such as a salt, a molecular weight regulator is preferably a terminal stopper such as phenol or p-tert-butylphenol such as an alkyl-substituted phenol, and the reaction temperature is usually 0 to 4 (TC, and the reaction time is several minutes to 5 hours, in the reaction. The pH is preferably maintained at 10 or more. As a result, the molecular chain ends are not necessarily all The structure has a structure derived from a terminal stopper. The transesterification reaction (melting 20 201122087 polymerization method) using a carbonic acid diester as a carbonate precursor, and heating a predetermined ratio of dihydric phenol and diester carbonate in the presence of an inert gas Stirring and distilling off the formed alcohol or phenol. The reaction temperature is different from that of the alcohol or the desired one; the point is usually in the range of 12 〇 to 350 ° C. The reaction is distilled off from the initial stage. The reaction is completed while the alcohol or phenol is formed. In the initial stage of the reaction, a terminal stopper is added simultaneously with the diphenol or the like or in the middle of the reaction. Further, in order to promote the reaction, a conventionally known transesterification reaction can be used. Catalyst. The dicarboxylic acid used in the transesterification reaction is, for example, a diacidic acid, a naphthalene carbonate, a dinonyl carbonate, a diethyl carbonate, a dibutyl carbonate, etc. The polyamine resin (PA) of the component A-2 may, for example, be a ring-opening polymer of a cyclic mesamine, a polymer of an aminocarboxylic acid, a polycondensate of a dibasic acid and a diamine, or the like. Specific example Long 6, nylon 66, nylon 46, nylon 61 〇, nylon 612, nylon 11, nylon 12 and other aliphatic polyamines, copolymers or mixtures thereof. Also exemplified by polyhexamidine (meth) Poly(metaxylene adipamide), p〇ly (hexaniethylene terephthalamide), poly(p-iethylene terephthalamide), p〇iy(nona_ methylene terephthalamide), Poly(hexamethylene isophthalamide), poly(tetramethylene isophthalamide) or other aliphatic/aromatic polyamines, copolymers thereof Or a mixture. The polyamine which can be used in the present invention is not particularly limited. The molecular weight of the polyamine resin is preferably 1.7 to 4.5, preferably 2.0 to 21 201122087 4.0, more preferably 2.0, in 98% sulfuric acid at a concentration of ι〇/0, 25 C. ~3.5. The polyolefin resin of the component A-2 is an olefin-based monomer or copolymer such as ethylene, propylene or butylene, or a copolymer of the olefins and a monomer component which can be copolymerized. Specific examples include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymerization, ethylene-α-olefin copolymer, An ethylene-propylene copolymer, an ethylene-butene copolymer, or the like. The molecular weight of the polyolefin resin is not particularly limited, but the high molecular weight is excellent in flame retardancy. The styrene resin of the Α-2 component is a monomer or copolymer of an aromatic vinyl monomer such as styrene, α-methyl styrene or vinyl fluorene, and these monomers are combined with acrylonitrile or methacrylic acid. a copolymer of a vinyl monomer such as a methyl ester, such that styrene and/or a styrene derivative is used in a diene rubber such as polybutadiene, an ethylene/propylene rubber, an acrylate rubber, or the like, or styrene and/or Or the styrene derivative is grafted with other ethylene monomers. Specific examples of the styrene-based resin include, for example, polystyrene, impact-resistant polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin). ), methyl methacrylate · butadiene styrene copolymer (MBS resin), methyl methacrylate acrylonitrile, butadiene styrene copolymer (MABS resin), acrylonitrile acrylate rubber A resin such as a styrene copolymer (AAS resin), an acrylonitrile-ethylene propylene rubber/styrene copolymer (AES resin), or a mixture thereof. From the viewpoint of impact resistance, a rubber-modified styrene resin is preferable, and a rubber-modified styrene resin is a rubber-like polymer which is dispersed into a particle form in a matrix formed of a vinyl aromatic polymer. a polymer, in the presence of a rubbery polymer in the presence of a rubbery polymer, in the presence of a rubbery polymer, in the presence of a rubbery polymer, a monomeric monomer, a bulk polymerization, a solution polymerization or an emulsion polymerization to obtain a monomer. mixture. Examples of the rubber-like polymer may, for example, be a diene rubber such as polybutylene dichloride, poly(styrene-butadiene) or poly(acrylonitrile-butadiene), and hydrogenated the above diene rubber. Acrylate rubber such as saturated rubber, isoprene rubber, gas butylene rubber, polybutyl acrylate, and ethylene/propylene-diene polymer ternary copolymer (EPDM), especially in diene rubber good. The above-mentioned rubbery polymer has an aromatic vinyl monomer which is an essential component in a monomer mixture which may undergo graft polymerization, such as styrene, α-mercaptostyrene, p-methylstyrene, etc. the best. Examples of the ethylene monomer which may be added as needed are acrylonitrile, decyl methacrylate and the like. The rubbery polymer in the rubber-modified styrene resin is from 1 to 50% by weight, preferably from 2 to 40% by weight. The monomer mixture which can undergo graft polymerization is 99 to 50 parts by weight. /. It is suitable to be 98 to 60% by weight. The polyphenylene sulfide resin (PPS) of the Α-2 component has a repetition of the following.

In the formula, n is an integer of 1 or more, and an integer of 50 to 500 is preferably an integer of 100 to 400, and each of a linear form and a crosslinked form may be used. An example of a method for producing a polyphenylene sulfide resin is a method of reacting polydichlorobenzene with sodium sulfide 23 201122087. It can be produced by polymerizing a polymer having a low degree of polymerization, heating it in the presence of air, partially cross-linking, and mass-producing a cross-linking method, and polymerizing it by polymerization. Straight chain. The polyether quinone imine resin (PEI)' of the component A-2 has a repeating unit represented by the following formula.

In the formula, Ar1 represents an aromatic dihydroxy compound residue, and Ar2 represents an aromatic diamine residue. The aromatic dihydroxy compound is exemplified by the above-mentioned polycarbonate resin, which is not particularly preferred. The aromatic diamine is exemplified by 'm-phenylenediamine, p-diphenylamine, 4,4,-diamine biphenyl, 3,4,-diamine biphenyl, 4,4'-diamine diphenyl ether, 3, 4,-Diamine diphenyl bromide, diamine diphenylmethane, diamine diphenyl sulfone and diamine diphenyl sulfide. η in the above formula represents an integer of 5 to 1 ’ 000, and preferably an integer of 1 〇 5 〇〇. Further, examples of the production method of the polyether oxime resin are described in U.S. Patent No. 3,847,867, U.S. Patent No. 3,847,869, U.S. Patent No. 3,850,885, and U.S. Patent No. 3 , 852, 242 and U.S. Patent No. 3,855,178, and the like. Among the above various bismuth-2 components, 'polyester resin (PEst), polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamine resin (PA) or styrene resin is preferred. 24 201122087 (Organic phosphorus compound: component B) In the present invention, the organophosphorus compound used as the component B is represented by the following formula (1).

In the formula, X1 and X2 are each independently an aromatic substituted alkyl group represented by the following formula (2). —(AL-HAr )n (2) wherein AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms. The aliphatic hydrocarbon group is preferably an alkanediyl group, a trivalent group or a pyridyl group. Ar is a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Ar can be bonded to any carbon atom in the AL. η is an integer of 1 to 3. The hydrazine component is preferably one or a mixture of two or more selected from the group of organophosphorus compounds represented by the following formulas (3) and (4).

0—CHo CH5 -0

0 R4I-U \ /\ / , 0-CH^ CH?-0 r6 (3) wherein R2 and R5 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Examples of the substituent group include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a halogen atom such as a fluorine atom, a gas atom or a bromine atom; and a carbon number of 6 to 12 such as a phenyl group or a naphthyl group; Aryl and the like. 25 201122087 R, R3, R4 and R6 are each independently a hydrogen atom, a branched or linear alkyl group having a carbon number of 丨4, a phenyl group which may have a substituent, a ginger group which may have a substituent or It may also have a thiol group of a substituent. The base of the hospital is methyl, ethyl, propyl or butyl. Examples of the substituents include an alkyl group having 1 to 6 carbon atoms such as a mercapto group, an ethyl group, a propyl group or a butyl group; a halogen atom such as a fluorine atom, a gas atom or a bromine atom; and a aryl group having a carbon number of 6 to 12 such as a phenyl group or a naphthyl group; Base. R11 (|r3)p Ar1—C—AL1- :k0—C<2/CH,. \S (ί'Γ

R 12 〇—ch2 ch2-o R1 (4) wherein, each of Ar1 and Ar2 is independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. The substituent group is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, and a halogen atom such as a fluorine atom, a gas atom or a bromine atom, or a carbon number of 6 to 12 such as a naphthyl group or a naphthyl group. Aryl and the like. R, R, R13 and R14 are each independently a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 丨3, a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a fluorenyl group which may have a substituent. . Examples of the substituents include an alkyl group having a carbon number of 丨~6 such as a mercapto group, an ethyl group, a propyl group or a butyl group, a halogen atom such as a fluorine atom or a halogen atom such as a halogen atom, and an aryl group having a carbon number of 6 to 12 such as a phenyl group or a naphthyl group. Wait. Each of AL1 and AL2 is independently a branched or straight-bonded aliphatic group of carbons. The alkane hydrocarbon group may, for example, be an alkanediyl group having 1 to 4 carbon atoms such as an anthracenylene group, an ethylene group or an acryl group. Further, a trivalent group having a carbon number of 1 to 4 such as a trisyl group or an ethylene trisylpropyltriyl group may be mentioned, and a pyridyl group having a carbon number of 1 to 4 such as a methyl group, an ethyl group or a propyl group may be exemplified. . 26 201122087

Ar3 and Ar4 are each independently 'stupyl, naphthyl or anthracenyl, and the like may have a substituent. Examples of the substituent group include a carbon group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a halogen atom such as a fluorine atom, a gas atom or a desert atom; and a carbon number of 6 to 12 such as a phenyl group or a naphthyl group; Aryl and the like. P and q are each independent and are integers of 〇~3. Ar3 and Ar4 may each be bonded to any of the carbon atoms of AL and AL2. Further, it is desirable to use a compound represented by the following formulas (5), (6), (7), and (8).

[mi 0 — , 八 /~~CH2-R22 〇—ch2 CH2-〇/ (5) wherein R and R22 are each independently a phenyl group, a naphthyl group or an onion group, and the like may have a substituent. The phenyl group, the phenyl group or the fluorenyl group of the phenyl group which is preferably a phenyl group may be substituted with a hydrogen atom of the 'aromatic ring', and the substituent may, for example, be methylethylpropyl or butyl. The bonding group of the ring is an aryl group having 6 to 14 carbon atoms having an oxygen atom, a sulfur atom or an aliphatic group having a carbon number of i to 4 as an intermediate group. P—C—R35 〇36 (6) •〒一p\ - | \ / \ O—CH2 CH2—(In the above formula (6), 'R3> R34 is independent, and is a chlorine atom or a fat with a carbon number of 1 to 4. Hydrocarbyl group. Hydrogen film, 7 | ^^ soil, a a milk in the methyl, ethyl is preferred, particularly suitable for the hydrogen atom 0 R33 and R36 long white Α ν. ώ, valley from independence, for An aliphatic hydrocarbon group having a number of 1 to 4. 27 201122087 Preferably, a methyl group or an ethyl group is used. R32 and R35 are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent. a substituent may be substituted on the moiety other than the moiety bonded to the phosphorus via a carbon atom on the aromatic ring, and is a thiol group, an ethyl group, a propyl group (including an isomer), and a butyl group (including an isomer). Or a group bonded to the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. In the above formula (6), R32 and Specific examples of R35 may, for example, be phenyl, decylphenyl, xylyl, triphenylphenyl, 4-phenoxyphenyl, cumyl, naphthyl, 4-benzylphenyl, etc., especially benzene. The base is good.

RI -CI R

11 T:)P〇L·—AL-R 12 Ο—CH2 CH〇&quot;0,\ / , C, /\ / 〇—ch2 ch2-o AL2-C—Ar2 R1 (7) Equation (7) above In the above, Ar1 and Ar2 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Rn, R12, R13 and R14 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a fluorenyl group which may have a substituent. . The phenyl group is preferably a substituent other than the moiety bonded to the phosphorus via a carbon atom on the aromatic ring, and is a methyl group, an ethyl group, a propyl group (including an isomer), The butyl group (including an isomer) or a group bonded to the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. In the above formula (7), specific examples of Ar1 and Ar2 include phenyl, tolyl, xylyl, trimethyl, 4-phenoxyphenyl, cumyl, naphthalene 28 201122087, 4- Phenylphenyl or the like, especially phenyl is preferred. In the above formula (7), each of AL1 and AL2 is independently a branched or linear aliphatic hydrocarbon group having 1 to 4 carbon atoms. Conveniently, a branched or linear aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a branched or linear aliphatic hydrocarbon group having 1 to 2 carbon atoms is particularly preferable. The aliphatic hydrocarbon group is exemplified by an alkylene group having 1 to 4 carbon atoms such as a methylene group, a vinyl group or a propenyl group. Further, an alkyltriyl group having 1 to 4 carbon atoms such as a trisyl group, a trisyl group or a propyltriyl group is exemplified. Further, a pyridyl group having a carbon number of 1 to 4 such as a tetracyl group, an ethylenetetrayl group or a propyltetrayl group is also mentioned. In the above formula (7), suitable specific examples of AL1 and AL2 include a mercapto group, a vinyl group, an ethylene group, a propyl group, a propylene group, an isopropylidene group, etc., especially a methylene group or a vinyl group. Ethylene is preferred. In the above formula (7), Ar3 and Ar4 are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent. It is preferred that the phenyl group has a substituent on the portion other than the portion in which the carbon atom on the aromatic ring is bonded to the phosphorus, and is a mercapto group, an ethyl group, a propyl group (including an isomer), The butyl group (including an isomer) or the bonding group on the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Ar3 and Ar4 can be bonded to any of the carbon atoms of AL1 and AL2, respectively. In the above formula (7), p and q are each independently and are an integer of 0 to 3. Preferably, p and q are 0 or 1, and particularly suitable is 0. R41 〇n-CH, CH,-n〇 R44

29 201122087 In the above formula (8), R41 and R44 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or may have The base of the substituent. It is preferably a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a phenyl group which may have a substituent. When R41 and R44 are a phenyl group, any substituent other than the moiety bonded to the phosphorus via a carbon atom on the aromatic ring may have a substituent, and is a mercapto group, an ethyl group, a propyl group (including an isomer), The butyl group (including the isomer) or the bonding group of the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. In the above formula (8), a suitable specific example of R41 and R44 may, for example, be a hydrogen atom, a decyl group, an ethyl group, a propyl group (including an isomer), a phenyl group, a tolyl group, a xylyl group or a tridecylphenyl group. Further, 4-phenoxyphenyl, cumylphenyl, naphthyl, 4-phenylene, etc., particularly preferably a hydrogen atom, a methyl group or a phenyl group. R42, R43, R45 and R46 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. It is preferred that the phenyl group has a substituent other than the moiety bonded to the phosphorus via a carbon atom on the aromatic ring, and is a methyl group, an ethyl group, a propyl group (including an isomer), The butyl group (including the isomer) or the bonding group of the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of an aliphatic hydrocarbon group having 1 to 4 carbon atoms. In the above formula (8), specific examples of R42, R43, R45 and R46 are phenyl, tolyl, diphenyl, trimethyl, 4-phenoxyphenyl, cumyl, naphthyl. 4-benzylphenyl or the like, especially phenyl. The organophosphorus compound (component B) represented by the above formula (1) exhibits an extremely excellent flame retarding effect with respect to the resins. In the range known to the inventors of the present invention, it is known that it is difficult to ignite due to the halogen-free of the resin, and it is difficult to use a small amount of the 30 201122087 flame retardant, and there are many problems in practical use. However, according to the present invention, it has been surprisingly found that the above-mentioned organophosphorus compound (component B) can easily achieve the flame retardancy of the resins by a small amount of itself, and does not impair the original properties of the resin. However, in the present invention, in addition to the component B, the phosphorus component other than the component B can be mixed because the ratio of the component B is lowered, the flame retardancy of the molded article is improved, the physical properties of the molded article are improved, the chemical properties of the molded article are improved, or other purposes are of course possible. , fluorine-containing resin or other additives. Other mixed components such as those are described in detail later. The organophosphorus compound (component B) of the flame retardant in the resin composition of the present invention is represented by the above formula (1), and the most preferable representative compound is represented by the following formulas (1-a) and (1-b). a compound represented by (1-c), (Ι-d). 0 0-CH〇CH〇-0 0

(1 — b) Ο

(1 - c) 31 201122087

(l-d) Next, a method of synthesizing the above-mentioned organophosphorus compound (component B) of the present invention will be described. The component B may be produced by a method other than the method described below. The component B is obtained, for example, by reacting a trichlorinated scale in pentaerythritol and then treating the oxidation reactant with an alkali metal compound such as sodium methoxide, followed by reacting an aralkyl-halide. Further, the aryl alcohol is reacted in a compound obtained by reacting an arylphosphonic acid dihydrate in pentaerythritol or a compound obtained by reacting phosphorus trichloride in pentaerythritol, followed by Arbuzov transfer at a high temperature. The method can be obtained by borrowing. The latter reaction is disclosed in, for example, U.S. Patent No. 3,141,032, Japanese Patent Application Laid-Open No. Hei. No. Hei. The specific synthesis method of the component B will be described below. However, since the synthesis method is merely illustrative, the component B used in the present invention may be synthesized by a change or other synthesis method in addition to the synthesis methods. A more specific synthesis method will be described in the preparation examples described later. (I) the above-mentioned organophosphorus compound of 〇_a) in component B; reacting tri-gasification in pentaerythritol, and then treating the oxidative reactant treated with t-butanol with sodium methoxide to obtain an inert reaction . 32 201122087 (II) The above-mentioned (i_b) organophosphorus compound in component B; reacting phosphorus trichloride in pentaerythritol, and then treating the oxidation reaction treated with t-butanol with sodium methoxide to give 1-bromoethyl group The benzene reaction is obtained. (III) the aforementioned (丨-c) organophosphorus compound in component B; reacting phosphorus trichloride in pentaerythritol, and then treating the oxidation reactant treated with t-butanol with sodium methoxide to obtain 2-bromoethyl group Stupid reactions are made. (IV) The above-mentioned (i-d) organophosphorus compound in the component B; obtained by reacting diphenylphosphoniumphosphonium dichloride in pentaerythritol. Further, another method is prepared by reacting phosphorus trichloride in pentaerythritol, and reacting the product obtained by heat treatment in the presence of a catalyst with diphenyl sterol. The acid value of the component B is preferably mg7 mgKOH/g or less, preferably 0.5 mgKOH/g or less. By using the component B having an acid value in this range, a molded article excellent in flame retardancy and hue is obtained, and a molded article having good heat stability is obtained. The component B is preferably the same as the acid value of 4.4 mgKOH/g or less. The acid value here means the amount (mg) of KOH necessary to neutralize the acid component in the lg sample (component B). Moreover, component B is suitably used in an amount of at least 90%, preferably at least 95%, based on its HPLC purity. Such high purity is excellent in flame retardancy, hue' and thermal stability of the molded article. Here, the measurement of the HPLC purity of the component B can be effectively measured by the following method. The column was subjected to Develosil ODS-7 300mmx 33 201122087 4mmc|) manufactured by Nomura Chemical Co., Ltd., and the column temperature was 4 (rc. The solvent was mixed with 5:1 (capacitance S ratio) of acetonitrile and water, and injected into 5 μl. Uv_26〇nm is used. The method of removing impurities in the component B is not particularly limited, but it is repulp washed by a solvent such as water or methanol (the solvent is repeatedly washed and filtered several times). The most effective, and cost is also the most advantageous. The content of the component B is 1 to 100 parts by weight, preferably 2 to 90 parts by weight, preferably 2, based on 1 part by weight of the resin component (component A). It is more preferably in the range of 3 to 50 parts by weight, and the content of the component b is selected according to the desired level of flame retardancy, the type of the resin component (component A), and the like. In addition to the components A and B of the composition, other components may be used as needed without impairing the object of the present invention, and other flame retardants, flame retardant aids, and fluorine-containing resins may be used to change the amount of the component B. In most cases, 'through these The blending ratio of the component B can be reduced. The flame retardant resin composition of the present invention can at least achieve V-2 in the flame retardant level of the UL-94 standard. (Preparation of a flame retardant resin composition) The flammable resin composition can be obtained by using a V-shaped ">man's machine, a high-speed mixer, a high-speed float mixer, a Henschel mixer, and the like, and the resin component (component A), the organophosphorus compound (component B), and The other components are pre-mixed as needed, and then prepared by melt mixing with a kneader. The mixer can use various melt mixers such as a kneader, a bicycle or a twin-screw extruder, etc., in which a biaxial extrusion is used. The machine is 220 to 28 〇. (:, ^ is suitable for melting the resin composition at a temperature of 230 to 270 ° C, and the liquid component is injected and extruded by a side feeder, and is granulated by a granulator. The method of granulation is suitable for use. (Application) The flame-retardant resin composition of the present invention is substantially free of _, has a very high flame retardancy, and is used as a component of a molded home appliance, electric power, electronic parts, automobile parts, machinery, and the like. Materials for various molded articles such as structural members and cosmetic containers are useful. Specifically, in crusher parts, switch parts, engine parts, ignition coil cases, power plugs, power outlets, bobbins, connectors, relay boxes, Fuse box, flyback transformer component, focus block (Focus block), distributor cover, wire connector, etc. Moreover, as a thinning development housing, housing or chassis, such as electronics It is useful for the cover, cover or chassis of electric power products (such as telephones, computers, printers, fax machines, copiers, televisions, video recorders, audio equipment, etc., OA equipment, or the like). In particular, it is useful as a housing, a fixing unit, a facsimile, and the like, and a mechanical or mechanical component of an OA product, which is required to have excellent heat resistance and flame retardancy. The injection molding, the blow molding, the press molding, and the like of the molding method are not particularly limited, and it is preferable to produce the granular resin composition by injection molding using an injection molding machine. The following examples are given to illustrate the invention', but the invention is not limited thereto. In addition, evaluation was performed by the following method. (1) Flame retardancy (UL-94 evaluation) Flame-retardant test piece with a thickness of 1/16 inch (1.6 mm) is used as a scale for evaluation of flame retardancy, and it is based on the vertical specified in UL-94 of the UL specification of the United States. Burning 35 201122087 Burning test for evaluation. Each test piece removes the fire of the fire and extinguishes it in ίο seconds. Moreover, the v_g is not caused by the fire, and the V-2 is the fire of the lesser. The standard is below n〇tv. (2) Acid value The measurement was carried out in accordance with JIS-K-3504. Preparation 1 Preparation of 2,4,8,10-tetraoxa-3,9-di-spiro[5 5]deca-m-based _3,9-dioxide (FR-1). In a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel, 816.9 g (6.0 mol) of pentaerythritol, pyrimidine i9.〇g (〇 24 mol), and toluene 2250.4 g (24.4 mol) were prepared and stirred. Using the dropping funnel, 1651.8 g (12 Torr) of phosphorus trioxide was added to the reaction vessel, and after completion of the addition, the mixture was heated and stirred at 6 ° C. After the reaction, the mixture was cooled to room temperature, and dioxane methane was added to the obtained reactant for 26.50 minutes, and 889.4 g (12.0 mol) of t-butanol and 150.2 g (1.77 mol) of methane methane were added dropwise while cooling with water. The crystals obtained were washed and filtered with terpene and di-methane. The obtained filtrate was dried for 12 hours with 卯 33×l 〇 2Pa to give a white solid 丨34i.ig (5.88 mole). The solid obtained was confirmed by 31p, ^H-NMR spectroscopy as 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydro·3. 9_ dioxide. 2,4,8,1〇-tetraoxa- 3,9-diphosphaspiro[5.5]undecane, 3,9-di prepared in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel Hydrogen_3,9-dioxide 1341.0 g (5.88 mol), DMF6534.2 g (89.39 mol) was stirred. Sodium decoxide 648·7 § (12·〇1 mol) was added to the reaction vessel under water cooling. After stirring for 2 hours under water cooling, 5 36 201122087 hours of stirring was carried out at room temperature. Then, after removing DMF, DMF 2613.7 g (35.76 mol) was added. To the reaction mixture, bromobenzyl 2,37,79 g (u 91 mol) was added dropwise under water cooling. After stirring for 3 hours under water cooling, DMF was removed, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and methanol were placed in a reaction vessel equipped with an electric grid and a mixer, and refluxed for about 2 hours. After cooling to room temperature, the crystals were filtered to separate them, and after washing with 2 L of methanol, the obtained filtrate was dried at 120 C, 1.33 x 10 2 Pa for 19 hours to obtain white scaly crystals of 1863.5 g (4 - 56 m). The crystals obtained by 31p, ifj-NMR spectroscopy and elemental analysis were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl. _3,9_ dioxide. The yield was 760 / 〇, and the ^-NMR purity was 99%. In addition, the HPLC purity determined by the method described herein was 99%. The acid value is 〇.〇6 mgKOH/g. W-NMRC DMSO-de, 300 MHz): δ7·2-7.4 (ιη, 10H), 4-l-4.5 (m-8H) ' 3.5 (d, 4 Η), 31P-NMR (DMSO-d6, 120 MHz): 523.1 (S) 'M.p.: 255-256 ° C ' Elemental analysis calculated: c, 55.89; Η ' 5.43, measured value: C ' 56.24 ; Η, 5.35 Preparation 2 2,4,8,10-tetraoxa- Preparation of 3,9-diphosphaspiro[5·5]undecane, 3,9-dibenzyl-3,9-dioxide (FR-2) in a reaction vessel with a stirrer, thermometer, capacitor Filled with 3,9-dibenzyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5 5]undecane 22.55 g (0.055 mol), benzyl bromide 19. 〇 lg (〇.U Mo) and xylene 33.54g (0_32 mol), stir at room temperature, and dry with nitrogen. Then start heating with oil bath 'at reflux temperature (about 13 〇. σ σ heat for 4 hours, stir mix. After force σ heat is completed, 37 201122087 cool to room temperature 'add xylene 20mL, then mix for 30 minutes) The precipitated crystal was separated by two steps of washing with 20 mL of xylene. The obtained crude product and 40 mL of methanol were added to a reaction vessel equipped with a capacitor and a stirrer to reflux for about 2 hours. After cooling to room temperature, it was filtered. The crystals were separated, washed with methanol 2 mL, and dried at 120 ° C, 1.33×10 2 Pa for 19 hours to obtain white scaly crystals. Mass spectrometry, 31P nuclear magnetic resonance spectroscopy and elemental analysis were used. The product was confirmed to be dibenzyl pentaerythritol diphosphonate, the yield was 20.60 g, the yield was 91%, and the 31 P-NMR purity was 99%. Further, the HPLC purity determined by the method described herein was 99 〇/〇. The valence was 0.05 mg KOH/g. H-NMR (DMSO-d6, 300 MHz): δ7·2-7.4 (ιη, 10H), 4.1-4.5 (m ' 8 Η), 3.5 (d ' 4 Η), 3l P-NMR (DMSO) -d6, 120MHz): 523.1(S), melting point: 257°C Preparation 3 2,4,8,10-tetramilo-3,9-diphosphorane [5.5] Preparation of Eleventh Institute, 3,9-dioxin-1-methylbenzyl-3,9-dioxide (FR-3) Prepare pentaerythritol 816.9 in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. g (6.0 mol), pyrimidine 19.0 g (〇24 mol), toluene 2250.4 g (24.4 mol), and stirred. Using the dropping funnel, three gasified scales 1651_8 g (12. 〇mol) were added to the reaction vessel. After the addition is completed, the mixture is heated at 6 ° C. (4). Anti-money, cooled to room temperature, and a gas-fired 518 〇 7 g (61 〇 Mo Er) is added to the obtained reaction mixture, and the water is cooled while the water is dripped. Alcohol 889.4g (12.0 moules) and two gas calcined 15 〇 2g (1 77 mo 曱 曱 及 及 及 及 及 及 及 及 及 及 及 及 及 c c c c c c c c c c c c c c c c c c c c c c c c c c c. The obtained filtrate of 38 201122087 was dried for 12 hours to obtain 1341 lg (5 88 mol) of a white solid. The solid obtained by 31P and iH NMR spectroscopy was confirmed to be 2,4,8,1 〇_tetraoxa _ 3,9-diphosphorus [5.5]undecane, 3,9-dihydro-3,9-dioxide. Prepared in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. 4,8,10-tetraoxa-3,9-diphosphorane [5.5] Undecane, 3,9-dihydro-3,9-dioxide 1341.0 g (5.88 mol), DMF6534_2 g (89.39 mol) was stirred. Sodium decyl 648 7g (12.01 moles) was added to the vessel under water cooling. After stirring for 2 hours with water cooling, stirring was carried out for 5 hours at room temperature. Then, after removing DMF, DMF 2613.7 g (35-76 mol) was added, and to the reaction mixture, hydrazine-bromoethylbenzene 22 〇 4 06 g (u 91 mol) was added dropwise under water cooling. After stirring for 3 hours under water cooling, DMF was removed, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and 4 L of decyl alcohol were placed in a reaction vessel equipped with a capacitor and a stirrer, and refluxed for about 2 hours. After cooling to room temperature, the crystals were filtered to separate them. After washing with 2 L of decyl alcohol, the obtained filtrate was dried at 120 ° C, 1.33×10 2 Pa for 19 hours to obtain white flaky crystals of 1845.9 g (4.23 Mo). ear). The crystals obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di-α- by 31p_NMR, h-NMR spectroscopy and elemental analysis.曱Benzyl_3,9-dioxide. The purity of 3lPNMR was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value is 〇.〇3 mgKOH/g. 'H-NMRCCDCIs» 300MHz) : 67.2-7.4(m * 10H) * 4.0-4.2(m &gt; 4H), 3.4-3.8(m,4H) ' 3.3(qd,4H),1.6(ddd,6H), 31P-NMR (CDC13 '120MHz): 528.7 (S), m.p.: ield: ield: ield: calc.: calc.: calc.: calc. Example 4 2,4,8,l〇-tetraoxa-3,9·diphosphaspiro[5 5]undecane, 3,9-di(2-phenethyl)-3,9-dioxide Preparation of (FR-4) In a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel, 816.9 g (6. 〇mol) of pentaerythritol, 9.0 g (0-24 mol) of pyrimidine, and 225 (K4g ( 24.4 mol), stirring. Using the dropping funnel, 1651.8 g (12 Torr) of phosphorus trioxide was added to the reaction vessel, and after the addition was completed, the mixture was stirred and heated at 6 ° C. After the reaction, it was cooled to room temperature. Add -chloromethane 518〇7g (61〇mol) to the prepared reaction, and add 889.4g (12.0 mol) of t-butanol and 15〇2g of di-methane (1 77 mol) while cooling with water. The crystallization of the obtained crystals is washed and filtered with benzene and dichloromethane, and the obtained filter is obtained by 80% (:, 1.33xl02pa). The material was dried for 12 hours to obtain 1341 lg (5 88 mol) of a white solid. The solid obtained by P'H-NMR spectroscopy was 2,4,8,1 〇_tetraoxa-3,9-diphosphorane snail. [5.5] Undecane, 3,9-dihydro-3,9-dioxide. Prepared in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. 2,4,8,1〇_4 Oxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydro-3,9-dioxide 1341 (^ (5.88 mol), DMF6534.2 g (89.39 mol) In the vessel, 648.7 g (12.01 mol) of sodium methoxide was added under water cooling. After stirring for 2 hours under water cooling, stirring was carried out for 5 hours at room temperature. Then, after removing DMF, DMF2613.7 g (35_76 Mo) was added. To the reaction mixture, 2183.8 g (li. 8 mol) of (2-bromoethyl)benzene was added dropwise under water cooling. After stirring for 3 hours under water cooling, 'DMF was removed, 8 L of water was added, and the precipitated solid was collected by filtration. 2 L of water was washed twice. The obtained crude purified product and methanol were added to a reaction vessel equipped with a capacitor and a stirrer, and refluxed for about 2 hours. After cooling 40 201122087 to room temperature, the crystal was separated and separated for use. After washing 2L of sterol, The obtained filtrate was dried at 120 C, 1.33 xl02Pa for 19 hours to obtain 1924.4 g (4.41 mole) of a white powder. It was confirmed by 3ip_NMR, lH_NMR spectroscopy and elemental analysis that the solid obtained was 2,4,8,1〇_tetraoxa-3,9-diphosphorus sulphide [now eudecane^"-bis(7)phenethyl) The purity of the bismuth oxide ^ 屮 ^ ^ ruler is 99%. Further, the purity of HpLC measured by the method described herein was 99%. The acid value was 0.03 mgKOH/g. 'H-NMR (CDC13 » 300MHz) : 67.1-7.4(m &gt; 10H) &gt; 3.85-4.65(m ' 8H) ' 2.90-3.05(m,4H),2.1-2.3(m,4H), 3IP- NMR (CDC13 '120MHz): S31.5 (S), mp.: 245-246 〇 C, calc.: C, 57.80; H, 6.01, calc.: C, 58.00; H, 6.07 Preparation 5 ,4,8,10-tetraoxa-3,9·diphosphorus [5.5]undecane, 3,9-bis(2-phenylethyl)-3,9-dioxide (FR-5 Preparation in a reaction vessel with a stirrer, thermometer, capacitor, filled with 3,9-bis(phenylethoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[ 5.5] 436.4 g (1.0 mol) of undecane and 370.1 g (2.0 mol) of 2-bromoethylbenzene were stirred at room temperature while drying with nitrogen. Heating was then started in an oil bath and maintained at an oil bath temperature of 180 ° C for 10 hours. The oil bath was then removed and cooled to room temperature. To the obtained white solid reaction, 2 ml of methanol was added and stirred for washing, and then a white powder was filtered using a sintered glass filter. Next, the filtered white powder and 4000 ml of methanol were placed in a reaction vessel equipped with a capacitor and a stirrer, and refluxed for about 2 hours. After cooling to room temperature, separation was carried out by filtration through crystallization. After washing with methanol 41 201122087 2000 mL, the obtained white powder was dried at 10 ° C, 120 ° C for 8 hours to obtain 2, 4, 8, 10- Tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3,9-dioxide 362.3 g. The mass spectrometry, 'Η, 31P NMR spectroscopy and elemental analysis confirmed that the product was bis 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 - bis(2-phenylethyl)-3,9-dioxide. The yield was 83%, the HPLC purity was 99.3%, and the acid value was 0.4.1 KOHmg/g.

'H-NMR (CDC13' 300MHz): δ7. l-7.4(m ΊOH) 0.85-4.65 (m ' 8H) ' 2.90-3.05 (m, 4H), 2.1-2.3 (m, 4H), 3IP-NMR ( CDC13, 120MHz): 531.5(S), melting point: 245-246°C Preparation 6 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 - Preparation of bis(diphenylmethyl)-3,9-dioxide (FR-6) in a three 10-liter flask with a stirring device, a stirring wing, a reflux cooling tube, a thermometer, and a diphenylmethyl group. Phosphonoyl gas 2058.5 g (7.22 mol) and pentaerythritol 468.3 g (3.44 mol), pyrimidine ii 69.4 g (l4_8 mol), tri-gas methane 8200 g 'heated to 6 ° C under a nitrogen stream, and stirred for 6 hours. After completion of the reaction, methane was replaced with di-methane, and 6 L of distilled water was added to the reaction mixture to stir to precipitate a white powder. The mixture was filtered by absorption, and the obtained white material was washed with methanol, and then dried at 10 Torr, ΐ.33 χ 102Pa for 10 hours to obtain a white solid 1156.2 liter. The solids obtained were confirmed to be 2,4,8,1 〇-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9- by 3IP-NMR, iH-NMR spectroscopy and elemental analysis. Bis(diphenylmethyl)-3,9-dioxide. The 3ip-NMR purity was 99%. Further, the HPLC purity of the determination of 42 201122087 was 99% by the method described herein. The acid value was 0.3 mg KOH/g ° 1H-NMR (DMSO-d6 5 3 〇〇 MHz): 67.20-7.60 (m &gt; 20H) » 5.25 (d, 2H), 4.15-4.55 (m, 8H), 31p- NMR (DMSO_d6, 120 MHz): δ 20.9, m.p.: 265 C, calc.: calc.: calc., calc., 5.39, calc.: C, 66.14; H '5·41 Preparation Example 7 2,4,8 , 10-tetraoxa-3,9-&gt;phosphorus spiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3,9-dioxide (FR-7) A stirrer, a thermometer and a capacitor were installed in three flasks under nitrogen flow, and 3,9-bis(diphenylphosphoniumoxy)-2,4,8,10-tetraoxa-3,9-di was added to the flask. Phosphorus [5.5] undecane 40.4 § (0.072 mol), diphenylmethyl bromide 35.5 g (0-14 mol), diphenylbenzene 48.0 g (0.45 m), at reflux temperature (about 130 ° C) Heat for 3 hours and stir. After the completion of the heating, the mixture was cooled to room temperature, and 30 mL of diphenylbenzene was added, followed by stirring for 3 minutes. The precipitated crystals were separated by filtration, and washed twice with 30 mL of one. The obtained crude product and l 〇〇 mL of sterol were placed in an eggplant flask, and a capacitor was mounted and refluxed for about 1 hour. After cooling to room temperature, the crystals were filtered and separated, washed twice with 5 mL of methanol, and then dried under reduced pressure at 120 °C. The solids obtained by 3ip_nmr, 丨H_NMR spectroscopy and elemental analysis were confirmed to be 2,4,8,1〇_tetraoxa-3,9·diphosphaspiro[5.5]undecane, 3,9-double (two Benzoyl)_3,9_ dioxide. The solid obtained was a white powder. The yield was 36.8 g, and the yield was 91%. The 31 P-NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.07 mgKOH/g. 'H-NMR (DMSO-d6 » 3〇〇MHz) : 87.2-7.6(m » 20H) &gt; 43 201122087 6.23(d, J=9Hz, 2H), 3.89-4.36(m,6H), 3.38-3.46 (m, 2H), 31P-NMR (CDC 13 ' 120 MHz): s.sup..sup..sup. 5.41 Preparation Example 8 Preparation of Polycarbonate (PC-1) In a reaction vessel, isosorbate 7307 parts by weight (5 Torr) and diphenyl carbonate 10709 parts by weight (50 moles) were added to prepare a polymerization catalyst. 4.8 parts by weight of tetradecyl ammonium hydroxide (1 χ 1 〇 4 moles relative to the diphenyl carbonate component) and 虱 sodium oxide 5.0xl 〇 3 parts by weight (relative to the diphenyl carbonate component) The ear is 0.25xl0_6 moles. 'It is heated and melted to 180 ° C under a nitrogen atmosphere at normal pressure. The mixture was gradually depressurized in a reaction bath for 30 minutes, and the pressure was reduced to 13.3 x 1 (T3 MPa) while distilling off the produced phenol. In this state, the reaction was allowed to proceed for 20 minutes and then the temperature was raised to 200 ° C. Then, the pressure was gradually reduced under reduced pressure for 20 minutes, and the reaction was carried out at 4.00 x 1 (T3 MPa for 2 Torr), then the temperature was raised to 220 ° C, the reaction was allowed to proceed for 30 minutes, and the temperature was raised to 25 Torr. The reaction was carried out for 30 minutes. Then, the pressure was gradually reduced, and the reaction was continuously carried out at 2.67 X 10-3 MPal for 0 minutes, 1.33×1 (T3MPalO minutes continuously) and then depressurized. If it reached 4 〇〇χ 10_5 MPa, the temperature was gradually raised to 260 ° C. The reaction was finally carried out for 1 hour at 2601, 6.66 x 10 - 5 MPa. The polymer after the reaction was granulated to obtain particles having a specific viscosity of 0.33. The glass had a glass transition temperature of 165. (:, 5% weight loss temperature was 355 ° C. Preparation of 9 Polycarbonate (PC-2) was prepared in the same manner as in Preparation Example 8 except that the reaction was carried out at 255 ° C and 6.66 x 1 (T5 MPa for 30 minutes) to obtain a specific viscosity of 〇. Particles of 23. The glass has a glass transition temperature of 158 ° C and a 5% weight loss The degree is 353. (: Preparation Example 10 Polycarbonate (PC-3) was prepared in addition to isosorbide 6722 parts by weight (46 moles) and diphenyl carbonate 1〇7〇9 parts by weight (50 moles) The 1,3-propanediol was treated in the same manner as in Reference Example 8 except for 304 parts by weight (4 moles), and the particles having a specific dryness of 0·28 were obtained. The glass had a glass transition temperature of 146 ° C and a 5% weight loss temperature. The following were used for each component used in the examples and the comparative examples. (I) Polycarbonate resin (component A) (i) Polycarbonate synthesized in Preparation Example 8 (hereinafter referred to as PC-1) (ii) Polycarbonate synthesized in Preparation Example 9 (hereinafter referred to as PC-2) (iii) Polycarbonate synthesized in Preparation Example 10 (hereinafter referred to as PC-3) (II) Organophosphorus compound (Part B) (i) 2,4,8,10·tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9·dibenzyl-3,9-di synthesized in Preparation Example 1. Oxide {phosphorous compound of formula (1-3) (hereinafter referred to as FR-1)} (ii) 2,4,8,1〇_tetraoxa*3,9-diphosphine synthesized in Preparation Example 2 Heterospiro[5.5]undecane, 3,9-di- benzyl-3,9-dioxide {phosphorus compound of formula (1_3) (hereinafter referred to as FR-2) } (iii) Preparation Example 3 Synthesis of 2,4,8,10-tetraoxa-3,9-diphosphaspene 45 201122087 [5_5]undecane, 3,9-diα-fluorenylbenzyl-3,9-dioxide Phosphorus compound of the formula (1_b) (hereinafter referred to as FR-3) } (iv) 2,4,8,1〇_tetraoxa-3,9_di-filled snail synthesized in Preparation Example 4 [5.5] A nonanesane, 3,9-bis(2-phenylethyl)-3,9-dioxide { s(1_c) phosphorus compound (hereinafter referred to as FR-4) } (v) Synthesis in Preparation 5 2,4,8,10-tetraoxa-3,9-diphosphorus [5.5] eleven, 3,9-bis(2-phenylethyl)-3,9-dioxide (1-(;) scaly compound (hereinafter referred to as FR-5) } (called 2,4,8,1〇-tetraoxa-3,9-two-disc snail synthesized in Preparation Example 6 [5.5] a non-dodecane, 3,9-bis(diphenylmethyl)-3,9-dioxide { s(1_d) phosphorus compound (hereinafter referred to as FR-6) } (vii) Synthesis in Preparation Example 7 2,4,8,1〇-tetraoxa-3,9-di-scale snail [5.5] eleven, 3,9-bis(diphenylmethyl)-3,9-dioxide Phosphorus-based compound (hereinafter referred to as FR-7)} (III) Other organophosphorus compounds (1) use triphenyl carbonate (TPP by Daihachi Chemical Industry CO., LTD) (hereinafter referred to as TPP) (li) between Diphenol [(2,6-dimethylphenyl)phosphate] (PX-200 manufactured by Daihachi Chemical Industry CO" LTD (hereinafter referred to as ρχ_2〇〇) Examples 1 to 22 and Comparative Examples 1 to 9 The amount (weight fraction) described in 1 to 3 was mixed with a large cup and the components described in Tables 1 to 3 were granulated by a 15 πππιφ biaxial extruder (manufactured by Technovel Corporation, KZW15). The obtained granules were dried by a hot air dryer at 130 ° C for 4 hours. The dried pellets were molded by an injection molding machine (J75EIII, manufactured by Sakamoto Steel Co., Ltd.) 46 201122087. The evaluation results are shown in Table 13 using a forming plate. 47 201122087, TV ' 9έ 001 3d

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CN 3έ 001 rud UIUI9; (Ν-Λ f#省驷5J 001 Tud UIm9) (n_a '^醉§§Μ·Μ. $ di fsn $ 寸 2η ία. si篓撬Example 22 PC-1 〇TH FR- 1 in (N 1.6mm 实施 Example 21 PC-3 〇TH FR-6 &lt;Ti 1.6mm V-2 Example 20 PC-3 〇FR-7 in 1.6mm V-2 Example 19 PC-3 〇FR -5 Τ) 1.6mm V-2 Example 18 PC-3 FR FR-4 1.6mm V-2 Example 17 PC-3 〇FR-3 1.6mm V-2 Example 16 PC-3 Ο FR-2 Ιη 1.6mm V-2 Example 15 PC-3 ο FR-1 1.6mm V-2 Example 14 PC-2 100 FR-7 1.6mm V-2 Unit type Weight by type Weight Weight Test piece thickness UL evaluation component A Component Β component UL-94 test composition flame retardant 48 22 1X 1X 20 £ Comparative injury PC-3 丨〇T-Η ΡΧ-200 1.6mm notV Comparative example 8 PC-3 〇ΤΡΡ 1.6mm notV Comparative example 7 PC- 2 〇ΡΧ-200 1.6mm notV Comparative Example 6 PC-2 ο ΤΡΡ in 1.6mm notV Comparative Example 5 PC-1 ο rH ΡΧ-200 1.6mm notV inch-Ο PC-1 Ο ΤΡΡ in 1.6mm notV Comparative Example 3 PC -3 Ο I 1 1.6mm notV Comparative example 2 PC-2 100 1 1 1.6mm notV Comparative example I PC-1 Ο 1 1 1.6mm notV Weight, type, weight, test piece thickness, UL evaluation component, A component composition, UL-94 test composition, flame retardancy, the effect of the present invention, the flame retardant resin composition of the present invention, and a molded article formed therefrom, which have been derived from plants in the past. The comparison of the resin composition of the raw materials gives the following advantages: Ο) The quality does not use the flame retardant containing the element and has a high degree of flame retardancy. (1 0 as a difficult organic compound, s is relative to use The resin derived from plant-derived raw materials has excellent sincerity, and the amount of use is also reduced to a V-2 level. (1 1 The structure and characteristics of the organic ruthenium compound used as a flame retardant are used. When the resin of the raw material of the plant is used at the time of resin molding or the use of the molded article, the resin which uses the plant-derived raw material hardly causes excellent heat and heat stability, and the flame retardant resin composition which is not praised is 'flammable. , machine (four) degree and heat record every __ is flat _, better. (iv) As a valuable compound, it is colorless and is compatible with a resin using a plant-derived raw material, so that a molded article excellent in transparency can be obtained. Industrial Applicability Because of the present invention The flame-retardant resin composition is substantially free of elements and has a very high level of viscous energy. Therefore, it is useful as a material for molding various parts such as molded m parts, electric and electronic products, automobile parts, machinery, mechanical parts, and cosmetic containers. c diagram simple description: j (none) [main component symbol description] (none) 50

Claims (1)

201122087 VII. Patent application scope: 1. A flame retardant resin composition containing, by weight, 100 parts by weight of at least 50% by weight of a polycarbonate comprising a unit represented by the following formula (A-1) (A-1) The resin component (component A) of the component) and the organophosphorus compound (component B) represented by the following formula (1) in an amount of from 1 to 100 parts by weight 0 〇—ch2 ch2 (A-1) -0 o V (1) V V Pc /V o-ch2 ch2 (wherein, X1 and X2 are each independently, which is an aromatic substituted alkyl group represented by the following formula (2)) - (AL Ar Ar ) n (2) (wherein, AL is a carbon number a branched or linear aliphatic hydrocarbon group of 1 to 5; Ar is a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent; Ar may be bonded to any carbon atom in the AL; η is 1 to 3 integers). 2. The resin composition according to claim 1, wherein the polycarbonate (Α-1 component) glass transition temperature (Tg) is from 100 ° C to 165 ° C, and the 5% weight loss temperature (Td) is 300 ° C ~ 400 ° C. 3. The resin composition as recited in claim 1, wherein the unit represented by the formula (A-1) is derived from isosorbide (1,4:3,6-dianhydro-D-sorbitol) unit. 51 201122087 4. 2 Please refer to the patent range. The resin compound (component B) is selected from the group consisting of at least 3 groups of organophosphorus compounds and (4) organic scales (3) VcH ^Vo7 P ... τίτ and right &amp; R are each independently 'p-phenyl, Tecaki or sulfhydryl, which have substituents; heart 3, heart 6 are independent, and are chlorine atoms, stones: branches of number 1~4 a linear or linear chain, a benzene which may also have a substituent, a decyl group which may have a substituent or an onion group which may have a substituent) Α, -r)f I \ 八 /P-ALLc-Ar2 R12 〇一% is called -. L (4) 丨 (wherein Ar 丨 and Ara are each independently, which is a phenyl group, a phenyl group or an onion group, and the like may have a substituent; Μ, r|2, RijRl are independent, and are a hydrogen atom, a carbon number of 1~ An aliphatic hydrocarbon group of 3, a stupid group which may have a substituent, a naphthyl group which may have a substituent or an anthracenyl group which may have a substituent; AL and AL are each independently 'branched having a carbon number of 1 to 4 or a linear aliphatic hydrocarbon group. Ar3 and Ar4 are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent; each of p and q is independently an integer of 〇~3; and Ar3 and Ar4 may be respectively bonded. Junction to any carbon atom of AL1 and AL2). 5. The resin composition according to claim 1, wherein the organic hydrazine compound (component B) is represented by the following formula (5) 52 201122087 (wherein, r21 and R22 are each independently and may have a substituent). The resin composition according to the first aspect of the invention, wherein the organic dish (substance B) is a compound represented by the following formula (1_a). The resin composition according to the first aspect of the invention, wherein the organophosphorus compound (component B) is represented by the following formula (6) R°° υ-^π2 〇Π2-〇1^36 (6) (wherein R and R are each independently 'a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms; and R33 and R36 are each independently a carbon number 1 to 4 of an aliphatic hydrocarbon group; R32 and R35 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent). 8. The resin composition according to claim 1, wherein the organophosphorus compound (component B) is a compound represented by the following formula (Ι-b) 53 201122087 Q ο CH3 (1-b) As the resin composition of the Scope of the Patent Application, in which the compound (B component) is represented by the following formula (7), -ΓίΤ-ynrcrL V_八AL_?-Ar2 0-CH2 CH2-0 R 14 (7) (wherein Ar1 and Ar2 are each independently a phenyl, naphthyl or anthracenyl group, and i may have a substituent; R&quot;, Ri2, ri3 and Rl4 are each independently a hydrogen atom. An aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a phenyl group which may have a substituent: a naphthyl group which may have a substituent or an onion group which may have a substituent; each of AL and AL is independently a carbon number 丨 4 a branched or linear aliphatic Fi group. Ar3 and Ar4 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent; p&amp;q is independently an integer of 〇~3; A〆 and Ar4 can be bonded to any of the carbon atoms of AL1 and AL2, respectively). 1. The resin composition as recited in claim 4, wherein the organic compound (component B) is a compound represented by the following formula (1-c), -03⁄4-pf, and 〇\f -CH2-CH2- ^~~\j (1 - C) 11. The resin composition as described in the scope of the patent application, wherein the organophosphorus compound (component B) is represented by the following formula (8) 54 201122087 R41 〇 (wherein R and R44 are each independently, and are a hydrogen atom, an aliphatic k group having a carbon number of 丨4 or a stupid group which may have a substituent, a group which may have a substituent or a substituent; And R42, R43, R45 and R46 are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent). 12. The resin composition as recited in claim 2, wherein the organophosphorus s material (component B) is a compound represented by the following formula (I·#) The resin composition according to claim 1, wherein the organic phosphorus compound (component B) has an acid value of 0.7 mgKOH/g or less. 14. The resin composition as recited in claim 1 is at least V_2 in the flame retardant level of UL-94. 15_ The resin composition as described in claim 1, wherein the component b is contained in a proportion of 2 to 7 〇 by weight based on 100 parts by weight of the component A. 16. A molded article formed from the resin composition described in the first paragraph of the patent application. 55 201122087 IV. Designation of Representative Representatives: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: