[go: up one dir, main page]

WO2000046299A1 - Composition résinique de polycarbonates aromatiques - Google Patents

Composition résinique de polycarbonates aromatiques Download PDF

Info

Publication number
WO2000046299A1
WO2000046299A1 PCT/JP2000/000681 JP0000681W WO0046299A1 WO 2000046299 A1 WO2000046299 A1 WO 2000046299A1 JP 0000681 W JP0000681 W JP 0000681W WO 0046299 A1 WO0046299 A1 WO 0046299A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
polymer
aromatic
flame retardant
component
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2000/000681
Other languages
English (en)
Japanese (ja)
Inventor
Hajime Nishihara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
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 Asahi Chemical Industry Co Ltd, Asahi Kasei Kogyo KK filed Critical Asahi Chemical Industry Co Ltd
Priority to DE10080144T priority Critical patent/DE10080144T1/de
Publication of WO2000046299A1 publication Critical patent/WO2000046299A1/fr
Priority to US09/717,060 priority patent/US6790887B1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention provides (A) a resin mixture of an aromatic polycarbonate or an aromatic polycarbonate and at least one other organic polymer resin; Or a cyclic aromatic group-containing silicone compound, wherein the component (B) contains a specific amount of an aromatic group.
  • the polycarbonate resin composition of the present invention not only has excellent flame retardancy, but also has excellent melt fluidity and stability during melt molding (quality stability of molded articles). Furthermore, when the polycarbonate resin composition of the present invention is molded, a molded article having excellent mechanical properties, light resistance, and appearance can be obtained. Conventional technology
  • Polycarbonate is used in a wide range of fields, including automobile parts, home appliances parts, and ⁇ A equipment parts, because of its light weight and excellent impact resistance. Its use is limited. : As a method of making a resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic-based flame retardant to the resin, thereby achieving a certain degree of flame retardancy. . However, in recent years, the demand for fire safety has been greatly increased, and advanced flame retardant technology has been developed. In addition, environmental problems and mechanical properties of resin molded products have also been increased. There is a strong demand for technological development that does not lead to a decline.
  • Japanese Unexamined Patent Publication No. 63-41565 discloses a smoke suppressant comprising hydrocarbon, silicon and zinc borate, and is disclosed in U.S. Pat. No. 7,925,5 and U.S. Pat. Nos. 4,387,176 disclose a flame-retardant resin composition containing dimethyl silicone.
  • the silicones described in the above publications have a very low aromatic group content (less than 5 mol%).
  • a flame retardant containing silicone having a low aromatic group content is blended with an aromatic group-containing resin to form a resin composition, the silicone has low compatibility with the resin.
  • the resin composition is phase-separated, and therefore, when the resin composition is molded, there are problems such as a decrease in mechanical properties such as impact resistance of the resulting molded article, and there is room for improvement in practical use.
  • Japanese Patent Application Laid-Open No. 63-1662756 discloses a resin composition for the purpose of improving abrasion, comprising aromatic poly-carbonate, polyolefin and silicone fluid. I have. In this gazette The silicones described also have very low aromatics content.
  • the resin compositions disclosed in this publication are also disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 63-41565, and the above-mentioned U.S. Pat. Nos. 4,497,925 and U.S. Pat. There was a problem similar to that of Japanese Patent Publication No. 87,176.
  • Japanese Patent Application Laid-Open Nos. H10-139964 and H11-140294 describe flame retardant compositions containing branched and Z- or cross-linked methylphenylsilicone.
  • Aromatic polycarbonate] A resin composition is disclosed.
  • the above methylphenylsilicone has a branched structure and / or a crosslinked structure, so that it has low compatibility with aromatic polycarbonate-based resins, and thus has poor dispersibility in the resin composition. was there.
  • the aromatic polycarbonate resin composition disclosed in this publication has another problem such as inferior flame retardancy.
  • methylphenylsilicone which has no branched or cross-linked structure, used as oil for diffusion pumps or oils for high-temperature oil baths.
  • silicones have been combined with aromatic polycarbonates to excel. There is no report that a polycarbonate composition having both the above-mentioned flame retardancy and mechanical properties was obtained.
  • a composition of polyphenylene ether and phenylsiloxane JP-A-5-76080
  • the product flame retardant is a linear aromatic group-containing polyorganosiloxane, which uses polyphenylene ether as the power resin, and is inferior in impact strength and light resistance, and solves the problem of polycarbonate. It does not disclose any technology that does. Summary of the Invention
  • the present inventor has not only the above-mentioned problems, but also excellent flame retardancy, excellent melt fluidity and stability during melt molding (quality of molded products).
  • the present inventors have conducted intensive studies to develop a poly-carbonate-based resin composition which can be advantageously used in the production of molded articles having excellent mechanical properties, light resistance and appearance.
  • the result is a straight-chain or cyclic aromatic group-containing silicone compound having a specific structure, which has a specific amount of aromatic group. It has been found that not only the flame retardancy can be dramatically improved, but also the physical properties other than the flame retardancy can be improved.
  • the present invention has been completed based on this finding.
  • the main object of the present invention is not only to have excellent flame retardancy, but also to have excellent melt fluidity and stability during melt molding (quality stability of molded articles) and mechanical properties
  • An object of the present invention is to provide an aromatic polycarbonate resin composition which can be advantageously used for producing a molded article having excellent light resistance and appearance.
  • an aromatic polycarbonate and a resin mixture of an aromatic polycarbonate and at least one other organic polymer resin are selected, and the aromatic polycarbonate of the resin mixture is selected from the group consisting of: 100 parts by weight of a resin component having a bone content of 50% by weight or more and (B) 0.1 to 100 parts by weight of a linear or cyclic aromatic group-containing silicone compound;
  • the aromatic group-containing silicone compound (B) is represented by the following formula (1) ′:
  • R 1 and R 2 each independently represent a hydrogen atom or a monovalent C i —C sa hydrocarbon group
  • R 3 and R 4 are each independently a hydrogen atom or monovalent or divalent C 2 . Wherein R 3 and R 4 are each independently divalent —C 2 . R 3 and R 4 are divalent at the same time and are bonded to each other Forming a ring;
  • At least one of R 1 , R 2 , R 3 and R 4 is C 6 —C 2 .
  • the aromatic group has a valency as defined above for RR 2 , R 3 or R 4 ;
  • n 1 or more, expressed as a number average n value.
  • the above polymer as the component (B) includes a monomer, a polymer or a mixture thereof represented by the following formula (2):
  • the repeating unit may be the same or different. Therefore, the above-mentioned polymer as the component (B) is a homopolymer or a copolymer, and In this case, the copolymer is a random copolymer, a block copolymer or an alternating copolymer,
  • the amount of the aromatic group in the component (B) is 5 to 100 mol% based on the total molar amount of R 1 R 2 , R 3 and R 4 ;
  • an aromatic polycarbonate resin composition characterized by the following features: Is done.
  • the aromatic group-containing silicone compound (B) has the following formula (1)
  • R 1 and R 2 each independently represent a hydrogen atom or a monovalent C i —C 2. Hydrocarbon group
  • R 3 and R 4 are each independently a hydrogen atom or monovalent or divalent mono C 2 . Wherein R 3 and R 4 are each independently a divalent C 1 -C 1. When representing a hydrocarbon group of R 3 and And R 4 are simultaneously divalent and are linked to each other
  • RR 2 one at least of the R 3 and R 4 are C 6
  • n is 1 or more, expressed as a number average n value.
  • the polymer as the component (B) is represented by the following formula (2):
  • the repeating unit may be the same or different. Therefore, the above-mentioned polymer as the component (B) is a homopolymer or a copolymer.
  • the copolymer is a random copolymer, a block copolymer or an alternating copolymer,
  • An aromatic polycarbonate-based resin composition comprising:
  • the flame retardant (C) is at least one flame retardant selected from metal salt flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, inorganic flame retardants, and fluorine flame retardants. 5.
  • the resin composition according to the above item 5 wherein the metal salt-based flame retardant is a metal salt of an organic sulfur compound. 7. The resin composition according to the above item 6, wherein the metal salt of the organic sulfur compound is a metal salt of an organic sulfonic acid.
  • the nitrogen-based flame retardant is at least one member selected from the group consisting of triazine-based compounds, triazole-based compounds, tetrazole-based compounds, phosphazene-based compounds, and diazo-based compounds.
  • the resin component (A) is composed of an aromatic polycarbonate, an aromatic vinyl polymer, an olefin polymer, a polyester polymer, a polyamide polymer, and a polyphenylene ether. 10.
  • the aromatic polycarbonate resin composition of the present invention is selected from the group consisting of (A) a aromatic polycarbonate and a resin mixture of an aromatic polycarbonate and at least one other organic polymer resin.
  • the aromatic polycarbonate content of the resin mixture is 50% by weight or more
  • the component (B) not only acts as a flame retardant for the resin component (A), but also provides the resin composition with excellent melt fluidity and stability during melt molding (quality stability of molded articles). And an effect of improving the mechanical properties, light resistance and appearance of a molded article of the resin composition.
  • the component (B) forms a silica coating on the surface of the molded product as soon as the composition of the present invention, in particular, the molded product starts burning, and the resin component (A) Improve the flame retardancy of
  • the component (B) can dramatically improve the flame retardancy of the resin component (A).
  • the reasons for the improvement in flame retardancy are considered as follows. .
  • the component (B) contains an aromatic group, the compatibility with the resin component (A) is improved, and as a result of the component (B) being finely dispersed in the resin component (A), the resin is dramatically improved.
  • the flame retardancy of the composition is improved.
  • the component (B) is a linear or cyclic aromatic group-containing silicone compound having no branched structure and no cross-linked structure, the molded product obtained from the resin composition of the present invention can be obtained.
  • the gas begins to burn, the molecular motion of the component (B) is activated, and the compatibility between the component (B) and the resin component (A) is improved. Therefore, the siloxane group and the resin component ( The reaction with the carbonate group of A) is promoted. to this Thus, the combustion of the resin component (A) is suppressed.
  • the silicon atom contained in the component (B) is an element having a low surface energy
  • the component (B) segregates on the surface of a molded article obtained from the resin composition of the present invention.
  • the component (B) is a linear or cyclic compound having no branched structure and no crosslinked structure
  • the mobility of the component (B) to the surface of the molded article is promoted.
  • the molded article obtained from the resin composition of the present invention starts burning, a high concentration of the component (B) is present on the surface, and excellent flame retardancy is exhibited. 5 O A (Angstrom) especially from the surface of the compact
  • the ratio of CZC 2 to (%) is 2 to 100, the molded product becomes an excellent flame retardant material.
  • the aromatic polycarbonate (hereinafter often referred to as “PC:”) used for the resin component (A) may be one or more different types of bifunctional phenolic compounds contained therein. Any of aromatic homopolycarbonate and aromatic copolycarbonate obtained by the above method may be used.
  • a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of caustic alkali and a solvent, or, for example, transesterification of a bifunctional phenolic compound with getyl carbonate in the presence of a catalyst Transesterification method It can be.
  • bifunctional phenolic compounds examples include 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis ( 4—Hydroxyphenyl) methane, 1,1′-bis (4—hydroxyphenyl) ethane, 2,2′-bis (4—hydroxyphenyl) butane, 2,2′-bis (4—hydroxy-3 , 5 —diphenyl) butane, 2,2'-bis (4-hydroxy35-dipropylpyrphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1, 1'-bis (4-hydroxyphenyl) ethane and the like, and 2,2'-bis (4-hydroxyphenyl) propane, which is known as bisphenol A, is particularly preferable.
  • the bifunctional phenolic compound may be used alone or in combination.
  • the PC preferably has a viscosity-average molecular weight in the range of 10,000 to 100,000.
  • the viscosity-average molecular weight of PC can be measured by gel permeation chromatography (GPC).
  • the PC content of the resin mixture is 50% by weight or more, preferably 70% by weight or more.
  • organic polymer resins other than PC examples include thermoplastic resins other than PC, rubbery polymers, and thermosetting resins. Among them, thermoplastic resins other than PC and rubbery polymers are preferred, and thermoplastic resins other than PC are particularly preferred.
  • thermoplastic resin other than the above-mentioned PC is not particularly limited as long as it can be dispersed uniformly with the PC.
  • aromatic vinyl polymer, polyphenylene ether polymer, olefin polymer, polyvinyl chloride polymer, polyamide polymer, polyester polymer, polyphenylene sulfide Polymers, polymethacrylate polymers, epoxy polymers, etc., or a mixture of two or more of them can be used.
  • the aromatic vinyl resin which can be used in the resin mixture as the component (A.) is a rubber-modified aromatic vinyl resin and a Z- or non-rubber-modified aromatic vinyl resin, particularly a rubber-modified aromatic resin. It is preferable that the resin be composed of a vinyl-based resin alone or a rubber-modified aromatic vinyl-based resin and a non-rubber-modified aromatic vinyl-based resin, and is not particularly limited as long as it can be uniformly dispersed with PC. Further, the rubber-modified aromatic pinyl-based polymer refers to a polymer in which a rubber component for modification is dispersed in a matrix composed of an aromatic vinyl-based polymer in the form of particles.
  • polystyrene examples include impact-resistant polystyrene (HIPS), ABS polymer (acrylonitrile-butadiene-styrene copolymer), AAS polymer (Acrylonitrile).
  • HIPS impact-resistant polystyrene
  • ABS polymer acrylonitrile-butadiene-styrene copolymer
  • AAS polymer Acrylonitrile
  • acrylic rubber-styrene copolymer examples include an acrylic rubber-styrene copolymer and an AES polymer (acrylonitrile ethylene propylene rubber-styrene copolymer).
  • the modifying rubber component preferably has a glass transition temperature (T g) of ⁇ 30 ° C. or lower, and if it exceeds 130 ° C., a molded article obtained from the composition of the present invention The impact resistance tends to decrease.
  • T g glass transition temperature
  • the glass transition temperature should be measured by the differential scanning calorimetry (DSC) described in the "Polymer Handbook" (edited by J. Brandrup, A Wiley-Interscience Publication, John Wiley S Sons, New York (1975)). Can be.
  • Examples of such rubber components for modification include gen-based rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile butadiene); saturated rubber obtained by hydrogenating the gen rubber; and isoprene rubber. , Chloroprene rubber, acrylic rubbers such as polybutyl acrylate, ethylene-propylene copolymer rubber, ethylene-propylene-monomer terpolymer rubber (EPDM), ethylene-octene copolymer Rubber etc. Gen-based rubbers are particularly preferred.
  • the aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the above-mentioned rubber component for modification is, for example, styrene, ⁇ -methylstyrene, paramethylstyrene, etc. Yes, styrene is most preferred, but the above-mentioned other aromatic vinyl monomers may be copolymerized mainly with styrene.
  • one or more other monomer components as described below, which can be copolymerized with an aromatic vinyl monomer can be introduced as desired.
  • an unsaturated nitrile monomer such as acrylonitrile and methacrylonitrile can be used.
  • an acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used.
  • a monomer such as acrylic acid, methacrylic acid, maleic anhydride, or ⁇ -substituted maleimide is copolymerized. May be.
  • the heat resistance can also be increased by using ⁇ -methylstyrene as at least a part of the aromatic vinyl monomer.
  • the content of the other monomer copolymerizable with the aromatic vinyl monomer in the polymerizable monomer mixture which is polymerized in the presence of the rubber component for modification described above is 0 to 40. % By weight.
  • the rubber component for modification in the rubber-modified aromatic vinyl polymer Preferably from 5 to 80% by weight, particularly preferably from 10 to 50% by weight, the graft-polymerizable monomer mixture is preferably from 95 to 20% by weight, more preferably from 90 to 90% by weight. It is in the range of 50% by weight. Within this range, the balance between impact resistance and rigidity of a molded article obtained from the composition of the present invention is improved. Further, the rubber-modified aromatic vinyl-based polymer has a rubber average particle diameter of preferably from 0.1 to 5.0 ⁇ m, and particularly preferably from 0.2 to 3.0 m. Within the above range, the impact resistance of a molded article obtained from the composition of the present invention is particularly improved.
  • Reduced viscosity of the polymer part which is a measure of the molecular weight of the rubber-modified aromatic vinyl polymer 7] sp / c (0.5 gd1, 30 ° C measurement: toluene when the matrix resin is polystyrene
  • sp / c 0.5 gd1, 30 ° C measurement: toluene when the matrix resin is polystyrene
  • the solution or the matrix resin is an unsaturated ditolyl-aromatic vinyl copolymer, use methylethyl ketone
  • Means for satisfying the above requirements for sp / c include adjustment of polymerization initiator amount, polymerization temperature, chain transfer agent amount, and the like. .
  • Syndiotactic styrene polymer which is a crystalline styrene polymer is preferable.
  • Syndiotactic styrene-based polymers have superior heat and chemical resistance characteristics compared to ordinary amorphous, atactic polystyrene. However, it is brittle and has poor impact resistance.
  • Syndiotactic structure means that the stereochemical structure is a syndiotactic structure, that is, a steric structure in which phenyl groups, which are side chains, are alternately located in the opposite direction to the polymer main chain formed from carbon-carbon bonds.
  • the tacticity one is quantified Ri by the nuclear magnetic resonance method according to carbon isotope (1 3 C-NMR method).
  • styrenic polymers include polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (alkoxy styrene), poly (vinyl benzoic acid), and mixtures thereof, or a mixture thereof.
  • poly (alkylstyrene) include poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), and poly (Yuichi-Shearylstyrene), and poly (halogenated styrene). Examples include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like. Examples of the poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
  • polystyrene poly (p-methylstyrene), poly (m-methylstyrene), poly (p-short-butylstyrene), poly (p-chlorostyrene), and poly (m —Chlorosperene), poly (p-fluorostyrene), and a copolymer of styrene and p-methylstyrene.
  • HIPS impact-resistant polystyrene
  • ABS polymer acrylonitrile-butadiene-styrene copolymer
  • compatibilizer a styrene-based copolymer described in WO95-353346 as a compatibilizer.
  • the polyphenylene ether resin which can be used in the resin mixture as the component (A) includes poly (2,6-dimethyl-1,4-phenylene).
  • PPE polyphenylene ether resin
  • the method for producing such PPE is not particularly limited, and examples thereof include a method for preparing a mixture of a cuprous salt and an amine by the method described in US Patent No. 3,306,874. It can be easily produced by oxidative polymerization of 2,6-xylenol using a plex as a catalyst.
  • U.S. Pat. No. 3,306,875 and U.S. Pat. No. 7, 357, U.S. Pat. No. 3,257, 358, Japanese Patent Publication No. 52-17880, and Japanese Patent Publication No. 50-511197 It can be easily manufactured by the method described.
  • the reduced viscosity of the above PPE is 7 sp / c (0.5 g / d 1, close-form solution, measured at 30 ° C). It should be in the range of 0.20 to 0.70 d 1 Zg. And preferably in the range of 0.30 to 0.60 dl Z g Is more preferred.
  • Means for adjusting the reduced viscosity of PPE to 77 sp / c; in the above-mentioned preferred range include means for adjusting the amount of catalyst in the production of PPE.
  • olefin-based polymer which can be used as an organic polymer resin other than PC in the resin mixture as the component (A)
  • a propylene-based resin is preferable, and a homo-isotactic polypropylene and propylene are preferred.
  • other ⁇ -olefins such as ethylene, butene-11, pentene-11, hexene-11, etc. (including block and random).
  • olefin polymer is a mixture obtained by mixing a crosslinkable rubber component and an olefin polymer and a polymer, for example, by melt-kneading in the presence of a crosslinking agent and a crosslinking assistant.
  • an ethylene ' ⁇ -olefin copolymer or a hydrogenated gen-based rubber is preferable.
  • ethylene- ⁇ one-year-old olefin copolymers ethylene and ⁇ -olefins having 3 to 20 carbon atoms are more preferable, and particularly ethylene and ⁇ -olefin having 6 to 1 carbon atoms produced using a meta-open catalyst.
  • the ⁇ -olefin copolymer of No. 2 is preferred because of its narrow molecular weight distribution.
  • random hydrogenated gen-based rubbers in which 50% or more of the total double bonds of the gen-based rubber are hydrogenated are preferable.
  • gen-based rubber is hydrogenated with 90% or more of the total double bonds, and 1,2—vinyl bonds after hydrogenation are 5% or less, and 1,4-bonds after hydrogenation are 5% or less. Certain random hydrogenated gen rubbers are more preferred.
  • an aromatic vinyl unit can be contained in the gen-based rubber.
  • the glass transition temperature (T g) of the rubber-like polymer is ⁇ 30 °. ⁇ It is preferable that the following is satisfied. If the Tg of the rubber-like polymer exceeds ⁇ 30 ° C., the impact resistance of the molded article obtained from the composition of the present invention tends to decrease.
  • Examples of such rubbery polymers include gen-based rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene); saturated rubbers obtained by hydrogenating the gen rubber; Acrylic rubbers such as isoprene rubber, chloroprene rubber, and polybutyl acrylate; ethylene-propylene copolymer rubber; ethylene-propylene-gen monomer terpolymer rubber (EPDM); Examples thereof include crosslinked rubber or non-crosslinked rubber such as butene copolymer rubber, and a thermoplastic elastomer containing the above rubber component.
  • gen-based rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene); saturated rubbers obtained by hydrogenating the gen rubber
  • Acrylic rubbers such as isoprene rubber, chloroprene rubber, and polybutyl acrylate
  • thermoplastic elastomers an aromatic vinyl-based thermoplastic elastomer is particularly preferable, and a block copolymer comprising an aromatic vinyl unit and a conjugated gen unit, or the conjugated gen unit portion A partially hydrogenated or epoxy-modified block copolymer or the like can be used.
  • thermoplastic elastomer By blending the above-mentioned thermoplastic elastomer into PC, it is possible to solve the problem that the impact strength is reduced when PC is formed into a thick molded body. At that time, by further blending the styrene-based copolymer as a compatibilizer, excellent impact strength is exhibited.
  • Examples of the aromatic vinyl monomer used to form the aromatic vinyl unit constituting the block copolymer include styrene, ⁇ -methylstyrene, paramethylstyrene, ⁇ -chlorostyrene, ⁇ -bromostyrene, 4, 5-tribromostyrene, etc., of which styrene is most preferred, but styrene may be the main component and other aromatic vinyl monomers may be copolymerized.
  • Examples of the conjugated diene monomer used to form the conjugated diene unit constituting the copolymer include 1,3-butanediene and isoprene.
  • a polymer block composed of an aromatic vinyl unit is represented by S
  • a polymer block composed of a conjugated gen and / or a partially hydrogenated unit thereof is represented by S.
  • X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, polyepoxy compound, etc.)
  • X part is the connection center It is preferably a star (star) blog copolymer.
  • a linear one block copolymer of SB type 2, SBS type 3, and SBSB type 4 is preferable.
  • thermosetting resins that can be used as an organic fluoropolymer resin other than PC in the resin mixture as the component (A) include phenol resins, amino resins, melamine resins, and imido resins. And epoxy polymers.
  • the weight average molecular weight of the organic polymer resin other than PC is preferably 50,000 to 1,000,000, and 100,000 to 500,000. More preferably, it is 0 0.
  • a particularly preferred example of the resin mixture as the resin component (A) is a mixture of PC and the above-mentioned aromatic vinyl polymer.
  • the aromatic group-containing silicone compound (B) has the following formula (1):
  • R 1 and R 2 each independently represent a hydrogen atom or a monovalent —C 2. Hydrocarbon group
  • R 3 and R 4 are each independently a hydrogen atom or monovalent or divalent —C 2 . Wherein R 3 and R 4 are each independently a divalent mono-C 2 . R 3 and R 4 are divalent at the same time, and combine with each other to form a ring;
  • RR 2 one at least of the R 3 and R 4 are C 6 one C 2.
  • the aromatic group has a valency as defined above for RR 2 , R 3 or R 4 ;
  • n 1 or more, expressed as a number average n value.
  • the above polymer as the component (B) includes a monomer, a polymer or a mixture thereof represented by the following formula (2):
  • R 1 and R 2 are each as defined in the formula (1).
  • the repeating unit may be the same or different. Therefore, the above-mentioned polymer as the component (B) is a homopolymer or a copolymer, and In this case, the copolymer is a random copolymer, a block copolymer or an alternating copolymer,
  • the amount of the aromatic group in the component (B) is from 5 to 100 mol% based on the total molar amount of RR 2 , R 3 and R 4 .
  • non-aromatic hydrocarbon group that can be contained in the component (B)
  • a methyl group, an ethyl group, and a butyl group are preferable, and a methyl group is more preferable.
  • the aromatic group in the component (B) is preferably a phenyl group.
  • the component (B) is a bifunctional D unit represented by the following formula (3) described in "Silicon Handbook" (edited by Nikkan Kogyo Shimbun, Kunio Ito (1990), Japan). Is a silicone compound having a linear or cyclic structure.
  • the silicone compound used as the component (B) in the present invention does not contain a structural unit that forms a branched structure or a crosslinked structure.
  • the flame retardancy of the resin component (A) cannot be sufficiently improved.
  • Branched or bridged structures Examples of the structural unit that forms the structure include a trifunctional T unit represented by the following formula (4) described in the above “Silicon Handbook”.
  • Fat component (A) 0.1 to 100 parts by weight, preferably 0.10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of component (B).
  • Ri Ah is necessary for the total moles of R 4 is a 5-1 0 0 mol%, preferably 1 0-9 0 mol%, further preferred properly 2 0-9 0 mol%, and most preferably 3 0 ⁇ 90 mol%.
  • N in the above formula (1) is preferably at least 10 and more preferably at least 100.
  • the aromatic group-containing silicone compound used as the component (B) preferably has a kinematic viscosity measured at 25 ° C. of 100 centistokes or more in accordance with JIS-K240, more preferably It is at least 300 centistokes, most preferably at least 1000 centistokes. The kinematic viscosity is 100 centi-cents. When full, component (B) becomes volatile and may not be desirable.
  • the upper limit of the kinematic viscosity of the component (B) is not particularly limited, and may be a gum that exceeds the measurement limit (1, 000, 000 centistokes).
  • the component (B) a mixture of a plurality of different aromatic group-containing silicone compounds satisfying the requirements of the present invention can be used.
  • the component (B) is a silicone compound containing the aromatic group in an amount of 5 mol% to less than 50 mol% based on the total molar amount of R 1 , R 2 , R 3 and R 4 ; It is preferably a mixture with a silicone compound containing 50% by mole or more of the aromatic group based on the total moles of RR 2 , R 3 and R 4 .
  • the above-mentioned silicone compound containing an aromatic group in an amount of 50 mol% or more is extremely advantageous for obtaining the excellent effects of the present invention, but is relatively expensive.
  • the above-mentioned silicone compound containing an aromatic group in an amount of 5 mol% to less than 50 mol% and the above-mentioned silicone compound containing an aromatic group in an amount of 50 mol% or more are mixed. It is preferred to use as component (B).
  • composition of the present invention may further contain (C) 0.001 to 100 parts by weight of a flame retardant.
  • Flame retardants (C) include silicon-based flame retardants, metal-salt-based flame retardants, halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, inorganic flame retardants, fibrous flame retardants, and char forming. At least one flame retardant selected from agents can be used. Of the above flame retardants (C), Silicone flame retardants, metal salt flame retardants, phosphorus flame retardants, nitrogen flame retardants, and inorganic flame retardants are particularly preferred.
  • silicon-based flame retardant polyorganosiloxane (silicon, organic silicate, etc.) other than the silicone-based compound used as the component (B), silica, and the like can be used.
  • Polyorganosiloxane is classified into oil, resin, and rubber according to their properties.
  • the polyorganosiloxane that can be used as the silicon-based flame retardant (C) in the present invention is a structural unit described in the above-mentioned “Silicon Had Book”, that is, M represented by monofunctional R 3 Si 2.
  • R 0 which contained 4 S i 0 2 represented by Q units, and alkoxy groups or ⁇ Li bite alkoxy group functional S at least one selected from the group consisting of an X unit represented by i O 2.0 and a Y unit represented by (RO) 2 Si 0 3.0 (R is a hydrocarbon having 1 to 20 carbon atoms)
  • R is a hydrocarbon having 1 to 20 carbon atoms
  • Such a polyorganosiloxane is a polyorganosiloxane having an oily branched structure or a silicone resin having a three-dimensional network structure.
  • the rubbery polyorganosiloxane is a vulcanized product of a high molecular weight gum-like linear polydiorganosiloxane.
  • the flame retardant (C) a modified form of the above-mentioned polyorganosiloxane or a complex with another substance may be used.
  • the body include a modified polyorganosiloxane modified with an epoxy, amino, mercapto, methyl group or the like.
  • the above-mentioned composite include a polycarbonate (PC) -silicon copolymer, an acrylic rubber-silicon composite, and the like.
  • R in the polyorganosiloxane that can be used as the flame retardant (C) is a hydrocarbon group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a butyl group, a phenyl group, or a benzyl group. Groups are preferred, and a methyl group and a phenyl group are particularly preferred.
  • the phenyl group is contained in an amount of 5 to 100 mol% based on the total molar amount of R.
  • Such a polyorganosiloxane not only has excellent compatibility with aromatic resins such as PC, but also improves the water resistance and thermal stability of the composition of the present invention.
  • Silica one of the silicon-based flame retardants, is amorphous silicon dioxide.
  • a hydrocarbon-based compound-coated silica obtained by treating the silica surface with a hydrocarbon-based silane-capping agent is preferable, and a vinyl-containing hydrocarbon-based compound-coated silica is more preferable.
  • silane coupling agents examples include p-styrilyltrimethoxysilane, vinyltrichlorosilane, vinyltris (jSmethoxylethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, Ryoichi Vinyl group-containing silanes such as methacryloxyprovir trimethoxyxylane, ⁇ - (3,4 epoxy Epoxysilanes such as (cyclohexyl) ethyl trimethoxysilane, aglycidoxypropyl trimethoxysilane, and aglycidoxypropyl triethoxysilane; and N— ⁇ (aminoethyl) aminopropyl Aminosilanes such as built-in trimethoxysilane, ⁇ -3 (aminoethyl) aminopropylmethyldimethoxysilane, amiaminopropyl triethoxysilane, and phenylaminopropyl
  • the treatment of the silane coupling agent on the silica surface is roughly classified into a wet method and a dry method.
  • the wet method is a method in which silica is treated in a silane coupling agent solution and then dried.
  • the dry method is a method in which silica is charged into a device capable of high-speed stirring such as a Henschel mixer, and the silane-based printing agent solution is slowly dropped while stirring, followed by heat treatment. .
  • the metal salt-based flame retardant as the flame retardant (C) is preferably an organic sulfur compound metal salt.
  • organic sulfur compounds include potassium tribenzene sulfonic acid, potassium perfluorobutanesulfonic acid, potassium disulfonic acid-3-sulfonic acid, and the like.
  • Organic sulfonic acid metal salts are exemplified.
  • metal salt-based flame retardants aromatic sulfonimide metal salts
  • a contained aromatic organic polymer can be used.
  • Alkali metals and alkaline earth metals can be used as the metals of the above metal salts.
  • Such a metal salt-based flame retardant promotes a decarboxylation reaction at the time of burning a molded article obtained from the composition of the present invention, and improves flame retardancy.
  • a metal sulfonate-containing aromatic organic polymer is particularly preferred.
  • the aromatic organic polymer containing a metal sulfonic acid salt is used as the flame retardant (C)
  • the metal sulfonic acid salt becomes a cross-linking point and forms a carbonized film when the molded product obtained from the composition of the present invention is burned.
  • halogen-based flame retardants examples include bisphenol phenol, aromatic halogen compounds, halogenated polycarbonate, halogenated aromatic vinyl polymer, and halogenated halogenated flame retardant.
  • examples include cyanurate resin and halogenated polyphenylene ether.
  • decabromodiphenyloxyside, tetrabromobisphenol A, an oligomer of tetrabromobisphenol A bisphenol bromide phenolic resin, bisphenol bromide polycarbonate, bromide Polystyrene, brominated cross-linked polystyrene, polyphenylene bromide, polydibromophenylene oxide, condensate of decabromdiphenyloxide with bisphenol, halogenated phosphoric acid ester It is preferable to use a fluorine resin or the like.
  • Examples of the phosphorus-based flame retardant as the flame retardant (C) include organic phosphorus compounds, red phosphorus, and inorganic phosphorus salts.
  • organic phosphorus compound examples include phosphine, phosphoxide, biphosphine, phosphonium salt, phosphinate, phosphinate, phosphite and the like. More specific examples include triphenyl phosphate, methyl neopentyl phosphite, henyl erythritol getyl diphosphite methyl neopentyl phosphonate, phenyl neopentyl phosphite Erythritol phenyldiphenyl diphosphate, dicyclopentyl hypophosphite, dineopentyl hypophosphite, phenylpyrophosphate phosphite, ethylpyrocatechol phosphate, zipiro Catechol hypothetic phosphate is an example.
  • organic phosphorus compound an aromatic phosphate ester monomer or an aromatic phosphate ester condensate is particularly preferred.
  • aromatic phosphate ester monomers among the aromatic phosphate ester monomers, those described in U.S. Pat. Phosphoric acid ester monomers or aromatic phosphoric acid ester monomers containing one or two or more phenolic hydroxyl groups in cresyl phosphate, triphenyl phosphate and the like are preferred. Or a long-chain alkyl such as tris (nonylphenyl) phosphate described in WO96-27736 Preferred is an aromatic phosphate ester monomer containing a hydroxyl group.
  • bisphenol A bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) and the like are preferable.
  • an aromatic phosphoric acid ester condensate produced by a method disclosed in Japanese Patent Application Laid-Open No. 5-17979 or the like is also preferable as the organic phosphorus compound.
  • a monofunctional phenol substituted at the 2- and 6-positions is reacted with oxyhalogenated phosphorus in the presence of a Lewis acid catalyst to obtain diaryl phosphorohalide, and then to obtain the resulting diaryl phosphorohalide.
  • the aromatic phosphate condensate obtained by reacting the compound with a bifunctional phenol in the presence of a Lewis acid catalyst can be suitably used as a phosphorus-based flame retardant.
  • Red phosphorus one of the phosphorus-based flame retardants mentioned above, is selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide in advance, in addition to ordinary red phosphorus.
  • Coated with a coating of a metal hydroxide to be coated coated with a coating of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide, and a thermosetting resin Or a double-coated thermosetting resin film on a metal hydroxide film selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. is there.
  • inorganic phosphate used as the above phosphorus flame retardant For example, ammonium phosphate is used.
  • the nitrogen-based flame retardant includes at least one selected from the group consisting of triazine-based compounds, triazole-based compounds, tetrazole-based compounds, phosphazene-based compounds, and diazo-based compounds. Seeds can be used.
  • triazine-based compounds include melamine, melamine, melem, melon (a product of deammonification of three molecules from three molecules of melem at 600 ° C. or higher), melamine cyanide Melamine phosphate, succinoguanamine, adipoguanamine, methylglutalogamine, melamine resin, BT resin, and the like, and melamine cyanurate are particularly preferred from the viewpoint of low volatility.
  • triazole-based compound examples include triazole, methyltriazole, and phenyltriazole.
  • the phosphazene compound as a nitrogen-based flame retardant is not particularly limited as long as it has a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond, and examples thereof include cyclic phosphazene and linear phosphazene.
  • phosphazenes phosphazenes containing an aromatic group as a substituent are preferred from the viewpoint of compatibility with aromatic polycarbonate. In terms of structure, linear phosphazene is preferred.
  • cyclic phosphazene examples include propoxyphosphazene, phenoxyphosphazene, aminophosphazene, and full Specific examples of linear phosphazenes include polyarylphosphazenes such as polyphenylphenylphosphazene, polyaryloxyphosphazenes such as polydiphenoxyphosphazene, polydiaminophosphazenes, and the like. And polydifluoroalkylphosphazene. These phosphazene compounds are produced by substituting the clog phosphazene with alcohols or phenols.
  • Te Torazo Ichiru compounds as nitrogen-based flame retardant 5 - full ⁇ two ruthenate Torazo Ichiru, 5, 5 '- Bisute Torazoru 2 Anmoniumu salt 5, 5' - Bisute Torazo Ichiru 2 amino Nogua two gin salt, 5, 5 '— bisestrazole piperazine salt, azoviste torazole 2 guanidine salt, azoviste tolazole 2 amino guanidine salt and the like.
  • diazo compounds examples include azodicarbonamide, azobisisobutyronitrile, diazoaminobenzene, and polyvinylazodicarboxylate.
  • inorganic flame retardants examples include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and basic magnesium carbonate.
  • Hydrates of inorganic metal compounds such as hydrates of zirconium hydroxide, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, Bismuth oxide, acid Metal oxides such as chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper , Tungsten, tin, antimony and other metal powders, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. These may be used alone or in combination of two or more. Among
  • Fibrous flame retardant as flame retardant (C) is a flame retardant used to prevent dripping of fire, and becomes fibrous when added or processed. Specific examples thereof include aramide fiber, polyacrylonitrile fiber, and fluororesin.
  • the above-mentioned aramide fiber preferably has an average diameter of 1 to 500 m and an average fiber length of 0.1 to 10 mm, and is preferably made of isophthalamide or polyparaphenylene terephthalamide. It can be produced by dissolving in a basic solvent or sulfuric acid and spinning the solution by a wet or dry method.
  • the polyacrylonitrile fiber as the fibrous flame retardant preferably has an average diameter of 1 to 500 m, an average fiber length of 0.1 to 10 mm, and dimethylformamide.
  • Dry spinning in which the polymer is dissolved in a solvent such as Is produced by a wet spinning method in which a polymer is dissolved in a solvent such as nitric acid and wet-spun in water.
  • the fluororesin as the fibrous flame retardant is a resin containing a fluorine atom in the resin.
  • a resin containing a fluorine atom in the resin include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene Z-hexafluoropropylene copolymer, and the like.
  • the fluorine-based resin may be obtained by copolymerizing a fluorine-containing monomer with a monomer which can be combined with the fluorine-containing monomer.
  • other methods for producing a fluororesin include melt-kneading a fluororesin, a thermoplastic resin, and a dispersant, if desired, to prepare a masterbatch, and then prepare a thermoplastic resin.
  • a two-step process for producing a master batch is preferable.
  • the novolak resin as a char forming agent one of the flame retardants (C), is an acid catalyst such as sulfuric acid or hydrochloric acid for phenols and aldehydes. Is a phenolic novolak resin obtained by condensation in the presence of water.
  • the phenols used in the production of novolak resins include phenol, 0—cresol, m—cresol, p—cresol, 2,5—dimethyl, 3,5—dimethyl, and 2 , 3, 5 — trimethylol, 3, 4, 5 — trimethyl-1, p-t — butyl, p — n — octyl, p — stearyl, ⁇ — fenuru, p — (2 — Phenylethyl), o—isopropyl—, p—isopropyl, m—isopropyl, p—methoxy, and p—phenoxyphenol, pyrocatechol, resorcinol, nose Quinone, salicylaldehyde, salicylic acid, p—hydroxybenzoic acid, methyl p—hydroxybenzoate, p—cyano—, and 0—cyanophenol, p—hydroxybenzenesulfonic acid, p
  • the aldehydes used in the production of novolak resins include formaldehyde, acetate aldehyde, n-propanal, n-butane nar, isopropanal, isobutyl aldehyde, 3-methylene n-butanal, benzaldehyde, p-tolylaldehyde, 2-phenylphenylaldehyde, etc.
  • the amount of the flame retardant (C) in the composition of the present invention is preferably 0.01 to 100 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the resin component (A). To 50 parts by weight, more preferably 3 to 20 parts by weight, and most preferably 5 to 15 parts by weight.
  • composition of the present invention may further contain (D) a processing aid, if desired.
  • Processing aids (D) include aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty alcohols, metal stones, organosiloxane-based waxes, polyolefin waxes, and polyproprolactones. At least one kind of mold release agent or melt flowability improver selected from the following can be used.
  • the amount of the processing aid (D) is preferably from 0.01 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the resin component (A). Most preferably, it is 1 to 5 parts by weight.
  • the molded article obtained from the composition of the present invention has high light resistance.
  • a lightfastness improver can be added to the composition of the present invention, if desired.
  • the lightfastness improver (E) is at least one selected from ultraviolet absorbers, hindered amine light stabilizers, antioxidants, active species scavengers, light-blocking agents, metal deactivators, and quenchers. Seeds can be used.
  • the amount of the light fastness improver (E) is preferably from 0.05 to 20 parts by weight, more preferably from 0 ::! To 100 parts by weight of the resin component (A). It is 10 parts by weight, most preferably 1 to 5 parts by weight.
  • Examples of the method for producing the resin composition of the present invention include a method in which the resin components (A) and (B) are mixed and melt-kneaded with an extruder.
  • the resin component (A) is first melted, and then (B) Ingredients are added and melt-kneaded in the same extruder.
  • the masterbatch after preparing a masterbatch in which the (B) component is blended with the resin component (A), the masterbatch and the remaining resin component (A) or There is a method of kneading the remaining component (B) or another flame retardant.
  • a twin-screw extruder As an extruder used in the method for producing the resin composition of the present invention, a twin-screw extruder is preferable, and the ratio L ZD of the screw length L to the cylinder inner diameter D is 20 to 50. It has two or more supply openings, namely a main feed opening and a side feed opening which differ in the distance from the tip of the twin-screw extruder. A knee portion between the end portions and between the tip portion and the supply opening at a distance close to the tip portion, and the length of the two-sided portion is 3D to 10D, respectively. But preferable.
  • the resin composition of the present invention As a preferable example of the resin composition of the present invention, as the resin component (A), 100 parts by weight of an aromatic polycarbonate alone or a mixture of an aromatic polycarbonate and an aromatic vinyl-based resin; 0.1 to 100 parts by weight of methylphenylsilicone oil which satisfies the requirements of the present invention described above, and an organic metal sulfonate such as potassium diphenylsulfon-3-sulfonic acid as a flame retardant (C). Examples thereof include a resin composition containing 0.001 to 10 parts by weight of a salt and a phosphazene compound, and 0.0001 to 10 parts by weight of polytetrafluoroethylene. This resin composition has particularly excellent balance properties of flame retardancy, continuous moldability, moldability (melt fluidity), impact resistance, and heat resistance.
  • the resin composition of the present invention may be, for example, a force obtained by melt-blending each of the above components with a commercially available single-screw extruder, twin-screw extruder, or the like.
  • Agents, lubricants, fillers, reinforcing agents such as glass fibers, coloring agents such as dyes and pigments, and the like can be added.
  • composition of the present invention thus obtained can be continuously molded for a long period of time using an injection molding machine or an extrusion molding machine, and the obtained molded article has flame retardancy, heat resistance and heat resistance.
  • the impact resistance is excellent.
  • the Izocl impact strength of a 1/8 inch test piece and a 1Z4 inch test piece was measured by the measurement method described in the above section (2), and the ratio was used as an index of thickness dependence. The closer the ratio is to 1, the less the thickness dependence, and the more stable the impact strength is.
  • melt molding stability ⁇ Molded product quality stability> Using a melt extruder, the resin composition was continuously melt-extruded for 10 hours, and the Izod impact strength of the molded product obtained every hour was measured, and the change rate (%) from the average strength was continuously measured. We evaluated melt molding stability (stability of molded product quality), which is an indicator of productivity.
  • the melt fluidity index was measured by a method in accordance with ASTM-D1238. It was determined from the extrusion rate (g / 10 minutes) per 10 minutes under the conditions of a load of 10 kg and a melting temperature of 260.
  • the SP value was calculated from the Fedors equation described in Polymer Engineering and Science, 14, (2), 147 (1974), and the data of ⁇ e 1 and ⁇ V 1 summarized in the literature.
  • ⁇ e 1 is the cohesive energy per unit functional group
  • ⁇ V 1 is the molecular volume per unit functional group
  • the unit of ⁇ is
  • the SP value of the copolymer or blend is assumed to satisfy the addition rule.For copolymers, the SP value of the monomer unit is used, or for blends, the SP value of each component is used. Calculated by proportional distribution of weight ratio, and this was used as the average SP value.
  • the light resistance test was performed by a method based on JISK 7102 using an ATLAS CI35W Weatherometer manufactured by ATLAS Electric Devices Co., USA as a light resistance tester. Irradiation conditions were as follows: internal temperature of the test machine was 55 ° (: 55% humidity, no rain, xenon light (wavelength: 340 nm, energy: 0.3 OW / m 2 ), 300 hours, Japan Using the SM Color Computer Model SM-3 manufactured by Koku Suga Test Instruments Co., Ltd., the color difference ⁇ E of the molded body before and after the test was determined by the L. a. B. Method, and the color tone change was evaluated. The smaller the is, the higher the light resistance.
  • the components used in Examples and Comparative Examples are as follows.
  • components (B) used in the comparative examples do not satisfy the requirements for the component (B) of the aromatic polycarbonate resin composition of the present invention. For convenience, these components are also used as the components (B). component Classified into
  • PC bisphenol A type polycarbonate
  • HIPS rubber-modified polystyrene (polybutadiene Z-postylene weight ratio: 10Z90) (manufactured by Asahi Kasei Kogyo Co., Ltd., Japan; trade name: Styron) (hereinafter referred to as HIPS) was used.
  • ABS resin ABS resin
  • ABS resin acrylonitrile polybutadiene styrene weight ratio: 24Z20Z56
  • SUIRAC ABS trade name: SUIRAC ABS
  • SEBS styrene-ethylene-butylene-styrene copolymer
  • m-SEBS maleic anhydride-modified styrene-ethylene-petit A styrene-styrene copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., Japan; trade name: Tuftec) (hereinafter referred to as m-SEBS) was used.
  • SB styrene-butadiene copolymer
  • ESB epoxy-modified styrene-butadiene copolymer
  • Syndiotactic polystyrene (SPS) having a melting point of 270 ° C and a weight average molecular weight of 320,000 was used.
  • PPE polyphenylene ether
  • PP polypropylene
  • Ethylene-octene copolymer (E ⁇ ) was used.
  • Commercially available ethylene-octene copolymer (Dupont, USA Dowelas Toma One; product name: Engage) (hereinafter referred to as EII).
  • the styrene copolymer produced by the following method was used as a compatibilizer.
  • the polymerization liquid was led to a devolatilizer at 230 ° C. to remove unreacted monomers and a solvent to obtain a random copolymer (hereinafter referred to as AS-1).
  • AS-1 a random copolymer
  • the obtained copolymer was analyzed by the method described in W95-35-346.
  • the ratio of the monomer components of the copolymer was 6% by weight of acrylonitrile unit and 94% by weight of styrene unit, and the average SP value was 10.75 (single amount).
  • the ratio of body components is determined by infrared absorption spectroscopy).
  • the distribution of the ratio of the monomer components of the copolymer was measured by liquid chromatography analysis to find that the acrylonitrile unit was 0 to 12% by weight.
  • the maximum SP value of the copolymer molecule was 11.0, the minimum SP value was 10.5, and the ⁇ SP value was 0.5.
  • PBT Polybutylene terephthalate
  • Epoxy polymer A commercially available thermoplastic non-halogen-substituted epoxy polymer (manufactured by Asahi Chiba Co., Ltd., Japan (hereinafter referred to as EP)) was used.
  • PA polyamide resin
  • KSS diphenyl sulfone 3-sulfonic acid
  • FBK potassium perfluorobutanesulfonate
  • FP resorcinol-derived aromatic condensed phosphoric acid ester
  • PTFE Polytetrafluoroethylene
  • MC Melamine cyanurate
  • PPP Polydiphenoxyphosphazene (melting point: 110 ° C.) (hereinafter referred to as PPP) was used.
  • HAP Hexakis (acryloyl ethoxy) phosphine
  • a screw a two-section screw having a kneading part before and after the inlet was used.
  • a molded body was produced by injection molding at a cylinder set temperature of 270 ° C. and a mold temperature of 60 ° C. under the following conditions, and was evaluated.
  • the results are shown in Tables 1 and 2.
  • Tables 1 and 2 in the resin composition of the aromatic polycarbonate and the silicon-based compound, even in the silicon-based compound silicone, the D-unit was more than the branched or cross-linked silicone resin having the T unit.
  • the resin composition according to the present invention which comprises a linear silicone having only 5 units and containing an aromatic group in an amount of 5 mol% or more, as the component (B), has not only excellent flame retardancy but also excellent melting properties.
  • a composition was prepared and evaluated in the same manner as in Example 1 except that the resin composition was changed as shown in Tables 3 to 6. The results are shown in Tables 3-6.
  • flame retardants selected from metal salts, phosphorus-based, silicon-based, silicon-based, inorganic-based, and fluorine-based flame retardants as the flame retardant (C) are added to the composition of the present invention. It can be seen that the properties are further improved.
  • a composition was prepared and evaluated in the same manner as in Example 1, except that the composition of the composition was changed as shown in Table 7.
  • Table 7 shows the results. According to Table 7, as long as the requirement of the component (B) of the composition of the present invention is satisfied, the silicone compound containing an aromatic group in an amount of 5 mol% to less than 50 mol% and the aromatic group in an amount of 50 mol% It can be seen that various excellent effects of the present invention are exhibited even when mixtures having various ratios with a silicon compound containing at least mol% are used as the component (B).
  • the meanings of the abbreviations in Tables 1 to 7 are as follows.
  • PC aromatic polycarbonate
  • PPE polyphenylene ether
  • HIPS rubber-modified polystyrene
  • ABS ABS resin
  • SEBS Styrene-ethylene-butylene-styrene copolymer
  • m-SEBS maleic anhydride-modified styrene-ethylene-butylene-styrene copolymer
  • S B Styrene-butadiene copolymer
  • ESB Epoxy-modified styrene-butadiene copolymer
  • SPS syndiotactic styrene polymer
  • PP polypropylene
  • PBT polybutylene terephthalate
  • KSS diphenylsulfone-3-potassium sulfonate
  • FBK potassium perfluorinated sulfonate
  • PPPP polydiphenoxyphosphazene
  • HAP Hexakis (acylethoxy) phosphazene '
  • Composition (B) amount-1 0
  • Product D unit / T unit (molar ratio) 1) 100/0 100/0 0/100 10/90 50/50 80/20 phenyl / methyl (molar ratio) 10/90 40/60 60/40 70 / 30 90/10 100/0 60/40 0/100 60/40
  • the flame-retardant materials obtained by using the resin composition of the present invention include VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio cassettes, video cassettes, video disc players, and the like.

Landscapes

  • 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 résinique de polycarbonates aromatiques, renfermant: A) un composant résinique choisi parmi les polycarbonates aromatiques et des mélanges de ceux-ci avec d'autres résines polymères organiques présentant une teneur en polycarbonates aromatiques supérieure ou égale à 50 % en poids, et B) un constituant siliconé aromatique linéaire ou cyclique, qui contient un monomère ou un polymère représenté par la formule générale (1), ou un mélange de ceux-ci, présentant une teneur en groupes aromatiques variant entre 5 et 100 % moléculaire sur la base de la quantité totale de R1 par rapport à R4.
PCT/JP2000/000681 1999-02-08 2000-02-08 Composition résinique de polycarbonates aromatiques Ceased WO2000046299A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE10080144T DE10080144T1 (de) 1999-02-08 2000-02-08 Aromatische Polycarbonatharz-Zusammensetzung
US09/717,060 US6790887B1 (en) 1999-02-08 2000-11-22 Aromatic polycarbonate resin composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP11/30030 1999-02-08
JP3003099 1999-02-08
JP11/329939 1999-11-19
JP32993999 1999-11-19

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US60184300A Continuation-In-Part 1999-02-08 2000-08-09

Publications (1)

Publication Number Publication Date
WO2000046299A1 true WO2000046299A1 (fr) 2000-08-10

Family

ID=26368293

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2000/000681 Ceased WO2000046299A1 (fr) 1999-02-08 2000-02-08 Composition résinique de polycarbonates aromatiques

Country Status (2)

Country Link
DE (1) DE10080144T1 (fr)
WO (1) WO2000046299A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001270983A (ja) * 2000-03-28 2001-10-02 Teijin Chem Ltd 難燃性ポリカーボネート樹脂組成物
JP2002088237A (ja) * 2000-07-11 2002-03-27 Ge Plastics Japan Ltd 難燃性ポリカーボネート樹脂組成物およびその成形品
WO2002051923A3 (fr) * 2000-12-27 2002-09-19 Gen Electric Procede de reduction du trouble dans une composition ignifuge au polycarbonate
US6541548B2 (en) * 2000-08-07 2003-04-01 Wacker-Chemie Gmbh Flame retardant aromatic polycarbonate resin composition
US6825264B2 (en) 2001-10-11 2004-11-30 Asahi Kasei Chemicals Corporation Flame retardant resin composition
JP2005200526A (ja) * 2004-01-15 2005-07-28 Teijin Chem Ltd 難燃性芳香族ポリカーボネート樹脂組成物
WO2006126670A1 (fr) * 2005-05-26 2006-11-30 Kaneka Corporation Composition de resine ignifuge
US7144935B2 (en) 2002-12-06 2006-12-05 Bayer Aktiengesellschaft Flame-resistant polycarbonate compositions containing phosphorus-silicon compounds
US7390450B2 (en) 2002-06-07 2008-06-24 General Electric Company Process for preparing a fire resistant polycarbonate composition
JP2010174121A (ja) * 2009-01-29 2010-08-12 Teijin Chem Ltd 難燃性芳香族ポリカーボネート樹脂組成物
WO2012091293A3 (fr) * 2010-12-30 2012-08-23 제일모직주식회사 Composition de résine de polycarbonate présentant une excellente résistance chimique
JP2013040237A (ja) * 2011-08-11 2013-02-28 Techno Polymer Co Ltd 熱可塑性樹脂組成物及び成形品
KR101333590B1 (ko) 2010-12-30 2013-11-28 제일모직주식회사 내화학성이 우수한 폴리카보네이트 수지 조성물
US9150725B2 (en) 2010-07-30 2015-10-06 Cheil Industries Inc. Flame retardant polycarbonate resin composition and molded product made using the same
JP2018523742A (ja) * 2015-09-09 2018-08-23 ダウ シリコーンズ コーポレーション 難燃性樹脂組成物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105814702B (zh) * 2013-10-17 2018-06-26 道康宁东丽株式会社 可固化有机硅组合物和光半导体装置

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4390651A (en) * 1974-09-16 1983-06-28 General Electric Company Phenyl-containing organopolysiloxanes
JPH06100785A (ja) * 1992-09-16 1994-04-12 Asahi Chem Ind Co Ltd 耐ドリップ性難燃耐熱耐衝撃性樹脂組成物
JPH06306265A (ja) * 1993-04-26 1994-11-01 Idemitsu Petrochem Co Ltd 難燃性ポリカーボネート樹脂組成物
JPH0987504A (ja) * 1995-09-21 1997-03-31 Teijin Chem Ltd ポリカーボネート樹脂組成物
JPH09111109A (ja) * 1995-10-19 1997-04-28 Mitsubishi Eng Plast Kk 難燃性ポリカーボネート樹脂組成物
JPH111574A (ja) * 1997-01-16 1999-01-06 Chisso Corp 難燃剤およびそれを含有した熱可塑性樹脂組成物
WO1999028387A1 (fr) * 1997-11-28 1999-06-10 Sumitomo Dow Limited Composition de resine de polycarbonate ignifuge

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4390651A (en) * 1974-09-16 1983-06-28 General Electric Company Phenyl-containing organopolysiloxanes
JPH06100785A (ja) * 1992-09-16 1994-04-12 Asahi Chem Ind Co Ltd 耐ドリップ性難燃耐熱耐衝撃性樹脂組成物
JPH06306265A (ja) * 1993-04-26 1994-11-01 Idemitsu Petrochem Co Ltd 難燃性ポリカーボネート樹脂組成物
JPH0987504A (ja) * 1995-09-21 1997-03-31 Teijin Chem Ltd ポリカーボネート樹脂組成物
JPH09111109A (ja) * 1995-10-19 1997-04-28 Mitsubishi Eng Plast Kk 難燃性ポリカーボネート樹脂組成物
JPH111574A (ja) * 1997-01-16 1999-01-06 Chisso Corp 難燃剤およびそれを含有した熱可塑性樹脂組成物
WO1999028387A1 (fr) * 1997-11-28 1999-06-10 Sumitomo Dow Limited Composition de resine de polycarbonate ignifuge

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001270983A (ja) * 2000-03-28 2001-10-02 Teijin Chem Ltd 難燃性ポリカーボネート樹脂組成物
JP2002088237A (ja) * 2000-07-11 2002-03-27 Ge Plastics Japan Ltd 難燃性ポリカーボネート樹脂組成物およびその成形品
US6541548B2 (en) * 2000-08-07 2003-04-01 Wacker-Chemie Gmbh Flame retardant aromatic polycarbonate resin composition
WO2002051923A3 (fr) * 2000-12-27 2002-09-19 Gen Electric Procede de reduction du trouble dans une composition ignifuge au polycarbonate
US6730720B2 (en) 2000-12-27 2004-05-04 General Electric Company Method for reducing haze in a fire resistant polycarbonate composition
US7288579B2 (en) 2000-12-27 2007-10-30 General Electric Company Method for reducing haze in a fire resistant polycarbonate composition
US6825264B2 (en) 2001-10-11 2004-11-30 Asahi Kasei Chemicals Corporation Flame retardant resin composition
US7390450B2 (en) 2002-06-07 2008-06-24 General Electric Company Process for preparing a fire resistant polycarbonate composition
US7144935B2 (en) 2002-12-06 2006-12-05 Bayer Aktiengesellschaft Flame-resistant polycarbonate compositions containing phosphorus-silicon compounds
JP2005200526A (ja) * 2004-01-15 2005-07-28 Teijin Chem Ltd 難燃性芳香族ポリカーボネート樹脂組成物
WO2006126670A1 (fr) * 2005-05-26 2006-11-30 Kaneka Corporation Composition de resine ignifuge
JP2010174121A (ja) * 2009-01-29 2010-08-12 Teijin Chem Ltd 難燃性芳香族ポリカーボネート樹脂組成物
US9150725B2 (en) 2010-07-30 2015-10-06 Cheil Industries Inc. Flame retardant polycarbonate resin composition and molded product made using the same
WO2012091293A3 (fr) * 2010-12-30 2012-08-23 제일모직주식회사 Composition de résine de polycarbonate présentant une excellente résistance chimique
KR101333590B1 (ko) 2010-12-30 2013-11-28 제일모직주식회사 내화학성이 우수한 폴리카보네이트 수지 조성물
US8987379B2 (en) 2010-12-30 2015-03-24 Cheil Industries Inc. Polycarbonate resin composition having excellent chemical resistance
JP2013040237A (ja) * 2011-08-11 2013-02-28 Techno Polymer Co Ltd 熱可塑性樹脂組成物及び成形品
JP2018523742A (ja) * 2015-09-09 2018-08-23 ダウ シリコーンズ コーポレーション 難燃性樹脂組成物

Also Published As

Publication number Publication date
DE10080144T1 (de) 2001-03-22

Similar Documents

Publication Publication Date Title
US6790887B1 (en) Aromatic polycarbonate resin composition
TWI300424B (fr)
WO2000046299A1 (fr) Composition résinique de polycarbonates aromatiques
CN101679739A (zh) 阻燃性聚碳酸酯树脂组合物及其成形品
JP3619193B2 (ja) 難燃性ポリカーボネート系樹脂組成物成形体
JP7386159B2 (ja) 熱可塑性樹脂組成物およびこれから形成された成形品
JP5290483B2 (ja) 難燃性芳香族ポリカーボネート樹脂組成物
JP2003096288A (ja) 芳香族ポリカーボネート樹脂組成物
WO2001072899A1 (fr) Composition de resine de polycarbonate anti-feu et article moule
JP2004137396A (ja) 熱可塑性樹脂組成物及び成形品
JP6055010B2 (ja) 軋み音を低減した熱可塑性樹脂組成物製接触用部品
JP2003292816A (ja) 無機系機能付与剤
JP5687466B2 (ja) 軋み音を低減した熱可塑性樹脂組成物製接触用部品
JP2011046843A (ja) 複合ゴム系グラフト共重合体、熱可塑性樹脂組成物および樹脂成形体
JPH11323063A (ja) 難燃性樹脂組成物
JPH11349758A (ja) 熱可塑性樹脂組成物
JP2000256566A (ja) ケイ素系非ハロゲン難燃性重合体組成物
JPH10130510A (ja) 難燃性熱可塑性樹脂組成物
JP2002114982A (ja) シリコーン系難燃剤
JP2002194197A (ja) 難燃性芳香族ポリカーボネート組成物
JPWO2000046299A1 (ja) 芳香族ポリカーボネート系樹脂組成物
JP2003292793A (ja) 難燃組成物
JP2001192557A (ja) 珪素系重合体組成物
JP2000248144A (ja) 難燃性樹脂組成物
JP2002338819A (ja) 難燃性重合体組成物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 09601843

Country of ref document: US

AK Designated states

Kind code of ref document: A1

Designated state(s): DE JP US

WWE Wipo information: entry into national phase

Ref document number: 09717060

Country of ref document: US

RET De translation (de og part 6b)

Ref document number: 10080144

Country of ref document: DE

Date of ref document: 20010322

WWE Wipo information: entry into national phase

Ref document number: 10080144

Country of ref document: DE

REG Reference to national code

Ref country code: DE

Ref legal event code: 8607