TWI448543B - A flame retardant resin composition and a molded article derived - Google Patents

Description

Flame retardant resin composition and molded article therefrom Field of invention

The present invention relates to a flame retardant resin composition derived from a plant material which is highly flame retardant and has good physical properties, and a molded article therefrom. More specifically, it relates to a flame retardant resin composition containing a predetermined organic phosphorus compound and substantially halogen-free, and a molded article therefrom.

Background of the invention

In order to obtain a raw material of a resin molded article, polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), polyamine (PA6, PA66), polyester (PET, PBT), and poly are generally used. A resin such as carbonate (PC). 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, and the production of resins using raw materials derived from biologically derived substances such as plants is required. . In particular, when considering the global environmental problem, it is inferred that the resin derived from plant material is used, even if it is burned after use, considering the amount of carbon dioxide absorbed by the plant when it is born, the idea of carbon neutrality neutral from the carbon balance is also It is a resin with a low load on the global environment.

On the other hand, when these resins derived from plant materials are used for industrial materials, particularly electric power/electronic related components, OA related components, or automobile parts, it is necessary to impart flame retardancy from the viewpoint of safety.

At present, various attempts have been made to use a resin derived from a plant material, particularly a flame retardancy of a polylactic acid resin, and a certain degree of flame retardancy has been achieved. However, these incombustible prescriptions use a large amount of flame retardant, which impairs the physical properties of the resin.

On the other hand, a polycarbonate resin derived from a plant material as a raw material which can be obtained from an ether diol residue which can be produced from a saccharide is used in addition to a polylactic acid resin.

For example, the following formula (a)

The ether diol shown is easily produced from, for example, saccharides and starch, 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" in the present specification) represented by the following formula (c) is exemplified.

Further, 1,4:3,6-dianhydro-L-idumitol (hereinafter referred to as "isoindole" in the present specification) represented by the following formula (d) is exemplified.

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 an isosorbide of an oligomer at a center and to combine it into a 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 melting point of 203 ° C using a melt transesterification method. However, the polymer has only insufficient mechanical properties.

As an example of high heat resistance, Patent Document 2 reports a polycarbonate having a glass transition temperature of 170 ° C or higher measured by a differential calorific value of a heating rate of 10 ° C /min, and is considered as a melt viscosity when considering a molding material having a high contrast viscosity. Too high a problem.

On the other hand, in Patent Document 3, a copolymerized polycarbonate of isosorbide and a linear aliphatic diol is described.

Regarding these polycarbonates formed from isosorbide, each of the literatures does not do any research on flame retardancy.

(Patent Document 1) British Patent Application Publication No. 1079686

(Patent Document 2) International Publication No. 2007/013463

(Patent Document 3) International Publication No. 2004/111106

Invention

A first object of the present invention is to provide a flame retardant resin composition derived from a plant material having high flame retardancy and good physical properties, 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 halogen-free, and a molded article therefrom.

According to the study of the present inventors, the object of the present invention is to use a resin containing at least 50% by mass of a polycarbonate (A-1 component) containing at least 50% by mass of a unit represented by the following formula (A-1). The component (component A) and the flame retardant resin composition containing the organophosphorus compound (B) component represented by the following formula (1) in an amount of from 1 to 100 parts by weight are obtained.

(wherein, X ¹ and X ² are each independently and are an aromatic substituted alkyl group represented by the following formula (2))

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms. Ar is a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Ar may be bonded to the AL. On any carbon atom, n is an integer from 1 to 3.)

According to the present invention, a flame retardant resin composition derived from a plant material can be obtained without impairing the original properties of the resin and achieving high flame retardancy.

The best form for implementing the invention

Hereinafter, the flame retardant resin composition of the present invention will be described in more detail.

(resin component: component A)

The resin component in the present invention mainly contains polycarbonate (component A-1). The content of the polycarbonate (component A-1) in the resin component is desirably 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 It is at least 90% by weight.

Other resin (component A-2) may be contained in the resin component (component A). The content of the other resin (component A-2) is preferably 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, most preferably 20% by weight or less, particularly preferably 10% by weight or less. the following. The other resin (component A-2) will be described in detail later.

(Polycarbonate: component A-1)

The polycarbonate (component A-1) in the present invention contains a carbonate unit represented by the following formula (A-1). In the percarbonate unit, the ratio of the unit represented by the following formula (A-1) is preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, and more preferably 80 mol% or more. Particularly suitable, 90% or more is the best.

The polycarbonate (component A-1) is preferably contained in an amount of 25% or more, preferably 50% or more, more preferably 70% or more, as measured according to ASTM D6866 05. 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 0.7 g of the polycarbonate (component A-1) in 100 ml of dichloromethane is preferably 0.14 or more, more preferably 0.20 or more, still more preferably 0.22 or more. Further, the upper limit is preferably 0.45 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.

Further, the polycarbonate (component A-1) has a melt viscosity measured by a capillary rheometer at 250 ° C, and is 0.08 × 10 ³ to 2.4 × 10 ³ Pa ‧ at a shear rate of 600 sec ^-1 . The range is preferably from 0.1 × 10 ³ to 2.0 × 10 ³ Pa s, and the range of from 0.1 × 10 ³ to 1.5 × 10 ³ Pa s is more preferable. When the melt viscosity is within this range, the mechanical strength is excellent, and the formation of silver at the time of molding without using the resin composition of the present invention is good.

In the polycarbonate (component A-1), the lower limit of the glass transition temperature (Tg) is preferably 100 ° C or higher, preferably 120 ° C or higher, and the upper limit is preferably 165 ° C or lower. When Tg is less than 100 ° C, heat resistance (especially heat resistance due to moisture absorption) is inferior, and when it exceeds 165 ° C, melt flowability at the time of molding using the resin composition of the present invention is inferior. Tg was measured by DSC (Model DSC2910) manufactured by TA Instruments.

Further, the lower limit of the 5% weight loss temperature of the polycarbonate (component A-1) is preferably 300 ° C or higher, more preferably 320 ° C or higher, and the upper limit is preferably 400 ° C or lower, preferably 390 ° C or lower. More preferably, it is 380 ° C or less. When the 5% weight loss temperature is within the above range, it is suitable that almost no decomposition of the resin is carried out by molding using the resin composition of the present invention. The 5% weight reduction temperature was measured by TGA (model TGA2950) manufactured by TA Instruments.

The polycarbonate (component A-1) preferably has a glass transition temperature (Tg) of from 100 ° C to 165 ° C and a 5% weight loss temperature (Td) of from 300 ° C to 400 ° C.

Polycarbonate (component A-1), which can be obtained by the following formula (a)

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

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-dianhydro-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 cyclohexanedimethanol are preferred. Further, since the resin composition of the present invention contains the above formula (a) which is a raw material obtained from a renewable resource such as a plant as a main component, a 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)-3,3,5-trimethylcyclohexane, 4,4'-(p-phenyldiisopropylidene)diphenol (4,4'-(m-Phenylenediisopropyridene) Diphenol), 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyl Phenyl)-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, the polycarbonate (component A-1) can be introduced into the end group without impairing its properties. Such a terminal group can be introduced by adding a corresponding hydroxy compound at the time of polymerization. The terminal group is preferably an end group represented by the following formula (i) or (ii).

In the above formula (i) (ii), R ⁴ 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 20 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the following formula (iii). 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. It is preferably 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. a is an integer of 1-5, suitably an integer of 1-3, especially 1 is preferable.

Further, in the above formula (iii), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 6 to 20 carbon atoms. A group of at least one of 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. It is preferable that each is independently a group selected from at least one of a group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms. In particular, it is preferred that the groups are at least one selected from the group consisting of a methyl group and a phenyl group. b is an integer of 0 to 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 50, and particularly preferably an integer of 8 to 50.

Since the polycarbonate (component A-1) has a carbonate unit using a raw material obtained from a renewable resource such as a plant in the main chain structure, it is obtained from such a hydroxy compound or a renewable resource such as a plant. Raw materials are preferred. The hydroxy compound produced by the plant is exemplified by a long-chain alkanol (cetyl alcohol, hard alcohol, behenyl alcohol) having a carbon number of 14 or more, which is obtained from vegetable oil.

Further, a bishydroxy compound and a carbonic acid diester containing an ether diol represented by the above formula (a) are mixed, and a melt polymerization of an alcohol or a phenol produced by a transesterification reaction is carried out under high temperature and reduced pressure, whereby a polycarbonate can be obtained. (A-1 ingredient).

The reaction temperature is to suppress the decomposition of the ether diol, and to obtain a high-viscosity resin having little coloration, and it is preferred to use a condition as low as possible, but in order to appropriately promote the polymerization reaction, the polymerization temperature is preferably in the range of 180 ° C to 280 ° C. It is preferably in the range of 180 ° C to 270 ° C.

Further, the ether diol and the carbonic acid diester are heated at normal pressure in the initial stage of the reaction to cause a pre-reaction, and then the pressure is gradually reduced, and the system is depressurized to about 1.3 × 10 ^-3 to 1.3 × 10 ^-5 MPa at the later stage of the reaction. Preferably, the method of removing the produced alcohol or phenol is preferred. The reaction time is usually about 1 to 4 hours.

Further, a polymerization catalyst can be used in order to increase 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. Further, a nitrogen-containing basic compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine or triethylamine may, for example, be mentioned. These may be used alone or in combination of two or more. Among them, it is preferred to use a nitrogen-containing basic compound and an alkali metal compound.

The amount of the polymerization catalyst used is preferably 1 × 10 ^-9 to 1 × 10 ^-3 equivalents, preferably 1 × 10 ^-8 to 5 × 10 ^- per mol of the carbonic acid diester component, respectively. Choose within a range of ⁴ equivalents. The reaction system is preferably maintained in an inert gas atmosphere with respect to a raw material such as nitrogen, a reaction mixture, and a reaction product. An inert gas other than nitrogen may, for example, be argon or the like. 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) includes an ester such as an aryl group having 6 to 20 carbon atoms, an aralkyl group or an alkyl group having 1 to 18 carbon atoms which may be substituted. Specific examples thereof include diphenyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(p-butylphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and carbonic acid. Butyl ester and the like, among which diphenyl carbonate is preferred.

The carbonic acid diester is preferably mixed in an amount of from 1.02 to 0.98, more preferably from 1.01 to 0.98, still more preferably from 1.01 to 0.99, based on the molar ratio of the total of the ether diol compound. When the molar ratio of the carbonic acid diester is more than 1.02, it is not preferable that the carbonate residue acts as a terminal blocking to obtain a sufficient degree of polymerization. Further, when the molar ratio of the carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.

A catalyst deactivator may also be added to the polycarbonate (component A-1) obtained by the above production method. A known catalyst deactivator is effectively used as the catalyst deactivator, and among them, an ammonium salt or a phosphonium salt of a sulfonic acid is preferred. Further, the above salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate or the above salts of p-toluenesulfonic acid such as tetrabutylammonium p-toluenesulfonate are preferred. Further suitable use of sulfonate methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate Ester, 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 of the alkali metal compound and/or the alkaline earth metal compound, preferably 0.5 to 10 moles. The ratio of the ear is preferably 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 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 or less. Particularly preferably, it is 10% by weight or less.

The component A-2 is exemplified by a polyester resin (PEst), a polyphenylene ether resin (PPE), a polycarbonate resin (PC), a polyamide resin (PA), a polyolefin resin (PO), and a styrene resin. A thermoplastic resin of at least one of the group consisting of polyphenylene sulfide resin (PPS) and polyether sulfimide resin (PEI). Among these A-2 components, polyester resin (PEst), polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO), and styrene are preferable. 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 one or a mixture of two or more selected from the group consisting of an aromatic polyester resin and an aliphatic polyester resin. Conveniently, the aromatic polyester resin is a polyester formed from a dicarboxylic acid component mainly composed of an aromatic dicarboxylic acid and a diol component mainly composed of an aliphatic diol having 2 to 10 carbon atoms. 80 mol% or more, preferably 90 mol% or more of a suitable dicarboxylic acid component is formed of an aromatic dicarboxylic acid component. On the other hand, the diol component is preferably 80 mol% or more, preferably 90 mol% or more, and is formed of an aliphatic diol component having 2 to 10 carbon atoms.

Suitable examples of the aromatic dicarboxylic acid component are terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, methyl isophthalic acid and 2,6-naphthalene dicarboxylic acid. Wait. These may be used alone or in combination of two or more. The secondary dicarboxylic acid other than the aromatic dicarboxylic acid may, for example, be an aliphatic acid such as adipic acid, sebacic acid, decane dicarboxylic acid, sebacic acid, dodecane dicarboxylic acid or cyclohexane dicarboxylic acid. Dicarboxylic acid or alicyclic dicarboxylic acid, and the like.

Examples of the aliphatic diol having 2 to 10 carbon atoms include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, and neopentyl glycol. Further, an alicyclic diol such as 1,4-cyclohexanedimethanol may be mentioned. Examples of the diol other than the aliphatic diol having 2 to 10 carbon atoms include p,p'-dihydroxyethoxy bisphenol 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.

a specific aromatic polyester resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and poly(p-naphthalene dicarboxylate) At least one of a group consisting of a glycol ester resin, a polybutylene terephthalate resin, a polytrimethylene terephthalate resin, and a polyparaphthalic acid propylene glycol ester resin is preferred.

Most preferably, it is 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 having a carbon number of 5 to 10 and H (OCH ₂ CH _{2 )} A diol having at least one of a group consisting of _i OH (i = 2 to 5) is formed, and a polyester or polycaprolactone having a melting point of 100 ° C or less or amorphous may be used.

Further, the main component is 80 mol% or more of the total dicarboxylic acid component or the total diol component, and suitably 90 mol% or more, and the main repeating unit is 80 mol% or more of the total repeating unit, suitably It is a repeating unit of 90 mol% or more.

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 measured at 35 ° C in o-chlorophenol is suitably 0.5 to 1.6 dl/g, more preferably 0.6 to 1.5. Dl/g.

Further, the aromatic polyester resin is advantageous in that the amount of terminal carboxyl groups (-COOH) is from 1 to 60 equivalents/T (1 T polymer). The amount of the terminal carboxyl group can be calculated by titrating the m-cresol solution with an alkali solution, for example, by potentiometric titration.

As the polyphenylene ether resin of the component A-2, a commonly known PPE resin can be used. Specific examples of such a PPE resin include (2,6-dimethyl-1,4-phenylene)ether, (2,6-diethyl-1,4-phenylene)ether, (2). ,6-dipropyl-1,4-phenylene)ether, (2-methyl-6-ethyl-1,4-phenylene)ether, (2-methyl-6-propyl-1) a monomer and/or a copolymer such as 4-phenylene ether or (2,3,6-trimethyl-1,4-phenylene) ether. Particularly preferred is (2,6-dimethyl-1,4-phenylene) ether. Alternatively, a copolymer of a styrene compound may be graft polymerized on the PPE. The method for producing such a PPE is not particularly limited, and 2,6-xylenol can be used as a catalyst by using a method of the first copper salt and an amine as a catalyst, for example, as described in U.S. Patent No. 3,306,874. It is easily produced by oxidative polymerization.

The reduced viscosity η _sp /C (0.5 g / dl, toluene solution, measured at 30 ° C) of the molecular weight scale of the PPE resin is 0.2 to 0.7 dl / g, preferably 0.3 to 0.6 dl / g. The PPE resin having a reduced viscosity in this range has a good balance between moldability and mechanical properties, and the reducing viscosity can be easily adjusted by adjusting the amount of the catalyst during the production of PPE.

The polycarbonate resin (PC) of the component A-2 is obtained by an interfacial polymerization reaction of various dihydroxyaryl compounds and carbon dichloride using a solvent such as dichloromethane. Further, a transesterification reaction of a dihydroxyaryl compound with diphenyl carbonate is also exemplified. Representative of a polycarbonate obtained by the reaction of 2,2'-bis(4-hydroxyphenyl)propane with carbon dichloride.

The dihydroxyaryl compounds forming the polycarbonate starting material are bis(4-hydroxyphenyl)methane, 1,1'-bis(4-hydroxyphenyl)ethane, 2,2'-bis(4-hydroxybenzene). Propane, 2,2'-bis(4-hydroxyphenyl)butane, 2,2'-bis(4-hydroxyphenyl)octane, 2,2'-bis(4-hydroxy-3-methyl Phenyl)propane, 2,2'-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2'-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2'-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2'-bis(4-hydroxy-3-methoxyphenyl)propane, 1,1'-bis (4- Hydroxyphenyl)cyclopentane, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 1,1'-bis(4-hydroxyphenyl)cyclododecane, 4,4'-dihydroxy Phenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'- Dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxydiphenylanthracene, bis(4-hydroxyphenyl)ketone, and the like. 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, dihydroxydiphenylanthracene, dihydroxydiphenylketone or the like. The most preferred dihydroxyaryl compound is 2,2'-bis(4-hydroxyphenyl)propane which forms a bisphenol A type aromatic polycarbonate.

Further, when a bisphenol A type aromatic polycarbonate is produced in a range that does not impair heat resistance, mechanical strength, or the like, a part of bisphenol A may be substituted by another dihydroxyaryl compound.

The molecular weight of the polycarbonate is not particularly limited, but the excessively high strength may be insufficient, and the excessively high melt viscosity may become high and difficult to form, so the viscosity average molecular weight is usually 10,000 to 50,000, and preferably 15, 000 to 30,000. Here, the viscosity average molecular weight (M) is obtained by taking the specific viscosity (η _sp ) calculated by dissolving a solution of 0.7 g of polycarbonate in 100 ml of dichloromethane at 20 ° C into the following formula.

η _sp /C=[η]+0.45×[η] ² C

[η]=1.23×10 ^-4 M ^0.83

(However, [η] is the intrinsic viscosity, and C is 0.7 in terms of polymer concentration)

A brief description of the basic method of making polycarbonate. The reaction is carried out by an interfacial polymerization method (solution polymerization method) using a carbonate precursor carbon dichloride, usually in the presence of an acid binder and an organic solvent. As the acid binder, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyrimidine is used. A halogenated hydrocarbon such as dichloromethane or chlorobenzene is used as the organic solvent. Further, a catalyst such as a tertiary amine or a fourth-order ammonium salt may be used to promote the reaction. As the molecular weight modifier, a terminal stopper such as phenol or p-tert-butylphenol such as an alkyl-substituted phenol is suitably used. The reaction temperature is usually from 0 to 40 ° C, the reaction time is from several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. As a result, it is not necessary for all of the molecular chain ends obtained to have a structure derived from a terminal stopper.

A transesterification reaction (melt polymerization method) using a carbonic acid diester as a carbonate precursor, and heating a predetermined ratio of a dihydric phenol and a carbonic acid diester in the presence of an inert gas, and distilling off the produced alcohol or phenol . The reaction temperature is different from the boiling point of the produced alcohol or phenol, and is usually in the range of 120 to 350 °C. The reaction is completed while distilling off the produced alcohol or phenol under reduced pressure from the initial stage. A terminal stopper is added simultaneously with the dihydric phenol or the like or in the middle of the reaction in the initial stage of the reaction. Further, in order to promote the reaction, a catalyst which is currently used in a transesterification reaction can be used. The carbonic acid diester used in the transesterification reaction may, for example, be diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate or dibutyl carbonate. Among them, diphenyl carbonate is preferred.

The polyamine resin (PA) of the component A-2 may, for example, be a ring-opening polymer of a cyclic indoleamine, a polymer of an aminocarboxylic acid, a polycondensate of a dibasic acid and a diamine, or the like. Specific examples thereof include aliphatic polyamides such as nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 11, nylon 12, and the like, or copolymers or mixtures thereof. Further, poly(metaxylene adipamide), poly(hexamethylene terephthalamide), poly(p-xylylenediamine), poly(p-xylylenediamine) (poly(nona-methylene terephthalamide), poly(hexamethylene isophthalamide), poly(tetramethylene isophthalamide), etc. The aromatic polyamine, the copolymer or the mixture of the above. The polyamine which can be used in the present invention is not particularly limited.

The molecular weight of such a polyamide resin is preferably from 1.7 to 4.5, preferably from 2.0 to 4.0, more preferably from 2.0 to 3.5, in a 98% sulfuric acid concentration of 1% and a relative viscosity measured at 25 °C.

The polyolefin resin of the component A-2 is an olefin-based monomer or copolymer such as ethylene, propylene or butene, 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 component A-2 is a monomer or copolymer of an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene, and these monomers are combined with acrylonitrile and methacrylic acid. a copolymer of a vinyl monomer such as an ester, such that the styrene and/or styrene derivative is in a diene rubber such as polybutadiene, an ethylene/acrylic rubber, an acrylate rubber, or the like, or styrene and/or The styrene derivative is grafted with other ethylene monomers.

Specific examples of the styrene resin include, for example, polystyrene, impact 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, an ethylene propylene rubber, a 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. The polymer is obtained by adding an aromatic vinyl monomer or a vinyl monomer as needed in the presence of a rubbery polymer, and preparing a monomer mixture by a known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization.

Examples of the rubber-like polymer may, for example, be a diene rubber such as polybutadiene, poly(styrene-butadiene) or poly(acrylonitrile-butadiene), and hydrogenated the above diene rubber. Acrylate rubber such as saturated rubber, isoprene rubber, chloroprene rubber, polybutyl acrylate, and ethylene-propylene-diene oligomer terpolymer (EPDM), especially diene rubber good.

The above-mentioned rubbery polymer has an aromatic vinyl monomer which is an essential component in a monomer mixture which may cause graft polymerization, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, etc., and styrene is the best.

Examples of the ethylene monomer which may be added as needed are acrylonitrile, methyl 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% by weight, preferably 98 to 60% by weight.

The polyphenylene sulfide resin (PPS) of the component A-2 has a repeating unit represented by 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 the method for producing the polyphenylene sulfide resin is a method of reacting polydichlorobenzene with sodium disulfide. 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 oxime resin (PEI) of the component A-2 has a repeating unit represented by the following formula.

In the formula, Ar ¹ represents an aromatic dihydroxy compound residue, and Ar ² represents an aromatic diamine residue. The aromatic dihydroxy compound is exemplified by the aromatic dihydroxy compound shown in the description of the above polycarbonate resin, and particularly preferably bisphenol A. The aromatic diamine is exemplified by m-phenylenediamine, p-phenylenediamine, 4,4'-diamine biphenyl, 3,4'-diamine biphenyl, 4,4'-diamine diphenyl ether, and 3. 4'-diamine diphenyl ether, diamine diphenylmethane, diamine diphenyl hydrazine and diamine diphenyl sulfide.

n in the above formula represents an integer of 5 to 1,000, and preferably an integer of 10 to 500.

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 A-2 components, a polyester resin (PEst), a polyphenylene ether resin (PPE), a polycarbonate resin (PC), a polyamide resin (PA) or a styrene resin is preferred.

(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, X ¹ and X ² are each independently an aromatic substituted alkyl group represented by the following formula (2).

In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms. The aliphatic hydrocarbon group is preferably an alkanediyl group, an alkanetriyl group or an alkanetetrayl 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. n is an integer of 1-3.

The component B 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).

In the formula, R ² and R ⁵ each independently represent a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Examples of the substituent 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 chlorine 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.

R ¹ , R ³ , R ⁴ and R ⁶ are each independently a hydrogen atom, a branched or linear alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, and a naphthalene which may have a substituent. Or a thiol group which may also have a substituent. The alkyl group is exemplified by methyl, ethyl, propyl, butyl and the like. Examples of the substituent 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 chlorine atom or a bromine atom; and a aryl group having 6 to 12 carbon atoms such as a phenyl group or a naphthyl group. Base.

In the formula, Ar ¹ and Ar ² are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Examples of the substituent 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 chlorine 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.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ 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 may have a substitution. Base base. Examples of the substituent 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 chlorine atom or a bromine atom; and a aryl group having 6 to 12 carbon atoms such as a phenyl group or a naphthyl group. Base.

Each of AL ¹ and AL ^{2 is} independently a branched or linear aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group may, for example, be an alkylene group having 1 to 4 carbon atoms such as a methylene group, a vinyl group or a propylene group. Further, an alkyltriyl group having 1 to 4 carbon atoms such as a methyltriyl group, a trisyl group or a propyltriyl group may be mentioned. Further, an alkanetetrayl group having 1 to 4 carbon atoms such as a tetrakisyl group, an ethylenetetrayl group or a propyltetrayl group may also be mentioned.

Ar3 and Ar4 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Examples of the substituent 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 chlorine 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.

p and q are each independently and are an integer of 0 to 3. Ar ³ and Ar ⁴ may each be bonded to any of the carbon atoms of AL ¹ and AL ² .

Further, a phosphorus-based compound represented by the following formulas (5), (6), (7), and (8) is preferable.

In the formula, R ²¹ and R ²² each independently represent a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Among them, phenyl is preferred. The phenyl, naphthyl or anthracenyl group of R ²¹ and R ²² may be substituted with a hydrogen atom of the aromatic ring, and the substituent may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group, or a bond of the aromatic ring. The group is an aryl group having 6 to 14 carbon atoms and having an oxygen atom, a sulfur atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms as an intermediate group.

In the above formula (6), R ³¹ and R ³⁴ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. A hydrogen atom, a methyl group or an ethyl group is preferred, and a hydrogen atom is particularly suitable. R ³³ and R ³⁶ are each independently and are an aliphatic hydrocarbon group having 1 to 4 carbon atoms. It is preferably a methyl group or an ethyl group. R ³² and R ³⁵ are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Preferably, the phenyl group may have a substituent on the moiety 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), and a butyl group. The 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), specific examples of R ³² and R ³⁵ may, for example, be phenyl, tolyl, xylyl, trimethyl, 4-phenoxyphenyl, cumyl, naphthyl, 4 -Benzylphenyl or the like, especially phenyl.

In the above formula (7), Ar ¹ and Ar ² are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ 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 may have a substitution. Base base. Preferably, the phenyl group may have 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 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 Ar ¹ and Ar ² are phenyl, tolyl, xylyl, trimethylphenyl, 4-phenoxyphenyl, cumylphenyl, naphthyl, and 4- Phenylphenyl or the like, especially phenyl is preferred.

In the above formula (7), each of AL ¹ and AL ^{2 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 propylene group. Further, an alkyltriyl group having 1 to 4 carbon atoms such as a trisyl group, a trisyl group or a propyltriyl group is also exemplified. Further, an alkanetetrayl group having 1 to 4 carbon atoms such as a tetrakis group, an ethyltetraki group or a propyltetrayl group is also mentioned.

In the above formula (7), specific examples of AL ¹ and AL ² include methylene, vinyl, ethylene, propyl, propylene, isopropylidene, etc., especially methylene, Vinyl and ethylene are preferred.

In the above formula (7), Ar ³ and Ar ⁴ 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 methyl group, an ethyl group, a propyl group (including an isomer), The butyl group (including an isomer) or a 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. Ar ³ and Ar ⁴ may be bonded to any of the carbon atoms of AL ¹ and AL ² , respectively.

In the above formula (7), p and q are each independently and are an integer of 0 to 3. Suitably p and q are 0 or 1, particularly suitably 0.

In the above formula (8), R ⁴¹ and R ⁴⁴ 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. A hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a phenyl group which may have a substituent is preferred. When R ⁴¹ and R ⁴⁴ are a phenyl group, any substituent other than a moiety bonded to the phosphorus via a carbon atom on the aromatic ring may have a substituent, and is a methyl group, an ethyl group, or a propyl group (including an isomer) The butyl group (including an 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 R ⁴¹ and R ⁴⁴ may, for example, be a hydrogen atom, a methyl group, an ethyl group, a propyl group (including an isomer), a phenyl group, a tolyl group, a xylyl group or a trimethylbenzene group. The group is 4-phenyloxyphenyl, cumylphenyl, naphthyl, 4-benzylphenyl or the like, and particularly preferably a hydrogen atom, a methyl group or a phenyl group.

R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ 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 oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (8), specific examples of R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ are phenyl, tolyl, xylyl, trimethylphenyl, 4-phenoxyphenyl, cumene. Or naphthyl, 4-benzylphenyl, etc., especially phenyl.

The organophosphorus compound (component B) represented by the above formula (1) exhibits an extremely excellent flame retarding effect with respect to these resins. In the range known by 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 flame retardant to be flammable, 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) is easily ignitable by a small amount of itself, and the original properties of the resin are not impaired.

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. The other mixed components such as these will be specifically described 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). Compounds represented by (1-c) and (1-d).

Next, the synthesis method of 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 phosphorus trichloride 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 aralkyl alcohol is reacted in a compound obtained by reacting an aralkylphosphonic acid dichloride 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 Laid-Open Publication No. SHO-54-157156, and No. Sho 53-39698.

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 modification 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) an organophosphorus compound of the above (1-a) in component B; reacting phosphorus trichloride in pentaerythritol, and then treating the oxidation reaction product treated with t-butanol with sodium methoxide to thereby react with benzyl bromide Got it.

(II) the above-mentioned (1-b) organophosphorus compound in component B; reacting phosphorus trichloride in pentaerythritol, and then treating the oxidation reaction product treated with t-butanol with sodium methoxide to obtain 1-bromoethyl group The benzene reaction is obtained.

(III) the above-mentioned (1-c) organophosphorus compound in component B; reacting tri-phosphorus phosphorus in pentaerythritol, and then treating the oxidation reaction product treated with t-butanol with sodium methoxide to obtain 2-bromoethyl group The benzene reaction is obtained.

(IV) The above-mentioned (1-d) organophosphorus compound in the component B; obtained by reacting diphenylmethylphosphonium dichloride in pentaerythritol.

In addition, other methods are carried out by reacting phosphorus trichloride in pentaerythritol, and reacting the product obtained by heat treatment in the presence of a catalyst with diphenylmethanol.

The acid value of the component B is preferably 0.7 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 one having an acid value of 0.4 mgKOH/g or less. The acid value herein means the amount (mg) of KOH necessary to neutralize the acid component in the 1 g sample (component B).

Further, the component B is preferably 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 HPLC purity of the component B can be measured by the following method.

The column was Develosil ODS-7 300 mm × 4 mm Φ manufactured by Nomura Chemical Co., Ltd., and the column temperature was 40 °C. The solvent was mixed with a 6:4 (volume ratio) solution of acetonitrile and water, and 5 μl was injected. The detector uses UV-260 nm.

The method of removing the impurities in the component B is not particularly limited, but the method of repulp washing with a solvent such as water or methanol (removing and filtering several times with a solvent) is most effective and cost. It 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 to 70 parts by weight, more preferably 3 to 50 parts by weight, per 100 parts by weight of the resin component (component A). The scope. The content of the component B is selected in accordance with the desired flame retardancy level, the type of the resin component (component A), and the like. In addition to the components A and B constituting 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 mixture of the components B. The amount, in many cases, can reduce the mixing ratio of the B component by using these. The flame retardant resin composition of the present invention can at least achieve V-2 in the flame retardant level of the UL-94 specification.

(Preparation of a flame retardant resin composition)

The flame retardant resin composition of the present invention can be a resin component (component A) or an organophosphorus compound (component B) by using a mixer such as a V-type mixer, a high-speed mixer, a high-speed float-up mixer, or a Henschel mixer. And pre-mixing other components as needed, and then melt-mixing with a kneader to prepare.

The mixer can use various melt mixers, such as kneaders, uniaxial or biaxial extruders, etc., in which a biaxial extruder is used to melt the resin at a temperature of 220 to 280 ° C, suitably 230 to 270 ° C. The method of injecting and ejecting a liquid component by a side feeder and granulating by a granulator is suitably used.

(use)

The flame-retardant resin composition of the present invention contains substantially no halogen and has a very high flame retardancy. The materials for various molded articles such as molded household electrical appliance parts, electric power, electronic parts, automobile parts, machinery, mechanical parts, and cosmetic containers are useful. Specifically, in the crusher component, the switch component, the engine component, the ignition coil case, the power plug, the power socket, the bobbin, the connector, the relay box, the fuse box, the flyback transformer component, the focus block, the focus block, Dispenser cover, wire connector, etc. Moreover, as a housing, housing, or chassis for thinning, such as electronic appliances, such as telephones, computers, printers, fax machines, photocopiers, televisions, video recorders, audio equipment, and the like. ‧ OA machines or such components, etc. are useful on the cover, cover or chassis. In particular, it is useful as a machine body, a mechanical unit, a mechanical component, a mechanical component, a fixing unit, a facsimile, etc., which are 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.

Example

The invention is illustrated by the following examples, which are not intended to limit the invention. In addition, evaluation was performed by the following method.

(1) Flame retardancy (UL-94 evaluation)

For the flame retardancy, a test piece having a thickness of 1/16 inch (1.6 mm) was used as an evaluation standard for flame retardancy, and it was evaluated according to the vertical burning test specified in UL-94 of the UL specification of the United States. The fire after each flame is removed from the test piece will be extinguished within 10 seconds. Moreover, if the cotton wool is not fired, it will be V-0, and within 30 seconds, the fire extinguisher will be V-2. The standard below is notV.

(2) Acid price

The measurement was carried out in accordance with JIS-K-3504.

Preparation Example 1

Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-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, 19.0 g (0.24 mol) of pyrimidine, and 2250.4 g (24.4 mol) of toluene were prepared and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added to the reaction vessel, and after completion of the addition, the mixture was heated and stirred at 60 °C. After the reaction, the mixture was cooled to room temperature, and dichloromethane (26.50 ml) was added to the obtained reaction mixture, and 889.4 g (12.0 mol) of t-butyl alcohol and 150.2 g (1.77 mol) of dichloromethane were added dropwise with water. The obtained crystals were washed and filtered with toluene and dichloromethane. The obtained filtrate was dried at 80 ° C, 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) as a white solid. The solid obtained by the ³¹ P, ¹ H-NMR spectrum was confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydro-3. , 9-dioxide.

Prepare 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydrogen in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. -3,9-dioxide 1341.0 g (5.88 mol), DMF 6534.2 g (89.39 mol), and stirred. In the reaction 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, DMF 2613.7 g (35.76 mol) was added, and to the reaction mixture, bromobenzyl 2037.79 g (11.91 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 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, 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 × 10 ² Pa for 19 hours to obtain white scaly crystals of 1863.5 g (4.56). Moore). The crystals obtained by ³¹ P, ¹ H-NMR spectroscopy and elemental analysis were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di. Benzyl-3,9-dioxide. The yield was 76%, and the ³¹ P-NMR purity was 99%. In addition, the HPLC purity determined by the method described herein was 99%. The acid value was 0.06 mgKOH/g.

^{1 H-NMR (DMSO-d} 6, 300MHz): δ7.2-7.4 (m, 10H), 4.1-4.5 (m-8H), 3.5 (d, 4H), 31 P-NMR (DMSO-d 6, 120MHz): δ23.1(S), melting point: 255-256°C, calculated for elemental analysis: C, 55.89; H, 5.43, measured: C, 56.24; H, 5.35

Preparation Example 2

Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-3,9-dioxide (FR-2)

In a reaction vessel with a stirrer, thermometer, and 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 19.01 g (0.11 mol) and xylene 33.54 g (0.32 mol), and stirred at room temperature while drying with nitrogen. Heating was then started with an oil bath, and the mixture was heated at a reflux temperature (about 130 ° C) for 4 hours and stirred. After the completion of the heating, the mixture was cooled to room temperature, and 20 mL of xylene was added, followed by stirring for 30 minutes. The precipitated crystals were separated by filtration and washed twice with 20 mL of xylene. The obtained crude product and 40 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, the mixture was separated by filtration, and washed with methanol (20 mL), and then filtered and dried at 120 ° C, 1.33 × 10 ² Pa for 19 hours to obtain white flaky crystals. The product was confirmed to be bisbenzyl pentaerythritol diphosphonate by mass spectrometry, ¹ H, ³¹ P nuclear magnetic resonance spectroscopy and elemental analysis. The yield was 20.60 g, the yield was 91%, and the ³¹ P-NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.05 mgKOH/g.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d, 4H), ³¹ P-NMR (DMSO-d ₆ , 120MHz): δ23.1(S), melting point: 257°C

Preparation Example 3

2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di-α-benzyl-3-,9-dioxide (FR-3) Preparation

In a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel, 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyrimidine, and 2250.4 g (24.4 mol) of toluene were prepared and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added using the dropping funnel, and after the addition was completed, the mixture was heated and stirred at 60 °C. After the reaction, the mixture was cooled to room temperature, and 5180.7 g (61.0 mol) of dichloromethane was added to the obtained reaction mixture, and 889.4 g (12.0 mol) of t-butanol and 150.2 g of methylene chloride (1.77 mol) were added dropwise while cooling with water. ear). The obtained crystals were washed and filtered with toluene and dichloromethane. The obtained filtrate was dried at 80 ° C, 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. The solid obtained by ³¹ P, ¹ H NMR spectroscopy confirmed 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydro-3,9 - dioxide.

Prepare 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. Hydrogen-3,9-dioxide 1341.0 g (5.88 mol), DMF 6534.2 g (89.39 mol), and stirred. In the vessel, 648.7 g (12.01 mol) of sodium methoxide was added 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 1-bromoethylbenzene 2204.06 g (11.91 mol) was added dropwise to the reaction mixture 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 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, the crystals were filtered to separate, and after washing with 2 L of methanol, 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). Moore). The crystals obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 by ³¹ P-NMR, ¹ H-NMR spectroscopy and elemental analysis. - bis-methylbenzyl-3,9-dioxide. ^{The 31} P NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.03 mgKOH/g.

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.2-7.4 (m, 10H), 4.0-4.2 (m, 4H), 3.4-3.8 (m, 4H), 3.3 (qd, 4H), 1.6 (ddd , 6H), ³¹ P-NMR (CDCl ₃ , 120 MHz): δ 28.7 (S), m.p.: 190-210 ° C, calc.: C, 57.80; H: 6.01, measured: C, 57.83; , 5.96

Preparation Example 4

2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3,9-dioxide (FR- 4) Preparation

In a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel, 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyrimidine, and 2250.4 g (24.4 mol) of toluene were prepared and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added using the dropping funnel, and after the addition was completed, the mixture was heated and stirred at 60 °C. After the reaction, the mixture was cooled to room temperature, and 5180.7 g (61.0 mol) of dichloromethane was added to the obtained reaction mixture, and 889.4 g (12.0 mol) of t-butanol and 150.2 g of methylene chloride (1.77 mol) were added dropwise while cooling with water. ear). The obtained crystals were washed and filtered with toluene and dichloromethane. The obtained filtrate was dried at 80 ° C, 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. The solid obtained by the ³¹ P, ¹ H-NMR spectrum was confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydro-3. , 9-dioxide.

Prepare 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. Hydrogen-3,9-dioxide 1341.0 g (5.88 mol), DMF 6534.2 g (89.39 mol), and stirred. 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, DMF 2613.7 g (35.76 mol) was added, and 2183.8 g (11.8 mol) of (2-bromoethyl)benzene was added dropwise to the reaction mixture 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 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, 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 × 10 ² Pa for 19 hours to obtain a white powder of 1924.4 g (4.41 m). . The solids obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 by ³¹ P-NMR, ¹ H-NMR spectroscopy and elemental analysis. - bis(2-phenylethyl)-3,9-dioxide. ^{The 31} P-NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.03 mgKOH/g.

_{^{1 H-NMR (CDCl 3,}} 300MHz): δ7.1-7.4 (m, 10H), 3.85-4.65 (m, 8H), 2.90-3.05 (m, 4H), 2.1-2.3 (m, 4H), 31 P-NMR (CDCl ₃ , 120 MHz): δ 31.5 (m), m.p.: 245 - 246 C, calc.

Preparation Example 5

2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3,9-dioxide (FR- 5) Preparation

In a reaction vessel with a stirrer, thermometer, and capacitor, filled with 3,9-bis(phenylethoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] 436.4 g (1.0 mol) of mono-alkane and 370.1 g (2.0 mol) of 2-bromoethylbenzene were stirred at room temperature, and dried with nitrogen. Heating was then started with 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, 2000 ml of methanol was added and stirred, and the 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, and after washing with methanol 2000 mL, the obtained white powder was dried at 100 Pa and 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. Mass spectrometry, ¹ H, ³¹ P 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 0.41 KOH mg/g.

_{^{1 H-NMR (CDCl 3,}} 300MHz): δ7.1-7.4 (m, 10H), 3.85-4.65 (m, 8H), 2.90-3.05 (m, 4H), 2.1-2.3 (m, 4H), 31 P-NMR (CDCl ₃ , 120 MHz): δ 31.5 (S), m.p.: 245-246.

Preparation Example 6

2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3,9-dioxide (FR-6 Preparation

In three 10-liter flasks with stirring device, stirring wing, reflux cooling tube, thermometer, 2058.5 g (7.22 mol) of diphenylmethylphosphonochloride and 468.3 g (3.44 mol) of pentaerythritol and pyrimidine 1169.4 were prepared. g (14.8 mol) and 8200 g of chloroform were heated to 60 ° C under a nitrogen stream and stirred for 6 hours. After completion of the reaction, methylene chloride was used instead of chloroform, and 6 L of distilled water was added to the reaction mixture, followed by stirring to precipitate a white powder. The mixture was filtered by absorption, and the obtained white material was washed with methanol, and then dried at 100 ° C and 1.33 × 10 ² Pa for 10 hours to obtain 1156.2 g of a white solid. The solids obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 by ³¹ P-NMR, ¹ H-NMR spectroscopy and elemental analysis. - bis(diphenylmethyl)-3,9-dioxide. ^{The 31} P-NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.3 mgKOH/g.

¹ H-NMR (DMSO-d6, 300MHz): δ 7.20-7.60 (m, 20H), 5.25 (d, 2H), 4.15-4.55 (m, 8H), ³¹ P-NMR (DMSO-d6, 120MHz) : δ 20.9, m.p.: 265 ° C, calc.: C, 66.43; H, 5.39, found: C, 66.14; H, 5.41

Preparation Example 7

2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3,9-dioxide (FR-7 Preparation

A stirrer, a thermometer and a capacitor were installed in three flasks, and under a nitrogen flow, 3,9-bis(diphenylmethoxy)-2,4,8,10-tetraoxa-3,9- was added to the flask. Diphosphorus [5.5] undecane 40.4g (0.072 moles), diphenylmethyl bromide 35.5g (0.14 moles), xylene 48.0g (0.45 moles), heated at reflux temperature (about 130 ° C) Stir for 3 hours. After the completion of the heating, it was cooled to room temperature, and 30 mL of xylene was added, followed by stirring for 30 minutes. The precipitated crystals were separated by filtration, and washed twice with 30 mL of xylene. The obtained crude product and 100 mL of methanol were placed in an eggplant type 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 50 mL of methanol, and then dried under reduced pressure at 120 °C. The solids obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 by ³¹ P-NMR, ¹ H-NMR spectroscopy and elemental analysis. - bis(diphenylmethyl)-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.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 7.2-7.6 (m, 20H), 6.23 (d, J = 9 Hz, 2H), 3.89 - 4.36 (m, 6H), 3.38 - 3.46 (m, ^{2H), 31 P-NMR (} CDCl 3, 120MHz): δ20.9 (S), melting point: 265 ℃, elemental analysis Calcd: C, 66.43; H, 5.39 , measurement values: C, 66.14; H, 5.41

Preparation Example 8

Preparation of polycarbonate (PC-1)

7307 parts by weight (50 moles) of isosorbide and 10709 parts by weight (50 moles) of diphenyl carbonate were added to the reaction vessel, and 4.8 parts by weight of tetramethylammonium hydroxide of the polymerization catalyst was prepared (relative to carbonic acid two) The phenyl ester component 1 mole is 1 × 10 ^-4 moles, and the sodium hydroxide 5.0 × 10 ^-3 weight fraction (relative to the diphenyl carbonate component 1 mole is 0.25 × 10 ^-6 moles), in the nitrogen The atmosphere was heated and melted to 180 ° C under normal pressure.

Under stirring, the reaction vessel was gradually depressurized for 30 minutes, and the resulting phenol was distilled off to reduce the pressure to 13.3 × 10 ^-3 MPa. In this state, the reaction was allowed to proceed for 20 minutes, and the temperature was further raised to 200 ° C. Then, the pressure was gradually reduced over a period of 20 minutes, and the reaction was allowed to proceed for 20 minutes at 4.00 × 10 ^-3 MPa while distilling off the phenol, followed by raising the temperature to 220. The reaction was allowed to proceed for 30 minutes at ° C, and the temperature was raised to 250 ° C to carry out the reaction for 30 minutes.

Then, the pressure was gradually reduced, and the reaction was continuously carried out at 2.67 × 10 ^-3 MPa for 10 minutes and 1.33 × 10 ^-3 MPa for 10 minutes, and then the pressure was reduced. When it reached 4.00 × 10 ^-5 MPa, the temperature was gradually raised to 260 ° C, and finally 260. The reaction was allowed to proceed for 1 hour at ° C, 6.66 × 10 ^-5 MPa. The polymer after the reaction was granulated to obtain particles having a specific viscosity of 0.33. The pellet had a glass transition temperature of 165 ° C and a 5% weight loss temperature of 355 ° C.

Preparation Example 9

Preparation of polycarbonate (PC-2)

The pellets having a specific viscosity of 0.23 were obtained in the same manner as in Production Example 8 except that the reaction was finally carried out at 255 ° C and 6.66 × 10 ^-5 MPa for 30 minutes. The pellet had a glass transition temperature of 158 ° C and a 5% weight loss temperature of 353 ° C.

Preparation Example 10

Preparation of polycarbonate (PC-3)

The same procedure as in Reference Example 8 except that isosorbide 6722 parts by weight (46 moles) and diphenyl carbonate 10709 parts by weight (50 moles) and 1,3-propanediol 304 parts by weight (4 moles) were prepared. Particles having a viscosity of 0.28. The pellet had a glass transition temperature of 146 ° C and a 5% weight loss temperature of 342 ° C.

The following materials were used for the respective components used in the examples and 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) Organic phosphorus compound (component B)

(i) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 1. A compound of the formula (1-a) (hereinafter referred to as FR-1)

(ii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 2. a phosphorus compound of the formula (1-a) (hereinafter referred to as FR-2)}

(iii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-diα-methylbenzyl-3,9 synthesized in Preparation Example 3. - dioxide {phosphorus compound of formula (1-b) (hereinafter referred to as FR-3)}

(iv) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3 synthesized in Preparation Example 4. , 9-dioxide {phosphorous compound of formula (1-c) (hereinafter referred to as FR-4)}

(v) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3 synthesized in Preparation Example 5. , 9-dioxide {phosphorus compound of formula (1-c) (hereinafter referred to as FR-5)}

(vi) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3 synthesized in Preparation Example 6, 9-dioxide {phosphorus compound of formula (1-d) (hereinafter referred to as FR-6)}

(vii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3 synthesized in Preparation Example 7, 9-dioxide {phosphorus compound of formula (1-d) (hereinafter referred to as FR-7)}

(III) Other organophosphorus compounds

(i) Use of triphenyl phosphate (TPP manufactured by Daihachi Chemical Industry Co., Ltd.) (hereinafter referred to as TPP)

(ii) Resorcinol [(2,6-dimethylphenyl) phosphate] (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) (hereinafter referred to as PX-200)

Examples 1 to 22 and Comparative Examples 1 to 9

The components described in Tables 1 to 3 were mixed in a large cup in the amounts (weight fractions) shown in Tables 1 to 3, and granulated by a 15 mm Φ biaxial extruder (KZW15, manufactured by Technovel Corporation). 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 Nippon Steel Co., Ltd.). The evaluation results are shown in Tables 1 to 3 using a forming plate.

Effect of the invention

The flame-retardant resin composition of the present invention and the molded article formed therefrom have the following advantages as compared with the resin composition of the plant-derived raw material in the past.

(i) Substantially no halogen-containing flame retardant is used and has a high degree of flame retardancy.

(i i) The organophosphorus compound as a flame retardant has an excellent flame retardant effect with respect to a resin using a plant-derived raw material, so that the V-2 level is achieved even with a relatively small amount of use.

(iii) The structure and characteristics of the organophosphorus compound used as a flame retardant, the resin using the plant-derived raw material hardly causes the use of the plant-derived raw material at the time of resin molding or the use of the molded article. Thermal deterioration and excellent thermal stability. Therefore, the flame retardant resin composition of the present invention is balanced and excellent in each of flame retardancy, mechanical strength and thermal stability.

(i v) The organophosphorus compound as a flame retardant is colorless and compatible with a resin using a plant-derived raw material, so that a molded article excellent in transparency can be obtained.

Industry availability

Since the flame-retardant resin composition of the present invention contains substantially no halogen and has a very high flame retardancy, it is variously formed as a component of a molded home appliance, an electric appliance, an electronic component, an automobile component, a machine, a mechanical component, a cosmetic container, and the like. The material of the product is useful.

Claims (15)

A flame retardant resin composition containing at least 50% by weight of a resin component (component A) comprising at least 50% by weight of a polycarbonate (component A-1) comprising a unit represented by the following formula (A-1) And an organophosphorus compound (component B) which is at least one selected from the group consisting of organophosphorus compounds represented by the following formulas (3) and (4) in an amount of from 1 to 100 parts by weight. (wherein R ² and R ⁵ are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent; and R ¹ , R ³ , R ⁴ and R ⁶ are each independently a hydrogen atom and a carbon number; a branched or linear alkyl group of 1 to 4, 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) (wherein Ar ¹ and Ar ² are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent; and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom and a carbon number; 1 to 3 of an aliphatic hydrocarbon group, a phenyl group which may have a substituent, a naphthyl group which may have a substituent or an anthracenyl group which may have a substituent; and each of AL ¹ and AL ^{2 is} independently a carbon number of 1 to 4 a branched or linear aliphatic hydrocarbon group; each of Ar ³ and Ar ^{4 is} independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent; and p and q are each independently, and are an integer of 0 to 3; Ar ³ and Ar ⁴ may be bonded to any of the carbon atoms of AL ¹ and AL ² respectively). The resin composition as described in claim 1, wherein the polycarbonate (A-1 component) has a glass transition temperature (Tg) of 100 ° C to 165 ° C, and a 5% weight loss temperature (Td) of 300 ° C to 400 °C. The resin composition according to claim 1, wherein the unit represented by the formula (A-1) is derived from a unit of isosorbide (1,4:3,6-dianhydro-D-sorbitol). The resin composition according to the first aspect of the invention, wherein the organophosphorus compound (component B) is represented by the following formula (5) (wherein R ²¹ and R ²² are each independently and may be a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent). The resin composition according to the first aspect of the invention, wherein the organophosphorus compound (component B) is a compound represented by the following formula (1-a) The resin composition according to claim 1, wherein the organophosphorus compound (component B) is represented by the following formula (6) (wherein R ³¹ and R ³⁴ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms; and R ³³ and R ³⁶ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms; and R ³² and R ^35; Each is independently a phenyl group, a naphthyl group or an anthracenyl group, which may also have a substituent). The resin composition according to the first aspect of the invention, wherein the organophosphorus compound (component B) is a compound represented by the following formula (1-b) The resin composition according to the first aspect of the invention, wherein the organophosphorus compound (component B) is represented by the following formula (7) (wherein Ar ¹ and Ar ² are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent; and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom and a carbon number; 1 to 3 of an aliphatic hydrocarbon group, a phenyl group which may have a substituent, a naphthyl group which may have a substituent or an anthracenyl group which may have a substituent; and each of AL ¹ and AL ^{2 is} independently a carbon number of 1 to 4. a branched or linear aliphatic hydrocarbon group; each of Ar ³ and Ar ^{4 is} independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent; and p and q are each independently, and are an integer of 0 to 3; Ar ³ and Ar ⁴ may be bonded to any of the carbon atoms of AL ¹ and AL ² respectively). The resin composition according to the first aspect of the invention, wherein the organophosphorus compound (component B) is a compound represented by the following formula (1-c) The resin composition according to claim 1, wherein the organophosphorus compound (component B) is represented by the following formula (8) (wherein R ⁴¹ and R ⁴⁴ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a phenyl group which may have a substituent, a naphthyl group which may have a substituent or may have a substituent. The fluorenyl group; R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent). The resin composition according to the first aspect of the invention, wherein the organophosphorus compound (component B) is a compound represented by the following formula (1-d) 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. The resin composition described in the first aspect of the patent application is at least V-2 in the flame retardant level of the UL-94 specification. In the resin composition according to the first aspect of the invention, the component B is contained in an amount of 2 to 70 parts by weight based on 100 parts by weight of the component A. A molded article is formed from the resin composition described in claim 1 of the patent application.