WO2011070689A1 - Composition ignifuge de résine et produits moulés de celle-ci - Google Patents

Composition ignifuge de résine et produits moulés de celle-ci Download PDF

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WO2011070689A1
WO2011070689A1 PCT/JP2009/071011 JP2009071011W WO2011070689A1 WO 2011070689 A1 WO2011070689 A1 WO 2011070689A1 JP 2009071011 W JP2009071011 W JP 2009071011W WO 2011070689 A1 WO2011070689 A1 WO 2011070689A1
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group
component
substituent
independently
resin composition
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PCT/JP2009/071011
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English (en)
Japanese (ja)
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山中　克浩
利往 三宅
瑞穂 齋藤
真美 木下
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帝人株式会社
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Priority to BR112012013048A priority Critical patent/BR112012013048A2/pt
Priority to US13/509,655 priority patent/US8618196B2/en
Priority to JP2011545044A priority patent/JPWO2011070689A1/ja
Priority to CN200980162785.XA priority patent/CN102666725B/zh
Priority to EP09852085.1A priority patent/EP2511338B1/fr
Priority to PCT/JP2009/071011 priority patent/WO2011070689A1/fr
Priority to KR1020127014673A priority patent/KR101745036B1/ko
Publication of WO2011070689A1 publication Critical patent/WO2011070689A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5337—Esters of phosphonic acids containing also halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5357—Esters of phosphonic acids cyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Definitions

  • the present invention relates to a flame retardant resin composition using a plant-derived raw material having high flame retardancy and good physical properties, and a molded product therefrom. More particularly, the present invention relates to a flame retardant resin composition containing a specific organophosphorus compound and substantially free of halogen, and a molded article therefrom.
  • polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), polyamide (PA6, PA66), polyester (PET, PBT), polycarbonate (PC), etc. are used as raw materials for resin molded products. Is used.
  • these resins are manufactured using raw materials obtained from petroleum resources. In recent years, there are concerns about problems such as depletion of petroleum resources and the global environment, and raw materials obtained from biological materials such as plants are used. There is a demand for the production of resin. Considering the problem of the global environment in particular, the resin that uses plant-derived raw materials is considered to be carbon neutral because it is neutral as a carbon balance, considering the amount of carbon dioxide absorbed during plant growth even if incinerated after use.
  • the resin has a low impact on the global environment.
  • a resin using these plant-derived raw materials is used for industrial materials, particularly electrical / electronic parts, OA-related parts, or automobile parts, it is necessary to impart flame retardancy for safety reasons.
  • various attempts have been made for flame retarding of resins using plant-derived materials, particularly polylactic acid resins, and some degree of flame retarding has been achieved.
  • these flame retardant prescriptions use a large amount of flame retardant and impair the original physical properties of the resin.
  • a resin using a plant-derived raw material a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide, in addition to a polylactic acid resin, has been studied.
  • the ether diols shown in 1) are easily made from, for example, sugars and starch, and three stereoisomers are known. Examples of stereoisomers include 1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”) shown in the following formula (b).
  • 1,4: 3,6-dianhydro-D-mannitol (hereinafter referred to as “isomannide”) shown in the following formula (c) can be mentioned.
  • 1,4: 3,6-dianhydro-L-iditol (hereinafter referred to as “isoidid” in the present specification) represented by the following formula (d) may be mentioned.
  • Isosorbide, isomannide, and isoidide are obtained from D-glucose, D-mannose, and L-idose, respectively.
  • isosorbide can be obtained by hydrogenating D-glucose and then dehydrating it using an acid catalyst.
  • Patent Documents 1 and 2 reports a homopolycarbonate resin having a melting point of 203 ° C. using a melt transesterification method.
  • Patent Document 2 reports a polycarbonate having a glass transition temperature of 170 ° C. or higher by differential calorimetry at a heating rate of 10 ° C./min. In some cases, the melt viscosity is too high.
  • Patent Document 3 describes a copolymerized polycarbonate of isosorbide and a linear aliphatic diol. Regarding these polycarbonates composed of isosorbide, none of these documents discuss flame retardancy.
  • a first object of the present invention is to provide a flame retardant resin composition using a plant-derived raw material having high flame retardancy and good physical properties, and a molded product therefrom.
  • a second object of the present invention is to provide a flame retardant resin composition containing a specific organophosphorus compound and substantially halogen-free, and a molded article therefrom.
  • the purpose of the present invention is 100 parts by weight of a resin component (component A) containing at least 50% by weight of a polycarbonate (A-1 component) containing a unit represented by the following formula (A-1) and an organophosphorus compound represented by the following formula (1) (Component B) Achieved by a flame-retardant resin composition containing 1 to 100 parts by weight.
  • X 1 and X 2 are each independently an aromatic substituted alkyl group represented by the following formula (2).
  • AL is a branched or straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • Ar is a phenyl group, a naphthyl group or an anthryl group, which may have a substituent. Ar can be bonded to any carbon atom in AL, and n is an integer of 1 to 3.
  • the resin component mainly contains polycarbonate (A-1 component).
  • the content of the polycarbonate (component A-1) in the resin component is preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight, even more preferably at least 80% by weight, particularly preferably. Is at least 90% by weight.
  • Other resin (A-2 component) may be contained in the resin component (A component).
  • the content of the other resin (component A-2) is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, still more preferably 20% by weight or less, particularly preferably 10%.
  • the polycarbonate (component A-1) contains a carbonate unit represented by the following formula (A-1).
  • the proportion of units represented by the following formula (A-1) in all carbonate units is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more. 90 mol% or more is most preferable.
  • Polycarbonate (component A-1) has a biogenic substance content measured in accordance with ASTM D686605, preferably 25% or more, more preferably 50% or more, and even more preferably 70% or more.
  • the lower limit of the specific viscosity at 20 ° C. of a solution obtained by dissolving 0.7 g of polycarbonate (component A-1) in 100 ml of methylene chloride is preferably 0.14 or more, more preferably 0.20 or more, and still more preferably 0.8. 22 or more.
  • the upper limit is preferably 0.45 or less, more preferably 0.37 or less, and still more preferably 0.34 or less.
  • Polycarbonate (component A-1) has a melt viscosity measured with a capillary rheometer at 250 ° C. and a share rate of 600 sec. -1 0.08 ⁇ 10 under the conditions of 3 ⁇ 2.4 ⁇ 10 3 It is preferably in the range of Pa ⁇ s, 0.1 ⁇ 10 3 ⁇ 2.0 ⁇ 10 3 More preferably in the range of Pa ⁇ s, 0.1 ⁇ 10 3 ⁇ 1.5 ⁇ 10 3 The range of Pa ⁇ s is more preferable.
  • the lower limit of the glass transition temperature (Tg) of polycarbonate (component A-1) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and the upper limit is preferably 165 ° C. or lower.
  • Tg is measured by DS Instruments (model DSC2910) manufactured by TA Instruments.
  • 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, more preferably 390 ° C. or lower. And more preferably 380 ° C. or lower. It is preferable that the 5% weight loss temperature is in the above range since there is almost no decomposition of the resin when molding using the resin composition of the present invention.
  • the 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).
  • the polycarbonate (component A-1) preferably has a glass transition temperature (Tg) of 100 ° C. to 165 ° C.
  • Polycarbonate (component A-1) is represented by the following formula (a) It can manufacture with the melt polymerization method from the ether diol and carbonic acid diester represented by these.
  • 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 substances obtained from natural biomass and are one of the so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.
  • a polycarbonate in which the carbonate unit comprises a unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol).
  • Isosorbide is an ether diol that can be easily made from starch, etc., and can be obtained in abundant resources. In addition, it is superior in terms of ease of manufacture, properties, and wide range of applications compared to isomannide and isoidide.
  • Polycarbonate (component A-1) may be copolymerized with aliphatic diols or aromatic bisphenols as long as the properties are not impaired.
  • linear aliphatic diols having 3 to 12 carbon atoms and alicyclic diols having 6 to 20 carbon atoms are preferably used.
  • linear diols such as 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol
  • alicyclic alkylenes such as cyclohexanediol and cyclohexanedimethanol.
  • 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol are preferred.
  • the resin composition of this invention has the said Formula (a) as a main component as a raw material obtained from renewable resources, such as a plant, plant-derived diol is also used preferably.
  • plant-derived diol is also used preferably.
  • Specific examples include diols containing a terpene component.
  • 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 '-(m-phenylenediisopropylidene) diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) decane, 1,3-bis ⁇ 2- (4 -Hydroxyphenyl) propyl ⁇ benzene and the like.
  • bisphenol A 1,1-bis (4-hydroxyphenyl) cyclohexane
  • 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane 4,4 '-(m-
  • polycarbonate (A-1 component) can be introduced with terminal groups as long as the properties are not impaired. Such end groups can be introduced by adding the corresponding hydroxy compound during polymerization.
  • the terminal group is preferably a terminal group represented by the following formula (i) or (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).
  • 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 amino bond and an amide bond. More preferably, it is at least one bond selected from the group consisting of a single bond, an ether bond and an ester bond. Of these, a single bond and an ester bond are preferable.
  • R 5 , R 6 , R 7 , R 8 And R 9 are independently an alkyl group having 1 to 10 carbon atoms, 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 7 carbon atoms. It is at least one group selected from the group consisting of ⁇ 20 aralkyl groups. Preferably, they are each independently at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms.
  • At least one group selected from the group consisting of a methyl group and a phenyl group is preferable.
  • b is an integer of 0 to 3, preferably an integer of 1 to 3, particularly preferably an integer of 2 to 3.
  • c is an integer of 4 to 100, preferably an integer of 4 to 50, particularly preferably an integer of 8 to 50.
  • Polycarbonate (component A-1) has carbonate units in the main chain structure using raw materials obtained from renewable resources such as plants, so these hydroxy compounds are also raw materials obtained from renewable resources such as plants. Preferably there is. Examples of hydroxy compounds obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.
  • the polycarbonate (component A-1) is a mixture of a bishydroxy compound containing an ether diol represented by the formula (a) and a carbonic acid diester, and alcohol or phenol produced by a transesterification reaction under high temperature and reduced pressure. It can be obtained by performing melt polymerization to distill.
  • the reaction temperature is preferably as low as possible in order to suppress the decomposition of the ether diol and obtain a highly viscous resin with little coloration, but the polymerization temperature is 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 270 ° C.
  • ether diol and carbonic acid diester were heated at normal pressure and pre-reacted, and then the pressure was gradually reduced to 1.3 ⁇ 10 3 at the end of the reaction. -3 ⁇ 1.3 ⁇ 10 -5
  • a method of reducing the pressure to about MPa and facilitating the distillation of the alcohol or phenol produced is preferable.
  • the reaction time is usually about 1 to 4 hours.
  • a polymerization catalyst can be used to increase the polymerization rate.
  • the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium salt or potassium salt of dihydric phenol.
  • alkaline-earth metal compounds such as calcium hydroxide, barium hydroxide, magnesium hydroxide, etc. are mentioned.
  • nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine, and triethylamine. These may be used alone or in combination of two or more. Among these, it is preferable to use a nitrogen-containing basic compound and an alkali metal compound in combination.
  • the amount of these polymerization catalysts used is preferably 1 ⁇ 10 to 1 mol of carbonic acid diester component.
  • the reaction system is preferably maintained in an atmosphere of a gas inert to the raw material such as nitrogen, the reaction mixture, and the reaction product.
  • Argon etc. can be mentioned as inert gas other than nitrogen.
  • the carbonic acid diester used for the production of the polycarbonate (component A-1) include optionally substituted esters such as an aryl group having 6 to 20 carbon atoms, an aralkyl group, or an alkyl group having 1 to 18 carbon atoms.
  • the carbonic acid diester is preferably mixed at a molar ratio of 1.02 to 0.98 with respect to the total ether diol compound, more preferably 1.01 to 0.98, and still more preferably 1.01 to 0.98. 0.99. If the molar ratio of the carbonic acid diester is more than 1.02, the carbonic acid ester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable.
  • a catalyst deactivator can also be added to the polycarbonate (A-1 component) obtained by the above production method.
  • known catalyst deactivators are effectively used. Among them, sulfonic acid ammonium salts and phosphonium salts are preferable.
  • dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid
  • paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluenesulfonic acid
  • esters of sulfonic acid methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, para Octyl toluenesulfonate, phenyl paratoluenesulfonate, and the like are preferably used.
  • tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used.
  • the amount of the catalyst deactivator used is 0.5 to 50 mol, preferably 0.5 to 10 mol, per mol of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds. It can be used in a proportion, more preferably in a proportion of 0.8 to 5 mol.
  • Resin component (A component) may contain other thermoplastic resin (A-2 component) in addition to polycarbonate (A-1 component).
  • the content of the other resin (component A-2) in the component A is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, and still more preferably 20%. % By weight or less, particularly preferably 10% by weight or less.
  • polyester resin (PEst) polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO), styrene resin, polyphenylene sulfide resin (PPS) and poly Examples thereof include at least one thermoplastic resin selected from the group consisting of etherimide resins (PEI).
  • polyester resin polyphenylene ether resin
  • PC polycarbonate resin
  • PA polyamide resin
  • PO polyolefin resin
  • styrenic resin styrenic resin
  • the thermoplastic resin as the component A-2 will be specifically described.
  • the polyester resin (PEst) as the component A-2 include one or a mixture of two or more selected from an aromatic polyester resin or an aliphatic polyester resin.
  • an aromatic polyester resin which is a polyester having an aromatic dicarboxylic acid as a main dicarboxylic acid component and an aliphatic diol having 2 to 10 carbon atoms as a main glycol component.
  • the dicarboxylic acid component is composed of an aromatic dicarboxylic acid component.
  • the glycol component is preferably 80 mol% or more, more preferably 90 mol% or more, of an aliphatic diol component having 2 to 10 carbon atoms.
  • Preferred examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, methyl isophthalic acid, and 2,6-naphthalenedicarboxylic acid. These can use 1 type (s) or 2 or more types.
  • secondary dicarboxylic acids other than aromatic dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, dodecanedicarboxylic acid, and cyclohexanedicarboxylic acid, and alicyclic dicarboxylic acids. it can.
  • aliphatic diol having 2 to 10 carbon atoms include aliphatic diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and neopentyl glycol.
  • alicyclic diols such as 1, 4- cyclohexane dimethanol
  • glycols other than aliphatic diols having 2 to 10 carbon atoms include p, p'-dihydroxyethoxybisphenol A and polyoxyethylene glycol.
  • Preferred examples of the aromatic polyester resin include at least one dicarboxylic acid selected from terephthalic acid and 2,6-naphthalenedicarboxylic acid as the main dicarboxylic acid component, and ethylene glycol, trimethylene glycol and tetramethylene glycol as the main diol component. It is polyester which has an ester unit which consists of at least 1 sort (s) of diol chosen from these.
  • Specific aromatic polyester resins include polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, polytrimethylene terephthalate resin, and polytrimethylene naphthalate resin. It is preferably at least one selected from the group consisting of Particularly 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 particularly preferable.
  • a polyester elastomer having the above repeating unit as the main repeating unit of the hard segment can be used.
  • dicarboxylic acid is selected from terephthalic acid, isophthalic acid, sebacic acid and adipic acid
  • the main component is a component of 80 mol% or more, preferably 90 mol% or more of the total dicarboxylic acid component or the total glycol component, and the main repeating unit is 80 mol% or more of the total repeating unit, preferably 90 mol%. It is a repeating unit of mol% or more.
  • the molecular weight of the aromatic polyester resin only needs to have an intrinsic viscosity that can be used usually as a molded product, and the intrinsic viscosity measured in orthochlorophenol at 35 ° C. is preferably 0.5 to 1.6 dl / g, More preferably, it is 0.6 to 1.5 dl / g.
  • the aromatic polyester resin advantageously has a terminal carboxyl group (—COOH) amount of 1 to 60 equivalents / T (1 ton of polymer).
  • the amount of the terminal carboxyl group can be determined, for example, by potentiometric titration of an m-cresol solution with an alkaline solution.
  • PPE resins those commonly known as PPE resins can be used. Specific examples of such PPE include (2,6-dimethyl-1,4-phenylene) ether, (2,6-diethyl-1,4-phenylene) ether, (2,6-dipropyl-1,4-phenylene).
  • Reduced viscosity ⁇ which is a measure of the molecular weight of PPE resin sp / C (0.5 g / dl, toluene solution, measured at 30 ° C.) is 0.2 to 0.7 dl / g, preferably 0.3 to 0.6 dl / g.
  • a PPE resin having a reduced viscosity in this range has a good balance between molding processability and mechanical properties, and the reduced viscosity can be easily adjusted by adjusting the amount of catalyst during the production of PPE.
  • polycarbonate resin (PC) as the component A-2 examples include those obtained by an interfacial polymerization reaction between various dihydroxyaryl compounds and phosgene using a solvent such as methylene chloride. Moreover, what is obtained by transesterification with a dihydroxyaryl compound and diphenyl carbonate is mentioned.
  • a typical example is a polycarbonate obtained by the reaction of 2,2'-bis (4-hydroxyphenyl) propane and phosgene.
  • dihydroxyaryl compound used as a raw material for polycarbonate examples include bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) propane, 2, 2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, 2,2'-bis (4-hydroxy-3-methylphenyl) 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-hydroxy) Enyl) cyclopentane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1,1′-bis (4-hydroxyphenyl) cyclo
  • dihydroxyaryl compounds can be used alone or in combination of two or more.
  • Preferred dihydroxyaryl compounds include bisphenols that form aromatic polycarbonates with high heat resistance, bis (hydroxyphenyl) alkanes such as 2,2′-bis (4-hydroxyphenyl) propane, and bis (4-hydroxyphenyl) cyclohexane.
  • a particularly preferred dihydroxyaryl compound is 2,2'-bis (4-hydroxyphenyl) propane which forms a bisphenol A type aromatic polycarbonate.
  • the molecular weight of the polycarbonate does not need to be particularly limited, but if it is too low, the strength is not sufficient, and if it is too high, the melt viscosity becomes high and it becomes difficult to mold, so the viscosity average molecular weight is usually 10,000 to 50,000, Preferably, it is 15,000 to 30,000.
  • the viscosity average molecular weight (M) here is a specific viscosity ( ⁇ obtained from a solution of 0.7 g of polycarbonate dissolved in 100 ml of methylene chloride at 20 ° C. sp ) Is inserted into the following equation.
  • ⁇ ⁇ Briefly explain the basic means of producing polycarbonate.
  • the reaction is usually performed in the presence of an acid binder and an organic solvent.
  • the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine.
  • the organic solvent for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
  • a catalyst such as a tertiary amine or a quaternary ammonium salt can be used.
  • a terminal terminator such as an alkyl-substituted phenol such as phenol or p-tert-butylphenol as the molecular weight regulator.
  • the reaction temperature is usually 0 to 40 ° C.
  • the reaction time is several minutes to 5 hours
  • the pH during the reaction is preferably maintained at 10 or more. It is not necessary that all of the resulting molecular chain ends have a structure derived from the end terminator.
  • a transesterification reaction (melt polymerization method) using a carbonic acid diester as a carbonate precursor, a predetermined proportion of dihydric phenol is stirred with the carbonic acid diester in the presence of an inert gas, and the resulting alcohol or phenol is distilled.
  • the reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C.
  • the reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning.
  • An end terminator is added simultaneously with the dihydric phenol or the like in the initial stage of the reaction or in the middle of the reaction.
  • the catalyst used for the transesterification reaction now well-known can be used.
  • the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
  • polyamide resin (PA) as the component A-2 examples include a ring-opening polymer of cyclic lactam, a polymer of aminocarboxylic acid, a polycondensate of dibasic acid and diamine, and the like. Specific examples include aliphatic polyamides such as nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 11 and nylon 12, and copolymers and mixtures thereof.
  • aliphatic-aromatic polyamides such as poly (meta-xylene adipamide), poly (hexamethylene terephthalamide), poly (nonamethylene terephthalamide), poly (hexamethylene isophthalamide), poly (tetramethylene isophthalamide), These copolymers and a mixture are mentioned.
  • the polyamide that can be used in the present invention is not particularly limited.
  • the molecular weight of such a polyamide resin is preferably 1.7 to 4.5, more preferably 2.0 to 4.0, and still more preferably relative viscosity measured at 25 ° C. in 98% sulfuric acid at a concentration of 1%. Is 2.0 to 3.5.
  • the polyolefin resin as the component A-2 is a homopolymer or copolymer of olefins such as ethylene, propylene and butene, or a copolymer of monomer components copolymerizable with these olefins. .
  • Examples thereof include a copolymer, an ethylene-propylene copolymer, and an ethylene-butene copolymer.
  • the molecular weight of these polyolefin resins is not particularly limited, but the higher the molecular weight, the better the flame retardancy.
  • the styrene resin as the component A-2 is a homopolymer or copolymer of an aromatic vinyl monomer such as styrene, ⁇ -methylstyrene or vinyltoluene, these monomers and acrylonitrile, methyl methacrylate or the like.
  • Styrene and / or styrene derivatives, or styrene and / or styrene derivatives and other vinyl monomers are graft-polymerized onto copolymers with vinyl monomers, diene rubbers such as polybutadiene, ethylene / propylene rubber, acrylic rubber, etc. It has been made.
  • styrenic resin examples include, for example, polystyrene, high-impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene.
  • HIPS high-impact polystyrene
  • AS resin acrylonitrile / styrene copolymer
  • ABS resin acrylonitrile / butadiene / styrene copolymer
  • ABS resin methyl methacrylate / butadiene / styrene
  • MVS resin Methyl methacrylate / Acrylonitrile / Butadiene / Styrene copolymer (MABS resin), Acrylonitrile / Acrylic rubber / Styrene copolymer (AAS resin), Acrylonitrile / Ethylene propylene rubber / Styrene copolymer (ABS resin) AES resin) or a mixture thereof.
  • MABS resin Methyl methacrylate / Acrylonitrile / Butadiene / Styrene copolymer
  • AS resin Acrylonitrile / Acrylic rubber / Styrene copolymer
  • ABS resin Acrylonitrile / Ethylene propylene rubber / Styrene copolymer
  • AES resin Acrylonitrile / Ethylene propylene rubber / Styrene copolymer
  • a rubber-modified styrene resin refers to a polymer in which a rubber-like polymer is
  • Aromatic vinyl monomer in the presence of rubbery polymer, and optionally vinyl monomer are added to obtain a monomer mixture by known block polymerization, block suspension polymerization, solution polymerization or emulsion polymerization. It is done.
  • the rubber-like polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubber, isoprene rubber, chloroprene rubber, polybutyl acrylate.
  • examples thereof include acrylic rubbers such as ethylene-propylene-diene terpolymer (EPDM), and diene rubbers are particularly preferable.
  • the aromatic vinyl monomer as an essential component in the graft copolymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, ⁇ -methylstyrene, paramethylstyrene, and the like. Styrene is most preferred. Examples of vinyl monomers that can be added as needed include acrylonitrile and methyl methacrylate.
  • the rubber-like polymer in the rubber-modified styrene resin is 1 to 50% by weight, preferably 2 to 40% by weight.
  • the monomer mixture capable of graft polymerization is 99 to 50% by weight, preferably 98 to 60% by weight.
  • the polyphenylene sulfide resin (PPS) as the A-2 component has a repeating unit represented by the following formula.
  • n is an integer of 1 or more, preferably an integer of 50 to 500, more preferably an integer of 100 to 400, which may be linear or crosslinked.
  • An example of a method for producing a polyphenylene sulfide resin is a method of reacting dichlorobenzene with sodium disulfide.
  • Cross-linked products can be produced by polymerizing a polymer with a low degree of polymerization and then heating in the presence of air to partially cross-link to increase the molecular weight. It can be manufactured by the method.
  • the polyetherimide resin (PEI) as the A-2 component has a repeating unit represented by the following formula.
  • Ar in the formula 1 Represents an aromatic dihydroxy compound residue
  • Ar 2 Represents an aromatic diamine residue.
  • an aromatic dihydroxy compound the aromatic dihydroxy compound shown by description of polycarbonate resin mentioned above is mentioned, Bisphenol A is especially preferable.
  • aromatic diamines m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl, 3,4′-diaminodiphenyl, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, diaminodiphenylmethane, Examples include diaminodiphenyl sulfone and diaminodiphenyl sulfide.
  • N in the above formula represents an integer of 5 to 1,000, preferably an integer of 10 to 500.
  • Examples of the method for producing the polyetherimide resin include US Pat. No. 3,847,867, US Pat. No. 3,847,869, US Pat. No.
  • polyester resin PET
  • PPE polyphenylene ether resin
  • PC polycarbonate resin
  • PA polyamide resin
  • styrene resin is preferable.
  • organophosphorus compound used as the component B is represented by the following formula (1).
  • X in the formula 1 , X 2 are each independently an aromatic substituted alkyl group represented by the following formula (2).
  • AL is a branched or straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • Ar is a phenyl group, a naphthyl group or an anthryl group, and these may have a substituent.
  • Ar can be bonded to any carbon atom in AL.
  • n is an integer of 1 to 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). Where R 2 , R 5 Each independently represents a phenyl group, a naphthyl group or an anthryl group, which may have a substituent.
  • Substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl groups, halogen atoms such as fluorine, chlorine and bromine, phenyl groups and naphthyl groups having 6 to 6 carbon atoms. And 12 aryl groups.
  • R 1 , R 3 , R 4 , R 6 Each independently has a hydrogen atom, a branched or straight chain alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a substituent.
  • An anthryl group may be used.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl groups, halogen atoms such as fluorine, chlorine and bromine, phenyl groups and naphthyl groups having 6 to 6 carbon atoms. And 12 aryl groups.
  • Ar 1 And Ar 2 Each independently represents a phenyl group, a naphthyl group or an anthryl group, which may have a substituent.
  • Substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl groups, halogen atoms such as fluorine, chlorine and bromine, phenyl groups and naphthyl groups having 6 to 6 carbon atoms. And 12 aryl groups.
  • R 11 , R 12 , R 13 And R 14 Each independently has 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 substituent.
  • An anthryl group may be used.
  • Substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl groups, halogen atoms such as fluorine, chlorine and bromine, phenyl groups and naphthyl groups having 6 to 6 carbon atoms. And 12 aryl groups.
  • AL 1 And AL 2 are each independently a branched or straight-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms. Examples of the aliphatic hydrocarbon group include alkanediyl groups having 1 to 4 carbon atoms such as a methylene group, an ethylene group, and a propyl group.
  • Ar 3 And Ar 4 Each independently represents a phenyl group, a naphthyl group or an anthryl group, which may have a substituent.
  • Substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl groups, halogen atoms such as fluorine, chlorine and bromine, phenyl groups and naphthyl groups having 6 to 6 carbon atoms. And 12 aryl groups.
  • P and q are each independently an integer of 0 to 3.
  • Ar 3 And Ar 4 Each is AL 1 And AL 2 To any carbon atom.
  • it is preferably a phosphorus compound represented by the following formulas (5), (6), (7), (8).
  • R 21 , R 22 Each independently represents a phenyl group, a naphthyl group or an anthryl group, which may have a substituent.
  • R 21 And R 22 In the phenyl group, naphthyl group or anthryl group, the hydrogen atom of the aromatic ring may be substituted, and as the substituent, methyl, ethyl, propyl, butyl or the bonding group of the aromatic ring is an oxygen atom, sulfur atom Alternatively, an aryl group having 6 to 14 carbon atoms via an aliphatic hydrocarbon group having 1 to 4 carbon atoms can be given.
  • R 31 And R 34 Are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • R 33 And R 36 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms. A methyl group or an ethyl group is preferable.
  • R 32 And R 35 Each independently represents a phenyl group, a naphthyl group or an anthryl group, which may have a substituent.
  • a phenyl group which may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • R 32 And R 35 Preferable specific examples include a phenyl group, a cresyl group, a xylyl group, a trimethylphenyl group, a 4-phenoxyphenyl group, a cumyl group, a naphthyl group, and a 4-benzylphenyl group, and a phenyl group is particularly preferable.
  • Ar 1 And Ar 2 are each independently a phenyl group, a naphthyl group or an anthryl group, and these may have a substituent.
  • R 11 , R 12 , R 13 And R 14 Each independently has 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 substituent.
  • An anthryl group may be used.
  • it represents a phenyl group, and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • Ar 1 And Ar 2 Preferable specific examples include a phenyl group, a cresyl group, a xylyl group, a trimethylphenyl group, a 4-phenoxyphenyl group, a cumyl group, a naphthyl group, and a 4-benzylphenyl group, and a phenyl group is particularly preferable.
  • AL 1 And AL 2 Are each independently a branched or straight-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • a branched or straight chain aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, and a branched or straight chain aliphatic hydrocarbon group having 1 to 2 carbon atoms is particularly preferred.
  • the aliphatic hydrocarbon group include alkanediyl groups having 1 to 4 carbon atoms such as a methylene group, an ethylene group, and a propyl group.
  • alkanetriyl groups having 1 to 4 carbon atoms such as methanetriyl group, ethanetriyl group, and propanetriyl group.
  • examples thereof include alkanetetrayl groups having 1 to 4 carbon atoms such as methanetetrayl group, ethanetetrayl group, and propanetetrayl group.
  • AL 1 And AL 2 Preferable specific examples include methylene group, ethylene group, ethylidene group, trimethylene group, propylidene group, isopropylidene group and the like, and methylene group, ethylene group and ethylidene group are particularly preferable.
  • Ar 3 And Ar 4 Each independently represents a phenyl group, a naphthyl group or an anthryl group, which may have a substituent.
  • it represents a phenyl group, and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) , Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • Ar 3 And Ar 4 Each is AL 1 And AL 2 To any carbon atom.
  • p and q are each independently an integer of 0 to 3.
  • p and q are preferably 0 or 1, particularly preferably 0.
  • R 41 And R 44 Each independently has 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 a substituent.
  • An anthryl group may be used.
  • a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a phenyl group which may have a substituent is preferable.
  • R 41 And R 44 Is a phenyl group, it may have a substituent in any part other than the part bonded to phosphorus through a carbon atom on the aromatic ring, and may be methyl, ethyl, propyl (including isomers),
  • the bonding group to butyl (including isomers) or an aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • it represents a phenyl group and may have a substituent in any part other than the part bonded to phosphorus via a carbon atom on the aromatic ring, and includes methyl, ethyl, propyl (including isomers) ), Butyl (including isomers) or a group bonded to the aromatic ring thereof is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • R 42 , R 43 , R 45 And R 46 Preferable specific examples include a phenyl group, a cresyl group, a xylyl group, a trimethylphenyl group, a 4-phenoxyphenyl group, a cumyl group, a naphthyl group, and a 4-benzylphenyl group, and a phenyl group is particularly preferable.
  • the organophosphorus compound (component B) represented by the formula (1) exhibits an extremely excellent flame retardant effect on the resin.
  • the organophosphorus compound (component B) can be easily made flame retardant by itself in a small amount, and does not impair the original properties of the resin.
  • a fluorine-containing resin or other additive is used to reduce the use ratio of the B component, improve the flame retardancy of the molded product, and the physical properties of the molded product.
  • the organophosphorus compound (component B) as a flame retardant in the resin composition of the present invention is represented by the above formula (1), and the most preferred representative compounds are the following formulas (1-a) and (1-b). , (1-c), (1-d).
  • the component B may be produced by a method other than the method described below.
  • the B component is obtained, for example, by reacting pentaerythritol with phosphorus trichloride, subsequently treating the oxidized reaction product with an alkali metal compound such as sodium methoxide, and then reacting with aralkyl halide. It can also be obtained by reacting pentaerythritol with aralkyl phosphonic acid dichloride, or reacting pentaerythritol with phosphorus trichloride and reacting aralkyl alcohol with a compound obtained by reacting pentaerythritol with phosphorus trichloride, followed by Arbuzov transfer at high temperature. . The latter reaction is disclosed, for example, in U.S. Pat. No.
  • (IV) the organophosphorus compound of the above (1-d) in component B It can be obtained by reacting pentaerythritol with diphenylmethylphosphonic acid dichloride. Alternatively, it can be obtained by reacting pentaerythritol with phosphorus trichloride and heat-treating the obtained product and the reaction product of diphenylmethyl alcohol in the presence of a catalyst.
  • the acid value of the aforementioned B component is preferably 0.7 mgKOH / g or less, more preferably 0.5 mgKOH / g or less.
  • the component B most preferably has an acid value of 0.4 mgKOH / g or less.
  • the acid value means the amount (mg) of KOH necessary for neutralizing the acid component in 1 g of the sample (component B).
  • the component B one having an HPLC purity of preferably at least 90%, more preferably at least 95% is used. Such a high-purity product is preferable because of excellent flame retardancy, hue, and thermal stability of the molded product.
  • the HPLC purity of the B component can be effectively measured by using the following method.
  • the column was Develosil ODS-7 300 mm ⁇ 4 mm ⁇ manufactured by Nomura Chemical Co., Ltd., and the column temperature was 40 ° C.
  • component B As a solvent, a mixed solution of acetonitrile and water 6: 4 (volume ratio) was used, and 5 ⁇ l was injected. The detector used was UV-260 nm.
  • the method for removing impurities in component B is not particularly limited, but a method of performing repulp washing with a solvent such as water or methanol (washing with a solvent, repeating filtration several times) is the most effective. It is also advantageous in terms of cost.
  • the content of component B is 1 to 100 parts by weight, preferably 2 to 90 parts by weight, more preferably 2 to 70 parts by weight, and even more preferably 3 to 50 parts by weight with respect to 100 parts by weight of the resin component (component A). Range.
  • the preferred range of the B component content is determined by the desired flame retardancy level, the type of resin component (A component), and the like. Even if it is other than the A component and the B component constituting these compositions, other components can be used as needed as long as the purpose of the present invention is not impaired.
  • the blending amount of the B component can also be changed by using the resin, and in many cases, the blending ratio of the B component can be reduced by using these resins.
  • the flame-retardant resin composition of the present invention can achieve at least V-2 at the flame-retardant level of UL-94 standard.
  • the flame retardant resin composition of the present invention comprises a resin component (component A), an organophosphorus compound (component B) and other components as necessary, such as a V-type blender, super mixer, super floater, Henschel mixer, etc.
  • a resin component component A
  • an organophosphorus compound component B
  • other components such as a V-type blender, super mixer, super floater, Henschel mixer, etc.
  • a kneader various melt mixers such as a kneader, a single-screw or twin-screw extruder can be used.
  • the resin composition is 220 to 280 ° C., preferably 230 to 270 ° C. using the twin screw extruder.
  • a method is preferably used in which a liquid component is injected by a side feeder, extruded by a side feeder, extruded, and pelletized by a pelletizer.
  • the flame retardant resin composition of the present invention is substantially free of halogen and has very high flame retardant performance, such as home appliance parts, electrical / electronic parts, automobile parts, mechanical / mechanical parts, cosmetic containers, etc. It is useful as a material for molding various molded articles. Specifically, breaker parts, switch parts, motor parts, ignition coil cases, power plugs, power outlets, coil bobbins, connectors, relay cases, fuse cases, flyback transformer parts, focus block parts, distributor caps, harness connectors, etc. Can be suitably used.
  • thinning housings, casings or chassis such as electronic / electrical products (for example, home appliances / OA equipment such as telephones, personal computers, printers, fax machines, copiers, televisions, VCRs, audio equipment, or parts thereof)
  • electronic / electrical products for example, home appliances / OA equipment such as telephones, personal computers, printers, fax machines, copiers, televisions, VCRs, audio equipment, or parts thereof
  • it is useful as a printer casing, a fixing unit component, a home appliance such as a fax machine, a mechanical / mechanical component of an OA product, etc. that require particularly excellent heat resistance and flame retardancy.
  • the molding method is not particularly limited, such as injection molding, blow molding, press molding, and the like, but is preferably manufactured by injection molding a pellet-shaped resin composition using an injection molding machine.
  • the product was confirmed to be bisbenzylpentaerythritol diphosphonate by mass spectral analysis, 1 H, 31 P nuclear magnetic resonance spectral analysis and elemental analysis.
  • the yield was 20.60 g, the yield was 91%, and the 31 P-NMR purity was 99%.
  • the HPLC purity measured by the method described in the text was 99%.
  • the acid value was 0.05 mgKOH / g.
  • reaction mixture was cooled to room temperature, and 5180.7 g (61.0 mol) of methylene chloride was added to the obtained reaction product, and 889.4 g (12.0 mol) of tertiary butanol and 150. 2 g (1.77 mol) was added dropwise.
  • the obtained crystals were washed with toluene and methylene chloride and filtered.
  • the obtained filtered product was dried at 80 ° C. and 1.33 ⁇ 10 2 Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid.
  • the obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide according to 31 P, 1 HNMR spectrum. confirmed. 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide obtained in a reaction vessel equipped with a thermometer, condenser and dropping funnel 1341.0 g (5.88 mol) and DMF6534.2 g (89.39 mol) were charged and stirred. Sodium methoxide 648.7 g (12.01 mol) was added to the reaction vessel under ice cooling.
  • the solid obtained is 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide according to 31 P, 1 H-NMR spectrum. I confirmed that. 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide obtained in a reaction vessel equipped with a thermometer, condenser and dropping funnel 1341.0 g (5.88 mol) and DMF6534.2 g (89.39 mol) were charged and stirred. Sodium methoxide 648.7 g (12.01 mol) was added to the reaction vessel under ice cooling.
  • the obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (diphenylmethyl) by 31 P-NMR, 1 H-NMR spectrum and elemental analysis. It was confirmed that it was ⁇ 3,9-dioxide.
  • the obtained solid was a white powder, the yield was 36.8 g, and the yield was 91%.
  • the 31 P-NMR purity was 99%.
  • the HPLC purity measured by the method described in the text was 99%.
  • the acid value was 0.07 mg KOH / g.
  • PX-200 1,3-phenylenebis [di (2,6-dimethylphenyl) phosphate]
  • PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.
  • Examples 1 to 22 and Comparative Examples 1 to 9 Each component described in Tables 1 to 3 was blended in a tumbler in the amount (parts by weight) described in Tables 1 to 3, and pelletized with a 15 mm ⁇ twin screw extruder (manufactured by Technobel, KZW15). The obtained pellets were dried with a hot air dryer at 130 ° C. for 4 hours. The dried pellets were molded with an injection molding machine (J75EIII, manufactured by Nippon Steel Works).
  • the results of evaluation using molded plates are shown in Tables 1 to 3. Effects of the Invention
  • the flame retardant resin composition of the present invention and a molded product formed therefrom have the following advantages compared to conventional resin compositions using plant-derived materials.
  • the resin using the plant-derived raw material hardly undergoes thermal degradation during the molding of the resin using the plant-derived raw material or the molded product. In addition, it has excellent thermal stability. Therefore, the flame retardant resin composition of the present invention is excellent in a balance between flame retardancy, mechanical strength and thermal stability.
  • the organophosphorus compound as a flame retardant is colorless and compatible with a resin using a plant-derived raw material, a molded product excellent in transparency can be obtained.
  • the flame retardant resin composition of the present invention contains substantially no halogen and has very high flame retardant performance, so that it is a home appliance part, electrical / electronic part, automobile part, machine / mechanical part, cosmetic container, etc. It is useful as a material for molding various molded articles.

Abstract

La présente invention concerne : une composition de résine ignifuge qui est préparée en utilisant un matériau brut dérivé de plante et qui présente un fort pourvoir ignifuge ainsi que d'excellentes propriétés physiques ; et des produits moulés de celle-ci. La composition de résine ignifuge comprend 100 parties en poids d'un composant de résine A (composant (A)) qui contient au moins 50 % en poids d'un polycarbonate (composant (A-1)) comprenant des motifs représentés par la formule (A-1) et 1 à 100 parties en poids d'un composé organophosphoreux (composant (B)) représenté par la formule générale (1). Dans la formule générale (1), X1 et X2 sont chacun indépendamment un groupe alkyle substitué par un aromatique représenté par la formule générale (2) [où AL est un groupe hydrocarboné aliphatique en C1-5 linéaire ou ramifié ; Ar est un groupe phényle, un groupe naphtyle, ou un groupe anthryle, ces groupes étant facultativement substitués ; n est un entier de 1 à 3 ; et Ar peut être lié à un atome de carbone quelconque de AL].
PCT/JP2009/071011 2009-12-10 2009-12-10 Composition ignifuge de résine et produits moulés de celle-ci WO2011070689A1 (fr)

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BR112012013048A BR112012013048A2 (pt) 2009-12-10 2009-12-10 composição de resina retardante de chama, e, artigo moldado
US13/509,655 US8618196B2 (en) 2009-12-10 2009-12-10 Flame retardant resin composition and molded article thereof
JP2011545044A JPWO2011070689A1 (ja) 2009-12-10 2009-12-10 難燃性樹脂組成物およびそれからの成形品
CN200980162785.XA CN102666725B (zh) 2009-12-10 2009-12-10 阻燃性树脂组合物及由其制成的成型品
EP09852085.1A EP2511338B1 (fr) 2009-12-10 2009-12-10 Composition ignifuge de résine et produits moulés de celle-ci
PCT/JP2009/071011 WO2011070689A1 (fr) 2009-12-10 2009-12-10 Composition ignifuge de résine et produits moulés de celle-ci
KR1020127014673A KR101745036B1 (ko) 2009-12-10 2009-12-10 난연성 수지 조성물 및 그것으로부터의 성형품

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GB1079686A (en) 1963-05-17 1967-08-16 Courtaulds Ltd Polyesters
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BR112012013048A2 (pt) 2016-11-22
KR101745036B1 (ko) 2017-06-08
EP2511338A4 (fr) 2014-01-15
US20130030095A1 (en) 2013-01-31
EP2511338B1 (fr) 2016-04-27
KR20120119906A (ko) 2012-10-31
JPWO2011070689A1 (ja) 2013-04-22
CN102666725A (zh) 2012-09-12
EP2511338A1 (fr) 2012-10-17
CN102666725B (zh) 2014-12-31

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