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WO2003018692A1 - Composition de resine organique ignifuge - Google Patents

Composition de resine organique ignifuge Download PDF

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Publication number
WO2003018692A1
WO2003018692A1 PCT/JP2002/008698 JP0208698W WO03018692A1 WO 2003018692 A1 WO2003018692 A1 WO 2003018692A1 JP 0208698 W JP0208698 W JP 0208698W WO 03018692 A1 WO03018692 A1 WO 03018692A1
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Prior art keywords
group
flame retardant
resin composition
organic resin
component
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PCT/JP2002/008698
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English (en)
Inventor
Koji Nakanishi
Hidekatsu Hatanaka
Haruhiko Furukawa
Koji Shiromoto
Hiroshi Ueki
Yoshitsugu Morita
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DuPont Toray Specialty Materials KK
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Dow Corning Toray Silicone Co Ltd
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Publication of WO2003018692A1 publication Critical patent/WO2003018692A1/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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to a flame retardant organic resin composition
  • a flame retardant organic resin composition comprising an organic resin with an aromatic ring, a branched organopolysiloxane, and an organopolysiloxane selected from a diorganopolysiloxane and an organopolysiloxane containing an epoxy group.
  • Organic resins with an aromatic ring such as an aromatic polycarbonate, are characterized by high mechanical strengths in combination with excellent electrical characteristics. Therefore, these resins find wide application in the manufacture of parts for office automation machines, automobiles, construction, and road building equipment. It has been known heretofore to impart flame retardant properties to organic resins that contain aromatic rings by mixing these resins with compounds containing chlorine or bromine atoms.
  • Kokai H10-139964 discloses a polycarbonate composition obtained by combining an aromatic polycarbonate resin with a high-molecular- weight silicone resin that comprising bi-functional siloxane units (D units) and tri-functional siloxane units (T-units) and has a weight-average molecular weight exceeding 10,000. Nevertheless, the Kokai HlO-139964 composition also possesses poor moldability and has insufficient flame retardant properties. In addition, it cannot be easily produced.
  • Kokai HI 1-140294 describes a flame retardant polycarbonate resin composition prepared by combining an aromatic polycarbonate with a silicone resin having more than 80 mole % of phenyl groups
  • Kokai HI 1-222559 discloses a flame retardant polycarbonate resin composition prepared by combining silicone resins with phenyl and alkoxy groups.
  • the above compositions have insufficient flame retardant properties, and also are unsatisfactory in use.
  • Kokai HI 1-140329 describes a flame retardant polycarbonate resin composition prepared from a silica powder admixed with an aromatic polycarbonate resin and a silicone resin that contains phenyl groups and alkoxy groups.
  • the Kokai HI 1-140329 compositions are disadvantageous in requiring the use of a silica powder and therefore is difficult in production.
  • the present inventors have found that flame retardant properties of organic resins with aromatic rings, such as aromatic polycarbonate resins, can be improved by combining them with certain organopolysiloxanes and a branched organopolysiloxane.
  • the present invention provides a flame retardant organic resin composition comprising:
  • R 1 3SiO 1 / 2 a (R 2 2 SiO 2 / 2 ) b (R 3 SiO 3/2 ) c (SiO 4 / 2 ) d (R 4 O 1/2 )e(HO 1/2 ) f
  • R 1 , R 2 , R 3 are independently monovalent hydrocarbon groups selected from an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms
  • R 4 is an alkyl group, the content of aryl groups in R being within the limits of 20 to 100 mole%
  • a, b, d, e,f are 0 or positive numbers
  • c is a positive number greater than zero
  • Component (A) is an organic resin that contains an aromatic ring.
  • resins such as an aromatic polycarbonate resin or its alloy; a polyphenylene ether resin or its alloy; a polysulfone resin; a polyarylate resin, polyethyleneterephthalate resin, polybutyleneterephthalate resin, or a similar aromatic polyester resin; an aromatic polyamide resin; a polyimide resin; a polyphenylenesulfide resin; a polystyrene resin, high-impact-resistant polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, or a similar styrene-type resin; or thermosetting resins such as a novolac-type epoxy resin.
  • the organic resin is a aromatic polycarbonate resin and related alloys.
  • Component (B) is a branched organopolysiloxane represented by the following average molecular formula:
  • R 1 3 SiO 1/2 a (R 2 2 SiO 2/2 ) b (R 3 SiO 3/2 ) c (SiO 4/2 ) d (R 4 O 1/2 ) e (HO 1/2 ) f
  • R 1 , R 2 , R 3 are monovalent hydrocarbon groups selected from an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms
  • R 4 is an alkyl group, the content of aryl groups in R 3 being within the limits of 20 to 100 mole%
  • a, b, d, e,f are 0 or positive numbers
  • c is a positive number greater than 0.
  • Component (B) may contain in one molecule tri-functional siloxane units (T- units) represented by the following formula: R S ⁇ O 3/2 , and, if necessary, monofunctional siloxane units (M-units) of formula R 1 3 SiO 1/2 and bifunctional siloxane units (D-units) of formula R 2 SiO 2/2 . If necessary, in addition to the aforementioned groups and within the limits not conflicting with the purposes of the present invention, component (B) may contain quatrofunctional units (Q-units) of formula SiO 4/2 .
  • T- units tri-functional siloxane units represented by the following formula: R S ⁇ O 3/2 , and, if necessary, monofunctional siloxane units (M-units) of formula R 1 3 SiO 1/2 and bifunctional siloxane units (D-units) of formula R 2 SiO 2/2 . If necessary, in addition to the aforementioned groups and within the limits not conflicting with the purposes of the present invention, component (B) may contain quatr
  • Component (B) may also preferably comprise a branched organopolysiloxane represented by the following average molecular formula: (R 2 2 SiO 2/2 ) b (R 3 SiO 3/2 ) c (SiO 4 / 2 ) d (R 4 O 1/2 ) e (HO 1/2 ) f (where R 2 , R 3 , R 4 , b, c, d, e, and f are the same as defined above), a branched organopolysiloxane represented by the following average molecular formula :
  • R 1 , R 2 , R 3 can be exemplified by methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, or similar alkyl groups; vinyl group, butenyl group, pentenyl group, hexenyl group, or similar alkenyl groups; phenyl group, tolyl group, xylyl group, naphthyl group, or similar aryl groups.
  • R 3 should contain aryl groups in an amount from 20 to 100 mole %, alternatively from 50 to 100 mole%, or alternatively from 70 to 100 mole %.
  • aryl groups of R 3 comprise phenyl groups.
  • R 3 comprises a phenyl group
  • their content should be within the range of 70 mole % to 100 mole %.
  • the amount of phenyl groups in all substituents typically this amount is within the range of 20 to 100 mole %, or alternatively 50 to 100 mole %.
  • the amount of phenyl groups in R 3 should be no less than 90 mole %.
  • Component (B) may contain silicon-bonded hydroxyl groups. Such groups may be contained in an amount of 0 to 8 wt.%, preferably in an amount of 1 to 7 wt.%. Component (B) may also contain silicon-bonded methoxy, et oxy, n-propoxy, isopropoxy, butoxy, or similar alkoxy groups with 1 to 12 carbon atoms. It is recommended for component (B) to have a weight-average molecular weight between 300 and 10,000. If the weight-average molecular weight of component (B) exceeds 10,000, the composition of the present invention will have poor moldability, pose problems during synthesis. Normally, the weight-average molecular weight is determined by gel permeation chromatography (GPC). [0012] Preferably, typical examples of component (B) are branched organopolysiloxane represented by the following average molecular formula :
  • Component (B) can be used in an amount of 0.01 to 20 parts by weight, alternatively 0.1 to 20 parts by weight, or alternatively 0.1 to lO parts by weight for each 100 parts by weight of component (A).
  • Component (C) is an organopolysiloxane selected from a diorganopolysiloxane and an organopolysiloxane that contains an epoxy group.
  • the diorganopolysiloxane can be preferably represented by the following average molecular formula: R 5 3 -SiO(R 6 2 SiO) n -SiR 5 3
  • R 5 is a substituted group selected from a monovalent hydrocarbon group, an alkoxy group, and a hydroxyl group
  • R 6 is a monovalent hydrocarbon group
  • n is a number which results in a viscosity which at 25°C is within the range of 10 to 1,000,000 mPa-s.
  • the monovalent hydrocarbon group of R5 can be exemplified by methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, or similar alkyl groups; vinyl group, allyl group, butenyl group, pentenyl group, hexenyl or similar alkenyl groups; phenyl group, tolyl group, xylyl group, naphthyl group or similar aryl groups; benzyl group, phenethyl group, or similar aralkyl groups.
  • the alkoxy groups can be represented by methoxy group, ethoxy group, n-propyl group, isopropyl group, and butoxy group.
  • the monovalent hydrocarbon of R may be exemplified by methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, or similar alkyl groups; vinyl group, allyl group, butenyl group, pentenyl group, hexenyl or similar alkenyl groups; phenyl group, tolyl group, xylyl group, naphthyl group or similar aryl groups; benzyl group, phenethyl group, or similar aralkyl groups.
  • methyl groups constitute 50 mole % or more, alternatively 70 mole % or more, or alternatively 90 mole % or more of R 6 .
  • the number n is such to provide the diorganopolysiloxanes with a viscosity within the range of 10 to 1,000,000 mPa-s, alternatively between 20 and 100,000 mPa-s at 25°C.
  • An appropriate diorganopolysiloxane may be represented by a dimethylpolysiloxane having both molecular terminals capped with trimethylsiloxy groups, a dimethylpolysiloxane having one molecular terminal capped with a trimethylsiloxy group and the other molecular terminal capped with a hydroxyl group, a dimethylpolysiloxane having one molecular terminal capped with a trimethylsiloxy group and the other molecular terminal capped with a methoxy group, a dimethylpolysiloxane having one molecular terminal capped with a trimethylsiloxy group and the other molecular terminal capped with a dimethylvinylsiloxy group, a dimethylpolysiloxane having both molecular terminals capped with hydroxyl groups, a dimethylpolysiloxane having both molecular terminals capped with methoxy groups, a dimethyl polysiloxane having both molecular
  • the silicon-bonded organic groups contained in the diorganopolysiloxane of component (C) are typically unsubstituted monovalent hydrocarbon groups.
  • the aforementioned monovalent hydrocarbon groups can be used in combination with a small amount of hydroxyl groups, alkoxy groups, or substituted monovalent hydrocarbons such as ⁇ -aminopropyl group, ⁇ - methacryloxypropyl group, or a similar acryl-substituted alkyl group; a ⁇ - polyoxyethylenepropyl group, or a similar polyoxyethylene-substituted alkyl group, ester- substituted alkyl group, etc..
  • a diorganopolysiloxane is used as component (C), it is typically used in an amount of 0.01 to 5 parts by weight, alternatively 0.05 to 2 parts by weight, or alternatively, 0.1 to 1 parts by weight for each 100 parts by weight of component (A). If the diorganopolysiloxane is used in an amount smaller than 0.01 parts by weight, it would be impossible to impart to the obtained thermoplastic resin composition the desired flame retardant properties. If, on the other hand, the diorganopolysiloxanes is used in an amount exceeding 5 parts by weight, the products molded from the composition of the present invention will have a reduced mechanical strength.
  • Component (C) can also be an organopolysiloxane containing an epoxy group.
  • the aforementioned epoxy group is connected to a silicon atom of the organopolysiloxane through a divalent hydrocarbon group.
  • epoxy-group-containing organic groups 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4- glycidoxybutyl group, 2-(3,4-epoxycyclohexyl) ethyl group, and 3-(3,4-epoxycyclohexyl) propyl group.
  • the organopolysiloxane containing an epoxy group can also contain other organic groups such as the following non-limiting examples: methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, or a similar alkyl group; vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, or a similar alkenyl group; phenyl group, tolyl group, xylyl group, naphthyl group, or a similar aryl group; benzyl group, phenethyl group, or a similar aralkyl group; chloromethyl group, 3-chloropropyl group, 3,3,3- trifluoropropyl group, nonafluorobutylethyl group, or a similar halogen-substituted alkyl group.
  • organic groups such as the following non-limiting examples: methyl group, e
  • the organopolysiloxane of component (C) may have a linear, branched, net-like, or ring-like molecular structure, but typically is a linear molecular structure.
  • component (C) has a weight-average molecular weight between 100 and 100,000, alternatively between 300 and 20,000.
  • Typical examples of organopolysiloxanes containing an epoxy group suitable for component (C) are compounds represented by the following general formulae (1) and (2), where /, m, and n are positive numbers:
  • the amount of epoxy groups contained in the organopolysiloxane of component (C) can be within the range of 0.01 to 60 mole %, alternatively between 0.1 and 15 mole % with respect to the amount of all silicon-bonded organic groups. If the amount of epoxy groups exceeds 60 mole %, the obtained organic resin composition would have low flowability and reduced moldability.
  • the organopolysiloxane containing an epoxy group is used as component (C), it can be used in an amount of 0.01 to 4 parts by weight for each 100 parts by weight of component (A).
  • the composition of the invention is prepared from components (A) through (C).
  • the composition may also be combined with component (D) in the form of an alkali-metal salt of an organic acid or an organic acid ester.
  • An organic acid suitable for component (D) may comprise an organic sulfonic acid, or an organic carboxylic acid.
  • An example of an organic acid ester is an organic phosphoric acid ester.
  • An alkali metal may comprise sodium, potassium, lithium, and cesium. Examples of alkali-earth metals are magnesium, calcium, strontium, and barium.
  • component (D) is selected from the above metal salts of an organic sulfonic acid, as well as metal salts of a perfluoroalkanesulfonic acid and aromatic sulfonesulfonic acid.
  • metals salts of a perfluoroalkanesulfonic acid a sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium perfluoromethylbutanesulfonate, potassium perfluoromethylbutanesulfonate, sodium perfluorooctanesulfonate, potassium perfluorooctanesulfonate, etc.
  • metals salts of an aromatic sulfonesulfonic acid a sodium salt of a diphenylsulfone-3-sulfonic acid, a potassium salt of a diphenylsulfone-3-sulfonic acid, a sodium salt of 4,4-dibromodiphenylsulfone-3- sulfonic acid, a potassium salt of 4,4-dibromodiphenylsulfone-3 -sulfonic acid, a disodium salt of diphenylsulfone-3,3-disulfonic acid, a dipotassium salt of diphenylsulfone-3,3-disulfonic acid, etc.
  • component (D) can be used in an amount of 0.01 to 1 wt.% for each 100 parts by weight of component (A).
  • component (E) typically a fluororesin, for improving the flame retardant properties of the composition.
  • the fluororesin is in a powdered form such as a fluorinated ethylene resin (a monomer having a hydrogen atom of the ethylene substituted by a fluorine atom, e.g., a tetrafluoro ethylene resin powder), trifluoroethylene resin, tetrafluoroethylene hexaethylenepropylene resin, fluorovinyl resin, fluorovinylidene resin, and a difluorinated ethylene dichloride resin.
  • a fluorinated ethylene resin a monomer having a hydrogen atom of the ethylene substituted by a fluorine atom, e.g., a tetrafluoro ethylene resin powder
  • trifluoroethylene resin tetrafluoroethylene hexaethylenepropylene resin
  • fluorovinyl resin fluorovinylidene resin
  • difluorinated ethylene dichloride resin a difluorinated ethylene dichloride resin.
  • composition of the invention can be further combined with conventional additives normally added to (A) organic resin containing an aromatic ring.
  • additives can be: glass fibers, glass beads, glass flakes, carbon black, calcium sulfate, calcium carbonate, calcium silicate, titanium oxide, alumina, silica, asbestos, talc, mica, quartz, or a similar inorganic filler; various synthetic resins, elastomers, or similar organic resin additives; hindered-phenol-type oxidation inhibitors, zinc phosphoric acid ester-type oxidation inhibitors, phosphoric acid ester-type oxidation inhibitors, amine-type oxidation inhibitors, or similar oxidation inhibitors; aliphatic carboxylic acid esters; paraffin, polyethylene wax, or a similar lubricant; organic or inorganic pigments or coloring agents; benzotriazol-type ultraviolet ray absorbers, benzophenone-type ultraviolet ray absorbers, or similar ultraviolet ray absorbers; hindered-amine-type light
  • composition of the invention is easily prepared by uniformly mixing components (A) through (C), or (A) through (D), or (A) through (E).
  • Mixing can be carried out with the use of a ribbon blender, Henschel mixer, B anbury mixer, drum tumbler, single- screw extruder, twin-screw extruder, kneader, multiple-axle screw extruder, etc.
  • Mixing can be carried out with heating to a temperature of 200 to 350°C.
  • composition of the invention possesses excellent moldability and flame retardant properties. Due to its properties, the composition of the invention is suitable as a material for manufacturing parts for domestic electrical appliances, housing for automobile interiors, electric and electronic devices, etc. [0027] The invention will be further described in detail with reference to the ensuing practical and reference examples. In these examples, flame retardant properties of the aromatic polycarbonate resin compositions were measured in accordance with JIS-K7201 "Non-Flammability Test of Plastics Based on Oxygen Index".
  • Another criterion for evaluation of flame retardant properties which was used in the examples was a flame-resistance criterion specified by UL94 Test (Underwriter Laboratory Test for Flammability of Plastic Materials for Parts In Devices and Appliances).
  • the UL-94 Test consists of evaluating flame retardant properties in terms of flame duration and drips of flaming particles after 10 sec. burner flame application to a vertically held specimen of a predetermined size. The ratings were classified as follows:
  • the aforementioned flame duration was measured as duration of flame after removal of the burning source from the specimen, while flame dripping was evaluated by observing whether specimen drips flaming particles to ignite the cotton located at a distance of about 300 mm from the lower end of the specimen.
  • the specimen used in this test had a thickness of 3 mm.
  • MI value melt index
  • Reference Example 1 and Reference Example 2 and branched organopolysiloxanes (SNR3, SNR4, SNR5, and SNR6) used in Reference Examples 3 to 6 were expressed by average molecular formulae shown in Table 1 and had characteristics shown in Table 2.
  • R designates ⁇ -glycidoxypropyl group
  • Me designates methyl group
  • Pr designates propyl group
  • Ph designates phenyl group.
  • Chemical structure analysis of the branched organopolysiloxanes used in the practical examples was carried out with the use of nuclear magnetic resonance (NMR) spectra.
  • a weight-average molecular weight was measured with the use of gel permeation chromatography (GPC). The obtained values of the weight-average molecular weight were recalculated to molecular weight of a known polystyrene used as a reference.
  • a 1 liter 4-neck flask equipped with a stirrer, cooler, dripping funnel, and thermometer was filled with 300 g of a dimethylpolysiloxane having on both molecular terminals silicon-bonded hydrogen atoms (60 dimethylsiloxane units), 150 g of toluene, and 16 g of an allylglycidyl ether.
  • An isopropanol solution of a chloroplatinic acid was then added by dripping in a catalytic quantity.
  • a saturated aqueous solution of sodium bicarbonate was added in an amount sufficient for neutralization of the acid. The mixture was then stirred with heating, and a reaction was carried out.
  • a 1 liter 4-neck flask equipped with a stirrer, cooler, dripping funnel, and thermometer was filled with 200 g of a copolymer of a methylhydrogensiloxane and a dimethylsiloxane having both molecular terminals capped with trimethylsiloxy groups (120 dimethylsiloxane units and 174 methylhydrogensiloxane units), 100 g of toluene, and 205 g of allylglycidyl ether.
  • An isopropanol solution of chloroplatinic acid was then added by dripping in a catalytic quantity.
  • a saturated aqueous solution of sodium bicarbonate was added in an amount sufficient for neutralization of the acid.
  • the mixture was then stirred with heating, and a reaction was carried out. Upon completion of the reaction, the solvent was removed by distillation, a non-dissolved residue was removed by filtering, and an epoxy- containing organopolysiloxane as component (C) was produced.
  • the obtained epoxy- containing organopolysiloxane (hereinafter referred to as SNR2) was analyzed. The result of the analysis showed a substance with an average structural formula given below. The weight- average molecular weight of the product was 39000, and an epoxy equivalent was 230.
  • the obtained branched organopolysiloxane (hereinafter referred to as SNR3) contained 70 mole % of PhSiO /2 units and 30 mole % of C 3 H 7 SiO 3/2 units. Content of hydroxyl groups was 6.0 wt.%, and the weight- average molecular weight was equal to 1,600.
  • a 1 liter 4-neck flask equipped with a stirrer, cooler, dripping funnel, and thermometer was filled with 110 g of toluene, 40g of methylethylketone, and 40 g of water. While the flask was cooled on an ice bath, a mixed solution containing 114.8 g of phenyltrichlorosilane, 17.5 g of dimethyldichlorosilane, and 40 g of toluene were added via a dripping funnel. Upon completion of dripping, the mixture was stirred for 30 min. at room temperature, and then for lhour was subjected to refluxing for completion of hydrolysis.
  • the obtained branched organopolysiloxane (hereinafter referred to as SNR4) contained 80 mole % of PhSiO /2 units and 20 mole % of Me 2 SiO 2/ units. Content of hydroxyl groups on the molecular terminals was 3.4 wt.%, and the weight-average molecular weight was equal to 4000.
  • a 1 liter 4-neck flask equipped with a stirrer, cooler, dripping funnel, and thermometer was filled with 90 g of toluene and 430 g of water. After heating to 80°C, a mixed solution consisting of 169 g of phenyltrichlorosilane and 26 g of dimethyldichlorosilane was added via a dripping funnel. The product was subjected to lhour refluxing for completion of hydrolysis. After cooling, the solution was kept intact, and an aqueous layer was removed. For washing the product, addition of water, stirring, retention in a static state, and removal of the aqueous layer were repeated three times.
  • the obtained organopolysiloxane solution was filtered, the non-solved residue was removed, and the product was dried. As a result, a solid organopolysiloxane as component (B) was obtained.
  • the obtained branched organopolysiloxane (hereinafter referred to as SNR5) contained 80 mole % of PhSiO 3/2 units and 20 mole % of Me SiO 2/ units. Content of hydroxyl groups on the molecular terminals was 1.7 wt.%, and the weight-average molecular weight was equal to
  • Flame retardant polycarbonate resin compositions were prepare by mixing the components given below in proportions shown in Tables 3 and 4: component (A) in the form of an organic resin with an aromatic ring (Toughlon A1900 of Idemitsu Petrochemical Co., Ltd.); component (C) in the form of epoxy-containing organopolysiloxanes SNR1 and SNR2 shown in Tables 1 and 2; component (B) in the form of branched organopolysiloxanes SNR3 and SNR4 to shown in Tables 1 and 2; component (D) in the form of sodium trichlorobenzenesulfonate; and component (E) in the form of a perfluoroethylene powder (Polyfuron MPA, FA-500 of Daikin Industries Co., Ltd.).
  • component (A) in the form of an organic resin with an aromatic ring
  • compositions were prepared as follows: an aromatic polycarbonate resin was loaded into a mixer ("Laboplastomill", Toyo Seiki Co., Ltd.) and melted by heating to 280-320°C. Branched organopolysiloxanes were loaded, mixed, and kneaded. In Practical Example 5, a fluororesin powder was added and kneaded. In Practical Examples 6 and 7, sodium trichlorobenzensulfonate was also added and kneaded. The obtained flame retardant polycarbonate resin compositions were tested with regard to their moldability (in terms of their melt index MI). [0039] The obtained compositions were then used for injection molding at 280 to 320°C. The molded articles were measured with regard to their oxygen index and transparency. The results of these measurements are given in Tables 3 and 4 below. Comparative Examples 1 to 8
  • compositions of these examples were prepared by using component (A) in the form of an aromatic polycarbonate resin (the product of Idemitsu Petrochemical Co., Ltd., trademark "Tafuron A1900") or a polycarbonate- ABS (acrylonitrile-butadiene-styrene copolymer) resin alloy (the product of Teijin Chemical Ltd., trademark "Multilon T3011”).
  • component (B) comprised branched organopolysiloxanes SNR3, SNR4, and SNR5 of Reference Examples 3 through 5.
  • Component (C) was represented by a polydimethylsiloxane (hereinafter referred to as SNR7) having both molecular terminals capped with trimethylsiloxy groups and having a 25°C viscosity of 12500 mPa-s or a dimethylpolysiloxane (hereinafter referred to as SNR8) having both molecular terminals capped with trimethylsiloxy groups and having a 25°C viscosity of 100 mPa-s.
  • Component (D) was represented by a sodium perfluorobutane sulfonate (the product of Dainippon Ink and Chemicals, Co., Ltd. trademark "Megafac FI 14".
  • Component (E) was represented by a fluororesin powder (a perfluoroethylene resin produced by Daikin Industries Co., Ltd. under trademark Polyfureon MPA, FA-500.
  • Flame retardant polycarbonate resin compositions were prepared by mixing the aforementioned components in proportions shown in Tables 3 and 4 given below. The compositions were prepared as follows: the polycarbonate resin or a polycarbonate -ABS resin alloy was loaded into a mixer ("Laboplastomill", Toyo Seiki Seisakusho Co., Ltd.), where it was heated and fused at 280 to 320°C. The mixer was loaded with the branched organopolysiloxane and/or dimethylpolysiloxane. The components were then kneaded.
  • the kneaded composition further contained a sodium perfluorobutane sulfonate and/or fluororesin.
  • flame retardant polycarbonate resin compositions were prepared. The obtained compositions were tested with regard to their moldability (MI index). The compositions were subjected to injection molding at 280 to 320°C, and the molded articles were tested with regard to their flame retardant properties. The results of the tests are shown in Tables 6, 7, 8, and 9.

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Abstract

Composition de résine organique ignifuge contenant une résine organique possédant une chaîne aromatique, un organopolysiloxane ramifié et un organopolysiloxane sélectionné dans un diorganopolysiloxane et un organopolysiloxane contenant un groupe époxy.
PCT/JP2002/008698 2001-08-28 2002-08-28 Composition de resine organique ignifuge Ceased WO2003018692A1 (fr)

Applications Claiming Priority (4)

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JP2001258333 2001-08-28
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JP2001-347860 2001-11-13
JP2001347860 2001-11-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090253856A1 (en) * 2006-12-29 2009-10-08 Cheil Industries Inc. Polycarbonate-Polysiloxane Copolymer Resin Composition with High Impact Strength at Low Temperature and Mechanical Strength and Method for Preparing the Same
EP3211050A1 (fr) * 2016-02-26 2017-08-30 Trinseo Europe GmbH Structures moulées de substrats à base de polycarbonate surmoulées avec des caoutchoucs de silicone

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090253856A1 (en) * 2006-12-29 2009-10-08 Cheil Industries Inc. Polycarbonate-Polysiloxane Copolymer Resin Composition with High Impact Strength at Low Temperature and Mechanical Strength and Method for Preparing the Same
US8293839B2 (en) * 2006-12-29 2012-10-23 Cheil Industries Inc. Polycarbonate-polysiloxane copolymer resin composition with high impact strength at low temperature and mechanical strength and method for preparing the same
EP3211050A1 (fr) * 2016-02-26 2017-08-30 Trinseo Europe GmbH Structures moulées de substrats à base de polycarbonate surmoulées avec des caoutchoucs de silicone
WO2017144656A1 (fr) * 2016-02-26 2017-08-31 Trinseo Europe Gmbh Structures moulées de substrats à base de polycarbonate surmoulés par des caoutchoucs de silicone
CN109153881A (zh) * 2016-02-26 2019-01-04 盛禧奥欧洲有限责任公司 经硅橡胶包覆模制的聚碳酸酯基基材的模制结构
US20190031916A1 (en) * 2016-02-26 2019-01-31 Trinseo Europe Gmbh Molded Structures of Polycarbonate Based Substrates Over Molded with Silicone Rubbers
JP2019515812A (ja) * 2016-02-26 2019-06-13 トリンゼオ ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング シリコーンゴムでオーバーモールドされたポリカーボネート系基材の成型構造体
CN109153881B (zh) * 2016-02-26 2020-11-17 盛禧奥欧洲有限责任公司 经硅橡胶包覆模制的聚碳酸酯基基材的模制结构
US11208574B2 (en) 2016-02-26 2021-12-28 Trinseo Europe Gmbh Molded structures of polycarbonate based substrates over molded with silicone rubbers

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