WO1999027016A1 - Composition de resine retardatrice de combustion - Google Patents

Composition de resine retardatrice de combustion Download PDF

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Publication number
WO1999027016A1
WO1999027016A1 PCT/JP1998/005256 JP9805256W WO9927016A1 WO 1999027016 A1 WO1999027016 A1 WO 1999027016A1 JP 9805256 W JP9805256 W JP 9805256W WO 9927016 A1 WO9927016 A1 WO 9927016A1
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WO
WIPO (PCT)
Prior art keywords
composition
weight
composition according
group
phosphate
Prior art date
Application number
PCT/JP1998/005256
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English (en)
Japanese (ja)
Inventor
Toshio Nakane
Hatsuhiko Harashina
Shinya Yamada
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Polyplastics Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co., Ltd. filed Critical Polyplastics Co., Ltd.
Publication of WO1999027016A1 publication Critical patent/WO1999027016A1/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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a flame-retardant resin composition having an excellent self-extinguishing property, and a flame-retardant resin composition of the present invention, which does not use a halogen-based flame retardant and has a high molecular weight material. High flame retardancy can be provided at the same time without lowering the mechanical properties.
  • Polybutylene terephthalate has excellent properties in terms of mechanical properties, heat resistance, electrical properties, and moldability, and is used as a engineering plastic for structural materials such as electrical parts, automotive parts, and precision mechanical parts. Widely used for. However, since polybutylene terephthalate alone burns relatively easily, a method of adding a halogen-based flame retardant, a phosphorus-containing flame retardant, a nitrogen-containing flame retardant, etc. as a flame retardant imparting flame retardancy. Many have been proposed.
  • a blend of a bromine compound such as decap mouth modifer, brominated polycarbonate, a brominated cyanuric ester compound, or a brominated epoxy compound as a flame retardant is often used.
  • a more excellent flame-retardant effect can be obtained by using a metal oxide such as antimony trioxide, aluminum hydroxide, or magnesium hydroxide, or a flame-retardant auxiliary such as hydroxide. Have been.
  • the halogen compound as described above is gradually reduced by heat or light. It decomposes to generate halogen radicals, and then performs a hydrogen abstraction reaction to generate hydrogen halide.
  • This radical or hydrogen hydride promotes the radical decomposition, hydrolysis, and transesterification of polybutylene terephthalate, which causes deterioration of the resin.
  • an inorganic compound represented by antimony trioxide also essentially acts as a catalyst for hydrolysis and transesterification, which adversely affects the heat resistance of polybutylene terephthalate.
  • a method of blending a large amount of a phosphorus compound as a method of making a resin flame-retardant without using a halogen-based flame retardant is known.
  • blending red phosphorus that can most effectively increase the phosphorus element content among phosphorus compounds has been studied for a long time.
  • JP-A-49-74240 discloses a technique for blending red phosphorus with polybutylene terephthalate to make it flame-retardant.
  • this method is satisfactory in terms of environmental improvement, the mechanical properties of the resin material are significantly reduced, making it unsuitable for structural materials such as electrical parts, automotive parts and precision mechanical parts, which are the original applications. .
  • JP-A-50-136341 discloses an example in which red phosphorus is added as a flame retardant to polybutylene terephthalate and polycarbonate.
  • red phosphorus is added to polybutylene terephthalate and polycarbonate during melt kneading. A single decomposition reaction is induced, and as a result, a reduction in the molecular weight of the resin composition is inevitable, and it is essential to use glass fibers and other inorganic fillers in combination for use as a resin material.
  • JP-A-5-287119 and JP-A-6-80885 disclose a technique of blending a rubbery polymer in order to suppress a decrease in mechanical properties due to blending of red phosphorus.
  • this method is expected to improve the impact resistance, the flexibility of the rubber-like polymer significantly lowers the rigidity of the entire resin, which also greatly restricts the application to structural materials.
  • JP-A-10-114856 which was distributed on May 6, 1998, discloses a resin composition containing polybutylene terephthalate, polycarbonate, coated red phosphorus, phosphite, and a fluororesin.
  • the present invention provides a flame-retardant resin composition which is a high-molecular material provided with excellent flame retardancy without using a halogen-based flame retardant and which does not cause deterioration in mechanical properties. With the goal.
  • the present inventors have studied the elimination of halogen-based flame retardants when imparting flame retardancy to thermoplastic resins.As a result, the presence of red phosphorus in polybutylene terephthalate and polycarbonate provided excellent self-extinguishing properties and excellent fire-extinguishing properties. The present inventors have found that a resin composition satisfying all of mechanical properties and heat resistance can be obtained, and have completed the present invention.
  • the present invention is a flame-retardant resin composition containing (A) polybutylene terephthalate, (B) polycarbonate, (C) a polymer containing red phosphorus and (E) fluorine.
  • the weight ratio of (A) and (B) is in the range of 95: 5 to 5:95, and (C) is 1 to 30 parts by weight based on 100 parts by weight of the total of (A) and (B). Parts, or 1-20 parts by weight, where (A) and (B) 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.1 to 2 parts by weight, based on the total of
  • (B) is preferably 5 to 50% by weight based on the total amount of (A). Further, 5 to 35% by weight is preferable.
  • the present invention is a process for producing the above composition, comprising: (C) kneading a resin composition obtained by previously kneading red phosphorus into (B), melt-kneading it into (A), and adding (E).
  • a method for producing the above composition which comprises melt-kneading (C) a resin composition obtained by previously kneading red phosphorus with (A), (K) with (B), and adding (E).
  • the above composition further comprises (D) a phosphorus compound.
  • the weight ratio of (A) and (B) is in the range of 85:15 to 60:40, and the amount of (C) is 3 to 10% by weight based on the total composition, and the amount of (D) is Is a composition prepared by melt-kneading so that 0.01 to 1% by weight of the total composition and 0.1 to 10% by weight of (E) based on the total amount of the composition are described in the specification.
  • the composition in which the difference in crystallization peak temperature upon repetition measured by the above method is 5 ° C. or less is also a preferred embodiment of the present invention.
  • the present invention relates to (A) polybutylene terephthalate, (B) polycarbonate, (C) red phosphorus, (D) phosphoric acid, phosphorous acid, phosphinic acid, phosphinic acid, and derivatives or metal salts thereof.
  • the composition is manufactured by melt-kneading so that the amount is 3 to 10% by weight with respect to the total composition, and the blending amount of the component (D) is 0.01 to 1% by weight with respect to the total composition. It may be a flame-retardant resin composition having a crystallization peak temperature difference of 5 ° C. or less at the time of repetition measured by the above method.
  • the (A) polybutylene terephthalate used in the present invention is a crystalline polyester obtained by polycondensation of terephthalic acid or a derivative thereof with 1,4-butanediol.
  • terephthalic acid derivative for example, a lower alcohol ester such as dimethyl ester is suitable.
  • the polycarbonate (B) of the present invention means a high molecular compound having a carbonate bond in the main chain, and is usually obtained by polycondensation of a dihydroxy compound with phosgene or transesterification of a dihydroxy compound with a carbonate ester. And may be any of aliphatic, alicyclic and aromatic polycarbonates.
  • Preferred polycarbonates include aromatic polycarbonates, especially bisphenol A-type polycarbonates such as bisphenol A-type polycarbonates.
  • the blending amount of (B) the polycarbonate is 15 to 40% by weight based on the total of (A) polybutylene terephthalate and (B) the polycarbonate.
  • the blending amount of the polyacrylonitrile is less than 15% by weight, a sufficient flame-retardant effect is not exhibited, and if it exceeds 40% by weight, the mechanical properties and heat resistance of the resin composition are significantly reduced. Not preferred. Further, considering the flame retardancy and the balance of physical properties, the preferred blending amount of (B) polycarbonate is 20 to 35% by weight based on the total amount of (A) polybutylene terephthalate.
  • the (C) red phosphorus used in the present invention preferably has an average particle diameter of 200 Urn or less and has a spherical shape without a crushed surface in order to achieve both high levels of flame retardancy and mechanical properties. Further, fine powder red phosphorus having an average particle size of 5 to 30 m and a particle size of 100 m or more and a content of 5 wt% or less is particularly preferable. However, when the content of particles having a particle size of 1 m or less is 5% by weight or more, the weight fraction of the coating material of red phosphorus is increased, and the flame retardancy is undesirably reduced.
  • thermoplastic resin thermosetting resin
  • aluminum hydroxide magnesium hydroxide
  • zinc hydroxide zinc hydroxide
  • titanium hydroxide titanium hydroxide
  • red phosphorus coated with two or more types is preferably used.
  • thermoplastic resin or thermosetting resin that can be used for coating include an epoxy resin, a phenol resin, a polyester resin, a silicone resin, a polyamide resin, and an acrylic resin. It is also preferable to use a coating of a metal hydroxide or a metal oxide and then a double coating of a coating made of a thermoplastic resin and / or a thermosetting resin. it can.
  • modified red phosphorus are excellent in heat stability and hydrolysis resistance, and can significantly reduce the generation of phosphine gas by a hydrolysis reaction in the presence of water or at a high temperature. It is preferable in terms of safety from the viewpoint of safety in the production.
  • the amount of (C) red phosphorus used in the present invention is in the range of 3 to 10% by weight, preferably 3.5 to 8% by weight, based on the total composition.
  • the blending amount of red phosphorus can be further reduced.
  • Phosphorus compounds other than red phosphorus include aromatic phosphate esters such as triphenyl phosphate tricresyl phosphate, aliphatic phosphate esters such as tridecyl phosphate, and condensed phosphate esters. it can.
  • the present invention provides, as the component (D), one or more phosphorus-based compounds selected from phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid and their derivatives or metal salts thereof.
  • polybutylene terephthalate can be blended in an amount of 0.01 to 1% by weight of the composition under conditions where the composition is subjected to high temperatures for a long time after molding. It is indispensable to obtain a composition that does not cause deterioration in physical properties due to the transesterification reaction between the resin and the polycarbonate.
  • the crystallization peak temperature difference during repetition is determined by the following method. It was measured. [Diagnosis peak temperature difference during repetition]
  • the crystallization temperature of the resin composition was measured with a Perkin Elmer DSC from 250 to 100 ° C at a temperature drop rate of ZCTCZmin, the peak temperature of the DSC curve was determined, and after the temperature was raised again to 250 ° C, the temperature was lowered.
  • the crystallization peak temperature when cooling at a rate of 20 ° CZmin is determined, and the difference between the crystallization peak temperatures is defined as the crystallization peak temperature difference during repetition, and the difference between polybutylene terephthalate and polycarbonate is determined. It was used as a guide for transesterification.
  • the difference in crystallization peak temperature during this repetition is large, the melt viscosity during production may become unstable, or the physical properties may decrease under conditions where the composition is subjected to high temperatures for a long time after molding. . Furthermore, the progress of the transesterification reaction hinders the high crystallinity of polybutylene terephthalate, causing a problem that the molding cycle is prolonged and the heat resistance of the resin is significantly impaired.
  • the difference should be kept at least within 5 ° C.
  • the component (D) used for such a purpose includes a phenyl erythritol diphosphite compound represented by the general formula (I), a triphenyl phosphate compound represented by the general formula ( ⁇ ), and a general formula (
  • the diphosphonite compounds represented by III) or alkaline earth metal salts of phosphoric acid (particularly calcium salts) are preferred.
  • I 1 and R 2 are selected from an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkoxy group. They may be the same or different.
  • R ′ and R 2 are preferably an alkyl group having 6 or more carbon atoms, a substituted alkyl group, an alkoxy group, or an aryl group or a substituted aryl group from the viewpoint of stability during processing. Particularly preferred is when R 1 R 2 is an aryl group or a substituted aryl group.
  • Examples thereof include a phenyl group, a naphthyl group, a diphenyl group and the like, or an alkyl, hydroxy and Z- or alkoxy-substituted product thereof.
  • An example of a specific compound is bis (2,4-di-tert-butylphenyl) pentaerythri] diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (Nonylphenyl) pentayl erythritol diphosphite, 4-phenoxy-19-a- (4-hydroxyphenyl) -1-p-cumenyloxy 3,5,8,10-tetraoxa4,9-diphosphaspiro [5.5] didecane And the like.
  • R 3 and R 4 are lower alkyl groups having 1 to 4 carbon atoms, and may be the same or different. good. Examples of specific compounds include triphenyl phosphate, tris (2,4-di-t-butylphenyl) phosphate, tris (2-t-butyl-1-methylphenyl) phosphate, and tris (2-t-t-phenyl).
  • RR 6 , R 7 , and R 8 are selected from an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkoxy group, each of which is the same. Or different.
  • R 5 , R 6 , R 7 and R 8 are preferably an alkyl group having 6 or more carbon atoms, a substituted alkyl group or an alkoxy group, or an aryl group or a substituted aryl group, from the viewpoint of stability during processing. Particularly preferred is a case where R 5 and RRR 8 are an aryl group or a substituted aryl group.
  • R 9 is a group selected from an alkylene group, a substituted alkylene group, an arylene group, and a substituted arylene group. Among them, preferred is a case where R 9 is an arylene group or a substituted arylene group. Examples thereof include a phenylene group, a naphthalene group, a biphenylene group, and a phenylene group. Or an alkyl, hydroxy, and Z or alkoxy substituent thereof. As an example of a specific compound, tetrakis (2,4-di-tert-butylphenyl) -14,4′-biphenylenediphosphonite is a typical example.
  • fluoropolymers examples include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylennohexafluoropropylene) copolymer, and tetrafluoroethylene Z perfluoropolymer.
  • Such polytetrafluoroethylene can be produced by known methods such as emulsion polymerization and suspension polymerization, and is widely marketed.
  • the polytetrafluoroethylene resin can be selected to have any degree of polymerization (viscosity) according to the purpose, such as dispersibility, processability of the composition, and other physical properties.
  • any shape can be used, from powdery and granular to fibrous, and the particle size can be adjusted over a wide range from 0.05 m to several mm.
  • the appropriate properties and particle size may be selected by experiments depending on the properties, desired properties, and effects.However, in terms of ease of handling in the process of preparing the composition, workability, productivity, etc., the average is used.
  • Granular particles having a particle size of 20 to 800 Hm, more preferably 100 to 00 m are preferred.
  • the amount of the component (E) added is preferably 0.1 to 10% by weight, more preferably 0.2 to 0.8% by weight, based on the total amount of the composition.
  • the fibrous filler By blending the fibrous filler within a range that does not deviate from the object of the present invention, the use can be further expanded.
  • the fibrous filler that can be used include glass fiber, carbon fiber, potassium titanate fiber, stainless fiber, steel fiber, and ceramic fiber. By adding these fillers, heat resistance and rigidity can be improved, and dimensional stability of a molded product can be achieved.
  • glass fibers are preferably used.
  • the type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, it can be selected from long fiber type or short fiber type chopped strand, milled fiber and the like.
  • the glass fibers may be coated or bundled with a thermoplastic resin such as ethylene-vinyl acetate copolymer or a thermosetting resin such as an epoxy resin. —It may be treated with a coupling agent such as a methacrylate or other surface treatment agents.
  • the amount of the fibrous filler to be added is preferably 5 to 40% by weight, more preferably 10 to 30% by weight in the composition. If it exceeds 40% by weight, the heat shock properties will deteriorate.
  • thermoplastic resins that is, stabilizers such as antioxidants, heat stabilizers, and ultraviolet absorbers
  • stabilizers such as antioxidants, heat stabilizers, and ultraviolet absorbers
  • an antistatic agent a coloring agent such as a dye or a pigment, a lubricant, a plasticizer, a crystallization accelerator, a nucleating agent, and an inorganic filler other than the fibrous filler.
  • Inorganic fillers include calcium carbonate, highly dispersible silicates, alumina, aluminum hydroxide, talc, clay, mai, glass flakes, glass powder, glass beads, quartz powder, silica sand, wollastonite, carbon black, sulfuric acid It includes powdery and granular materials such as barium, plaster of Paris, silicon carbide, alumina, boron nitrite and silicon nitride, plate-like inorganic compounds, whiskers and the like. These inorganic fillers can be used alone or in combination of two or more as necessary.
  • thermoplastic resin in the resin composition of the present invention, it is possible to use a small amount of another thermoplastic resin in a supplementary manner as long as its purpose is not hindered.
  • Any other thermoplastic resin may be used as long as it is stable at high temperatures.
  • polyamide, ABS, polyphenylene oxide, polyalkyl acrylate, polyether, polysulfone, polyether sulfone, polyether imide, polyether ketone and the like can be mentioned.
  • thermoplastic resins can be used as a mixture of two or more kinds.
  • an epoxy compound can be further added for the purpose of imparting excellent hydrolysis resistance.
  • an oligomer type and a phenol nopolak type based on bisphenol are preferably used.
  • the addition amount is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less based on 100 parts by weight of the total of (A) and (B). Exceeding 10 parts by weight adversely affects heat shock resistance. You.
  • the composition of the present invention is prepared by known equipment and methods generally used as a conventional resin composition preparation method. That is, after mixing each component of (A) polybutylene terephthalate, (B) polycarbonate, (C) red phosphorus and (E) preferably (D) a phosphorus compound, the mixture is kneaded and extruded by an extruder to form pellets.
  • the method include a method of preparing, and a method of preparing a Z or a pellet having a different composition once, mixing the pellet in a predetermined amount, subjecting the mixture to molding, and obtaining a molded article having a desired composition after molding.
  • red phosphorus induces the transesterification reaction between (A) polybutylene terephthalate and (B) polycarbonate, and the melt viscosity becomes unstable, Since physical properties may be deteriorated, (A) a part of polybutylene terephthalate, a master batch in which (C) 20% by weight or more of red phosphorus is kneaded in advance, (A) polybutylene terephthalate, It is preferably produced by a master batch method in which B) polycarbonate, E) preferably (D) a phosphorus compound is melt-kneaded.
  • melt-knead (A) polybutylene terephthalate with (A) a polybutylene terephthalate, which is previously kneaded with (C) red phosphorus in (B) polycarbonate, because it is not so effective in improving flame retardancy. Absent.
  • the excellent flame-retardant resin composition comprising red phosphorus, polybutylene terephthalate, polycarbonate and phosphorus-based compound without using a halogen-based flame retardant as in the present invention can be used for combustion.
  • This is an extremely preferable molding resin composition that does not have the problem of toxic gas generation and environmental destruction when subjected to heat, and does not impair the flame retardancy and mechanical properties even under severe temperature conditions. Therefore, the composition of the present invention is suitably used for precision structural parts and mechanical parts that require flame retardancy in electrical equipment, automobiles, other general equipment, and the like. Extremely preferred as a material Things. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
  • the physical property evaluation methods shown in the following examples are as follows. •Flame retardance
  • Notched Izod impact strength was measured according to ASTM D-256.
  • the crystallization temperature at the time of initial melting and the crystallization temperature at the time of repetition of melting and solidification were determined, and the crystallization peak temperature difference ( ⁇ ) at the time of repetition was measured.
  • HDT -Heat deformation temperature

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine retardatrice de combustion qui renferme (A) du polybutylène téréphtalate, (B) un polycarbonate, (C) du phosphore rouge et (E) un fluoropolymère, et qui contient éventuellement (D) un composé de phosphore. La composition est exempte de substance halogénée retardatrice de combustion, et présente d'excellentes caractéristiques mécaniques et retardatrices de combustion.
PCT/JP1998/005256 1997-11-20 1998-11-20 Composition de resine retardatrice de combustion WO1999027016A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP31960097 1997-11-20
JP9/319600 1997-11-20
JP10/166953 1998-06-15
JP16695398 1998-06-15

Publications (1)

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WO1999027016A1 true WO1999027016A1 (fr) 1999-06-03

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0994155A3 (fr) * 1998-09-29 2000-04-26 Idemitsu Petrochemical Co., Ltd. Composition de résine de polycarbonate ignifugée et ses pièces moulées par injection
JP2002060597A (ja) * 2000-08-11 2002-02-26 Toray Ind Inc 難燃性ポリブチレンテレフタレート樹脂組成物および成形品
US6649674B2 (en) 2001-06-27 2003-11-18 Bayer Aktiengesellschaft Flame-proof polyester molding compositions comprising hydrotalcite, red phosphorus and melamine cyanurate

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JPS50136341A (fr) * 1974-04-06 1975-10-29
JPS5883051A (ja) * 1981-10-28 1983-05-18 チバ−ガイギ−・アクチエンゲゼルシヤフト 熱可塑性成形用組成物及びその用途
JPS63265949A (ja) * 1987-04-24 1988-11-02 Adeka Argus Chem Co Ltd ポリエステル・ポリマ−ブレンド組成物
JPS63291947A (ja) * 1987-04-24 1988-11-29 ビーエーエスエフ　アクチェンゲゼルシャフト 防火加工した熱可塑性成形材料及びその製法
JPH0292961A (ja) * 1988-08-25 1990-04-03 Dow Chem Co:The 抗着火性改質熱可塑性組成物及び製造方法
JPH04132763A (ja) * 1990-09-21 1992-05-07 Polyplastics Co 熱可塑性ポリエステル樹脂組成物
JPH07133412A (ja) * 1993-11-09 1995-05-23 Kuraray Co Ltd 難燃性ポリブチレンテレフタレート系樹脂組成物およびその製造方法
JPH08295796A (ja) * 1995-04-26 1996-11-12 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
JPH08325449A (ja) * 1995-06-01 1996-12-10 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
JPH0959502A (ja) * 1995-08-21 1997-03-04 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
JPH10114856A (ja) * 1996-10-11 1998-05-06 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物
JPH10130510A (ja) * 1996-10-28 1998-05-19 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物
JPH10168295A (ja) * 1996-12-13 1998-06-23 Kanegafuchi Chem Ind Co Ltd 難燃性樹脂組成物
JPH10168297A (ja) * 1996-12-16 1998-06-23 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50136341A (fr) * 1974-04-06 1975-10-29
JPS5883051A (ja) * 1981-10-28 1983-05-18 チバ−ガイギ−・アクチエンゲゼルシヤフト 熱可塑性成形用組成物及びその用途
JPS63265949A (ja) * 1987-04-24 1988-11-02 Adeka Argus Chem Co Ltd ポリエステル・ポリマ−ブレンド組成物
JPS63291947A (ja) * 1987-04-24 1988-11-29 ビーエーエスエフ　アクチェンゲゼルシャフト 防火加工した熱可塑性成形材料及びその製法
JPH0292961A (ja) * 1988-08-25 1990-04-03 Dow Chem Co:The 抗着火性改質熱可塑性組成物及び製造方法
JPH04132763A (ja) * 1990-09-21 1992-05-07 Polyplastics Co 熱可塑性ポリエステル樹脂組成物
JPH07133412A (ja) * 1993-11-09 1995-05-23 Kuraray Co Ltd 難燃性ポリブチレンテレフタレート系樹脂組成物およびその製造方法
JPH08295796A (ja) * 1995-04-26 1996-11-12 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
JPH08325449A (ja) * 1995-06-01 1996-12-10 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
JPH0959502A (ja) * 1995-08-21 1997-03-04 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
JPH10114856A (ja) * 1996-10-11 1998-05-06 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物
JPH10130510A (ja) * 1996-10-28 1998-05-19 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物
JPH10168295A (ja) * 1996-12-13 1998-06-23 Kanegafuchi Chem Ind Co Ltd 難燃性樹脂組成物
JPH10168297A (ja) * 1996-12-16 1998-06-23 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0994155A3 (fr) * 1998-09-29 2000-04-26 Idemitsu Petrochemical Co., Ltd. Composition de résine de polycarbonate ignifugée et ses pièces moulées par injection
US6331584B1 (en) 1998-09-29 2001-12-18 Idemitsu Petrochemical Co., Ltd. Flame-retardant polycarbonate resin composition and its injection moldings
JP2002060597A (ja) * 2000-08-11 2002-02-26 Toray Ind Inc 難燃性ポリブチレンテレフタレート樹脂組成物および成形品
US6649674B2 (en) 2001-06-27 2003-11-18 Bayer Aktiengesellschaft Flame-proof polyester molding compositions comprising hydrotalcite, red phosphorus and melamine cyanurate

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