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WO1993022382A1 - Composition a base de resine de polycarbonate - Google Patents

Composition a base de resine de polycarbonate Download PDF

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Publication number
WO1993022382A1
WO1993022382A1 PCT/JP1993/000533 JP9300533W WO9322382A1 WO 1993022382 A1 WO1993022382 A1 WO 1993022382A1 JP 9300533 W JP9300533 W JP 9300533W WO 9322382 A1 WO9322382 A1 WO 9322382A1
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WIPO (PCT)
Prior art keywords
weight
component
resin composition
parts
composition according
Prior art date
Application number
PCT/JP1993/000533
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English (en)
Japanese (ja)
Inventor
Akihiro Saito
Hiroshi Miyake
Original Assignee
Ge Plastics Japan, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Priority claimed from JP35815192A external-priority patent/JP2977690B2/ja
Application filed by Ge Plastics Japan, Ltd. filed Critical Ge Plastics Japan, Ltd.
Publication of WO1993022382A1 publication Critical patent/WO1993022382A1/fr

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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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates

Definitions

  • the present invention relates to a resin composition containing polycarbonate, and more particularly, to a polycarbonate resin composition imparted with flame retardancy and / or low-temperature impact resistance.
  • Polycarbonate resins are used in various applications because of their excellent heat resistance, impact resistance, etc., but suffer from drawbacks such as high molding temperature, poor fluidity, and large thickness dependence of impact strength. Have, there, polycarbonate (PC) resin to ABS (acrylonitrile)
  • PCABS alloy is excellent in moldability and impact resistance, but because of its insufficient flame retardancy, various attempts have been made to improve the flame retardancy (Japanese Patent Publication No. 54-30417, (Kaisho 61-62556)
  • a first object of the present invention is to provide a polycarbonate-based resin composition having improved flame retardancy.
  • a second object of the present invention is to provide a polycarbonate-based resin composition having improved impact resistance at low temperatures.
  • R and R ′ are each independently a halogen atom or a monovalent hydrocarbon group
  • X is a divalent aliphatic group having a carbon number of ⁇ to 18, and b is 0 or 1.
  • (A-2) 9 to 0 parts by weight of a copolymer containing (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component as components of the copolymer; (A) For 100 parts by weight,
  • (B) (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and.) A copolymer containing a rubbery polymer as a component of the copolymer. ⁇ 40 parts by weight.
  • This resin composition has excellent flame retardancy
  • X is a divalent aliphatic group having 6 to 18 carbon atoms
  • b is 0 or 1) 1 to 99 parts by weight of a Kovories pre-carbonate-based resin having a structural unit represented by: and
  • This resin composition is excellent in impact resistance at low temperature.
  • the flame-retardant resin composition which is the first resin composition of the present invention will be described.
  • This resin composition is characterized in that component ( ⁇ ) is combined with two types of rubber components, (() and (C), and flame retardant (I)). If any one of (D) to (D) is missing, good flame retardancy cannot be obtained.
  • the component (II) used here (II-1) is a polycarbonate resin and / or copolyestercarbonate.
  • Polycarbonate is an aromatic polycarbonate produced by a known phosgene method or a melt method (for example, see JP-A-63-215763 and JP-A-2-124934).
  • the carboxyester 'carbonate has a structural unit represented by the above formulas (I) and ( ⁇ ).
  • the structural unit represented by (I) is a diphenol composed of a diphenol component and a carbonate component.
  • the diphenols that can be used to introduce the components are shown in the following formula ( ⁇ )
  • R, R ', W, n, ri' and b are as defined above.
  • R and R ' first, as a halogen atom, for example, a chlorine atom or a bromine atom
  • the monovalent hydrocarbon group include an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a decyl group; a cycloalkyl group having 4 to 8 carbon atoms.
  • a cyclopentyl group, a cyclohexyl group, etc . an aryl group having from 1 to 12 carbon atoms, for example, a phenyl group, a naphthyl group, a biphenyl group and the like; an aralkyl group having 7 to 14 carbon atoms, for example, And an alkaryl group having 7 to 14 carbon atoms, such as a drill group and a cumenyl group, and preferably an alkyl group.
  • the hydrocarbon group of the hydrocarbonoxy group include the aforementioned hydrocarbon groups.
  • hydrocarbonoxy group examples include an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group and an aryloxy group, and an a / recoxy group and an aryloxy group are preferred.
  • W When W is a divalent hydrocarbon group, it has 2 to 30 carbon atoms, such as an alkylene group having from 30 to 30 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, and an octamethylene group.
  • An alkylidene group for example, an ethylidene group, a propylidene group, or a cycloalkylene group having 6 to 16 carbon atoms, for example, a cyclohexylene group, a cyclododecylene group, or a cycloalkylidene group, for example, a cyclohexylidene group And so on.
  • the di'phenols useful in the present invention include, for example, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol / le-A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl) Aropan: 2.2-bis (3.5-dimethyl-4-hydroxy-) aroban: 1,1-seven's (4-tdroxyphenyl) cyclohexane: 1.1-bis (3,5-dimethyl-4) -t droxyphene / cyclohexane: 1.1-bis (4-hydroxyphenyl) decane: 1.
  • Examples of the precursor for introducing the carbonate component include, for example, phosgene, diphenyl carbonate, and the like.
  • the same diphenol as described above can be used for the introduction of the diphenol component composed of the diphenol component and the diacid component.
  • the monomer used for introducing the diacid component is a diacid or an equivalent thereof.
  • the divalent acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms.
  • the diacid or its equivalent may be linear, branched or cyclic.
  • the aliphatic diacid is preferably 6.-dicarboxylic acid.
  • the acid is preferably, for example, a linear saturated aliphatic dicarboxylic acid such as sebacic acid (decandioic acid), dodecanedioic acid, tetradecandioic acid, octadecandioic acid, and eicosantioic acid. Sebacic acid and dodecandioic acid are particularly preferred.
  • Preferred equivalent substances include the above-mentioned divalent acids, for example, acid halides such as acid chloride, and di-homogene esters such as diphenyl ester. However, the number of carbon atoms in the ester portion of the ester is not included in the above acid number carbon number.
  • the above divalent acids or their equivalents may be used alone or in combination of two or more.
  • the copolyester-carbonate used in the present invention needs to be expressed by the above (1) and ( ⁇ ). It is preferable to have the following two types of structural units in the following proportions: That is, the amount of the structural unit represented by (I) is preferably 2 to 30 moles of the total amount of (I) and (E).
  • the weight average molecular weight of the copolyestercarbonate which is more preferably 5 to 25 mol%, and still more preferably 7 to 20 mol%, is usually 10,000 to 100.000, preferably 18,000 to 40,000. is there.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography) using polystyrene corrected for polycarbonate.
  • the above copolyester carbonate is a known method for producing polycarbonate. For example, it can be produced by an interfacial polymerization method using phosgene, a melt polymerization method, or the like. For example, it may be prepared by the method described in U.S. Pat. No. 4,238,596 to Quinn and in U.S. Pat. No. 4,238,597 to (1 ⁇ 62 1) be able to. Specifically, first, an acid halide is formed prior to the reaction between the ester forming group and diphenol, and then reacted with phosgene.
  • a pyridine solvent can be used, and dicarboxylic acid / levonic acid is used. Melt polymerization using ⁇ , ⁇ -dicarboxylic acid (eg, sebacic acid) diesters (eg, diphenyl esters) can also be used.
  • a preferred method of manufacture is the modification of Kochanowski, U.S. Pat. No. 4.286.
  • a lower diacid such as adihinic acid is preliminarily converted into a salt form (preferably an alkali metal salt such as a sodium salt) and added to a phosgene which is added to a reaction vessel in which diphenol is present.
  • the aqueous phase is maintained at an alkaline pH, preferably about pH 8-9, and is then allowed to react with phosgene. At the remaining minimum of about 5%, raise PH 10 to 11
  • catalyst systems include amines such as tertiary amines, amidines or guanidines. Tertiary amines are commonly used, of which trialkylamines such as triethylamine are particularly preferred.
  • copolyestercarbonate has sufficient impact strength even when its terminal is phenol, but ⁇ - ⁇ -butyl: ⁇ -nor, isononyl phenol ', izoctylphenol, m- or cumylphenol Introducing a bulkier end group such as (preferably polycumylphenol) or a chromanyl compound, for example, chromane, can provide a copolyestercarbonate having better low-temperature impact resistance.
  • a bulkier end group such as (preferably polycumylphenol) or a chromanyl compound, for example, chromane
  • the polycarbonate component preferably has a specific viscosity of 0.32 to 0.05 dl / g measured at 25 C in methylene chloride.
  • Component (A) may optionally contain (A-2) a copolymer comprising (a) an aromatic vinyl / vinyl monomer component and ib) a cyanide vinyl / vinyl monomer component. it can.
  • the component (A-2) is not essential for improving the flame retardancy of the resin composition, but it is preferable to include the component (A-2) because the moldability (fluidity) is improved.
  • the (a) aromatic vinyl monomer component in the A-2J copolymer includes, for example, styrene, a-methylstyrene, o-, m- or [) -methylstyrene, pinylxylene, monochlorostyrene. Dichlorostyrene ', monobromostyrene. Dibutene styrene, phthalocyanine, p-tert-butylstyrene. Using the al least one, preferably ⁇ styrene, a -. A methylstyrene styrene ⁇
  • Examples of the vinyl cyanide monomer-dependent component include acrylonitrile, methacrylonitrile and the like, and one or more of these may be used.
  • composition ratio of (a) / (b) is not particularly limited, but preferably (a) is 95 to 50% by weight and (b) is 5 to 50% by weight in the component (A-2). More preferably, (a) is 92 to 65% by weight, and (b) is 8 to 35% by weight.
  • (A-2) Preferred examples of the copolymer include a SAN resin (styrene-acrylonitrile copolymerization).
  • the method for producing the copolymer is not particularly limited, and generally known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization are used. It can also be obtained by blending separately copolymerized resins.
  • the mixing ratio of (A-1) and (A-2) in the component (A) is (A-1) 1-1.
  • (A-2) is 99 to 0 parts by weight with respect to 00 parts by weight, preferably (A-1) 90 to 1 parts by weight with respect to (A-1) 10 to 99 parts by weight.
  • a copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component and (c) a rubbery polymer is used as the component (B).
  • a copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component and (c) a rubbery polymer is used as the component (B).
  • the components (a) and (b) of the copolymer are preferably the same as the components (a) and (b) of the copolymer (A-1) described above. it can.
  • rubbery polymerization includes random copolymerization of polybutadiene, polyisoprene, and styrene-butadiene, and block copolymers, hydrogenated copolymers of the block copolymers, and atarilonitrile-butadiene copolymers.
  • Rubbers such as styrene, butadiene-icreasene copolymers, random copolymers and block copolymers of ethylene-propylene Ethylene-butene random copolymers and block copolymers, copolymers of ethylene and polyolefin, ethylene-unsaturated carboxylic acid esters such as ethylene-methacrylate, ethylene-butyl acrylate, etc.
  • Ethylene-propylene non-conjugated diene polymer such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer, butylene-isoprene copolymer, and chlorinated polyethylene. Use one or more of these.
  • Preferred rubbery polymers are ethylene-propylene rubber, ethylene-propylene non-conjugated diene terpolymer, gen-based rubber and acryl-based elastic polymer, particularly preferably polybutadiene and styrene-butadiene copolymer,
  • the styrene content in the styrene-butadiene copolymer is preferably 50% by weight or less.
  • composition ratio of each component (a), (b) and (c) is not particularly limited, and each component is blended according to the use.
  • -Component (B) includes the above components (a), (b) ) And (c), (d) monomers copolymerizable with these components can be used as long as the object of the present invention is not impaired.
  • ⁇ -unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, buty / re (meth) acrylate, 2-ethyl ( ⁇ ) ⁇ -unsaturated carboxylic acid esters such as meth) acrylate and 2-ethylhexyl methacrylate; maleic anhydride 1 ⁇ , and ⁇ , / 3-unsaturated dicarboxylic anhydrides such as itaconic anhydride: male Mid, ⁇ -methylmale Mid, ⁇ -ethylmale Mid, ⁇ -Hue Examples of imid compounds of, 3-unsaturated dicarboxylic acids, such as Nyl-maleimide, N-0-chlorophenyl maleimide, etc .; Used in more than species ,.
  • component (B) copolymer (c) a graft copolymer in which other components are graft-copolymerized in the presence of a rubbery polymer, and the like, and more preferably an ABS resin (acrylonitrile-butadiene) -AES resin (Atallonitrile-ethylene-propylene-styrene copolymer), ACS resin (Acrylonitrile-Chlorinated polyethylene-Styrene copolymer), AAS resin (Acrylonitrile-) acrylic elastic polymer salary - styrene copolymer) in which ⁇
  • component (II) copolymer there is no particular limitation on the method for producing the component (II) copolymer, and generally known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization are used. It is also possible to obtain a component ( ⁇ ) by blending separately copolymerized resins.
  • Component ( ⁇ ) is used in an amount of 0.5 to 40 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts of component ( ⁇ ).
  • the amount of component ( ⁇ ) used is less than the above range. In other words, the effect of the present invention, that is, the effect of improving flame retardancy is not exhibited.
  • the component (C) contained in the flame-retardant resin composition of the present invention is a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl / (meth) acrylate polymer component are entangled with each other to form a composite and integrated structure. Further, it is a composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers.
  • Such a composite rubber is suitable to be produced by an emulsion polymerization method.
  • a latex of a polyorganosiloxane rubber is prepared, and then a monomer for synthesizing an alkyl- (meth) acrylate rubber is impregnated into rubber particles of a polyorganosiloxane rubber latex. It is preferable to polymerize a monomer for rubber synthesis.
  • the polyorganosiloxane rubber component can be prepared by emulsion polymerization using, for example, the following organosiloxane and a crosslinking agent (i).
  • a crosslinking agent (i) can be used in combination.
  • organosiloxane examples include a chain organosiloxane such as dimethylsiloxane.
  • various cyclic o / reganosiloxanes having three or more members, preferably three to six members, can be used.
  • hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclo Te tiger siloxanes these organosiloxanes ⁇ mentioned can be used alone, or two or more kinds.
  • the amount of these used is preferably 50% by weight or more, more preferably 70% by weight or more, in the polyorganosiloxane rubber component.
  • crosslinking agent (i) examples include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxy silane, triethoxy phenyl silane, 1,000 meth ethoxy silane, tetra ethoxy silane, and tetra silane. - ⁇ -Huh. Roboxy silane, tetrabutoxy silane and the like can be used. Particularly, a tetrafunctional crosslinking agent is preferable, and among them, tetraethoxy silane is particularly preferable. The agents may be used alone or in combination of two or more. Dose using the rack ⁇ is Helsingborg organosiloxane rubber component 0.1 to 3 0% by weight is not to preferred ( As a graft crossing agent ( ⁇ ), the following formula:
  • R 1 represents a lower alkyl group, for example, a methyl group, an ethyl group, an aryl / alkyl group, or a phenyl group
  • R 2 represents a hydrogen atom or a methyl group
  • n represents (Represents 0, 1 or 2
  • P represents an integer of 1 to 6.
  • a compound capable of forming a unit represented by the formula (1) is used.
  • (Meth) atalyloyloxysiloxane capable of forming a unit of the above formula (i-1) has a high grafting efficiency, and therefore forms an effective graft chain.
  • the methacryloyl siloxane is particularly preferable as a compound capable of forming the unit of the formula (i-11).
  • methacryloyl siloxane examples include: -methacryloyloxyshethyldimethoxymethylsilane, r-methacryloyloxymethylpyrmethoxydimethylsilane, a-methacryloyloxypropyldimethoxymethylsilane.: R-methacryloyloxypropyl trimethoxysilane , A-Methacryloyloxy arohill ethoxy decyl silani r-Methacryloyl Sialopyrethoxymethylsilane, 0, -methoxy
  • ⁇ For the production of the latex of the polyorganosiloxane rubber component, a method described in, for example, U.S. Patent Nos. 2891920 and 3294725 can be used.
  • a mixed solution of an organosiloxane, a crosslinking agent (i) and, if desired, a graft crossing agent i> is mixed in the presence of a sulfonic acid emulsifier such as an alkylbenzenesulfonic acid or an alkylsulfonic acid.
  • Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and also serves as a polymerization initiator.
  • a metal salt of an alkylbenzene sulfonic acid, a metal salt of an alkyl sulfonic acid, or the like in combination, since this is effective in maintaining the polymer stably during the graft polymerization.
  • the polyalkyl (meth) acrylate rubber component constituting the composite rubber can be synthesized using the following alkyl (meth) acrylate, a crosslinking agent (ii), and a graft crossing agent (I). .
  • alkyl (meth) acrylate examples include alkyl acrylates and hexyls such as methyl acrylate / reacrylate, ⁇ -propyl acrylate, ⁇ -butyl acrylate 2-ethylhexyl acrylate, and the like.
  • alkyl methacrylates such as methacrylate, 2-ethylhexyl methacrylate, and n-lauryl / methacrylic acid acrylate, and the use of II-butyl acrylate is particularly preferred.
  • crosslinking agent (ii) examples include ethylene glycol dimethacrylate propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and the like.
  • agent (ii) examples include aryl methacrylate, triaryl cyanurate, triallyl isocyanurate and the like.
  • Le-methacrylate can also be used as a bridge.
  • These crosslinking agents and graft crossing agents may be used alone or in combination of two or more.
  • the polymerization of the poly (acrylic) (meth) acrylate rubber component is carried out by adding the alkyl (meth) into the latex of the polyorganosiloxane rubber component that has been neutralized by adding an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, or sodium carbonate. ) Addition of acrylate, cross-linking agent and graft-linking agent. After impregnating polyorganosiloxane rubber particles, it is carried out by the action of a usual radical polymerization initiator.
  • polyalkyl (meth) acrylate rubber As the polymerization progresses, a cross-linked network of polyalkyl (meth) acrylate rubber is formed, which is entangled with the polyorganosiloxane rubber network, and is virtually inseparable.
  • Polyorganosiloxane rubber component and polyalkyl (meth) Note ⁇ latex of a composite rubber of Atari rate rubber component is obtained in the practice of the present invention has a main skeleton dimethylsiloxane Me m Ri return units Helsingborg organosiloxane rubber component in this composite rubber, Composite rubbers in which the main skeleton of the polyalkyl (meth) acrylate rubber component has repeating units of ⁇ -butyl acrylate are preferably used.
  • the composite rubber prepared by emulsion polymerization in this manner can be graft copolymerized with a vinyl monomer.
  • the gel content of this composite rubber measured by extracting it with 90.C for 12 hours with toluene is as follows. 80% !: It is preferable that the content is not less than%.
  • the polyorganosiloxane rubber component and polyalkyl (meth) in the above composite rubber are required.
  • the ratio of acrylate rubber component is 3 to 90% by weight of the former.
  • the latter is preferably 97 to 10% by weight
  • the average particle size of the composite rubber is preferably 0.08 to 0.6 zm.
  • Examples of the vinyl monomer to be graft-polymerized to the above-mentioned composite rubber include aromatic alkoxy compounds such as styrene, para-methylstyrene and vinyltoluene; methyl methacrylate; 2-ethylhexyl methacrylate; Methacrylates; acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate: various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; These can be used alone or in combination of two or more.
  • a particularly preferred vinyl monomer is methyl methacrylate.
  • the vinyl monomer is preferably contained in a proportion of 5 to 70% by weight based on 30 to 95% by weight of the composite rubber.
  • Composite rubber graft copolymer (C> is a composite rubber graft copolymer obtained by adding the above vinyl monomer to the above composite rubber latex and polymerizing it in one or more stages by radical polymerization technology.
  • the latex can be separated and recovered by pouring it into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salting out and coagulating.
  • Such a composite rubber-based graft copolymer (C) is commercially available, for example, from Mitsubishi Rayon Co., Ltd. as methaprene S-201.
  • Component (C) is used in an amount of 0.5 to 40 parts by weight, preferably 0.5 to 30 parts by weight, per 100 parts by weight of component (A). That is, the effect of improving the flame retardancy is not exhibited, and if it is more than the above range, the rigidity decreases.
  • the flame-retardant resin composition of the present invention further comprises a component (D) a phosphate compound as a flame retardant.
  • the phosphate compound is represented by the following formula: OR 1 OR 2
  • examples of the organic group include an alkyl group, which may or may not be substituted, a cycloalkyl group, and an aryl group.
  • examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, a halogenated aryl group, and the like. Substituting a combined group (eg, arylalkoxyalkyl group, etc.) or a combination of these substituted groups with an oxygen atom, a zeo atom, a nitrogen atom, etc.
  • the divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-mentioned organic groups.
  • the relative positions of the free valences particularly preferred is arbitrary, t Dorokinon, resorcinol / Lecinol, Jifue two Ronoremetan, Jifue two roles - dimethyl methane, di t mud carboxy diphenyl, [- dihydroxydiphenols Phenylsulfone, dihydroquinidinaphthalene, etc.
  • phosphoric ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyshethyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl phenyl phosphate.
  • main butoxy Etoki And propoxy, or preferably polyphosphates such as (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate, and the like. And preferably triphenyl phosphate and various polyphosphates.
  • polyphosphates such as (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate, and the like.
  • polyphosphates such as (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate, and the like.
  • the above component (D) is added in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the total of components (A) to (C). If it is less than the above range, the effect of the present invention, that is, the flame retardant effect is not sufficiently exhibited, and if it is more than the above range, heat resistance is impaired.
  • the flame-retardant resin composition of the present invention may further contain an anti-drip agent-fluorinated polyolefins that can be used as such an anti-drip agent are commercially available or available. Alternatively, it can be prepared by known methods, for example, using a free-radical catalyst (eg sodium or potassium benzoxinisulfate or ammonium). A pressure of 100 to 1000 psi and 0 to 200 preferably in an aqueous medium
  • the preferred polytetrafluoroethylene is called Type 3 according to the ASTM, so it is actually from EIDupont de Nemours and Company that Teflon 6 (Teflon & ) As Commercially available or commercially available as Teflon 30 J of Mitsui Dubon Fluorochemicals Co.
  • the fluorinated polyolefin is preferably used in an amount of 0.01 parts by weight based on 100 parts by weight of the component (A). 0.1 to 5 parts by weight, more preferably 0.1 to 5 parts by weight.
  • the second resin composition of the present invention is a resin composition having improved impact resistance at a low temperature.
  • the present inventors have developed two specific rubbers, namely, the above-mentioned component ( ⁇ ) It has been found that when combined with (C) and (C) is added to component ( ⁇ ), it is possible to significantly improve the impact resistance, which could not be predicted when each was used alone, especially at low temperatures.
  • ( ⁇ -1) and ( ⁇ -2) in the component ( ⁇ ) correspond to the first resin composition (flame-retardant resin group) of the present invention described above. Products)-the same as those described as ⁇ -1) and ( ⁇ -2) Can be used.
  • the mixing ratio of (A-1) and (A-2) is (A-1) 1 to 99 parts by weight and (A-2) 99 to 9 parts by weight. 1 part by weight, preferably (A-1) 10 to 99 parts by weight, (A-2) 90 to: L parts by weight.
  • the copolymer described as the component (B) in the flame-retardant resin composition of the present invention can be used as the component (B).
  • the component (B) is The component (A) is added in an amount of 0.5 to 40 parts by weight, preferably ⁇ to 30 parts by weight, based on 100 parts by weight of the component (B). The effect, that is, the effect of improving the low-temperature impact resistance is not exhibited, and if it is more than the above range, the rigidity is reduced.
  • the component (C) the composite rubber-based graft copolymer described as the component (C) in the flame-retardant resin composition of the present invention described above is used. it can.
  • the component (C) is used in an amount of 0.5 to 40 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of the component (A).
  • the amount is less than the above range, the effect of the present invention, that is, the effect of improving the impact resistance at low temperatures is not exhibited, and when the amount is more than the above range, the rigidity is reduced.
  • any of the resin compositions of the present invention may contain other conventional additives, such as a resin, according to the purpose, at the time of mixing or molding the resin, as long as the physical properties are not impaired.
  • a resin according to the purpose, at the time of mixing or molding the resin, as long as the physical properties are not impaired.
  • Pigments, dyes, reinforcing agents glass fiber, carbon fiber, etc.
  • fillers carbon black, silica, titanium oxide, etc.
  • heat stabilizers antioxidant inhibitors
  • weathering agents lubricants
  • mold release agents crystal nucleating agents
  • plastics agents flow improvers
  • flow improvers can be added ⁇ inhibitor such as ⁇
  • the method for producing the resin composition of the present invention there is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be used satisfactorily. However, in general, the melt-mixing method is preferable. Although it is possible to use a small amount of a solvent, the equipment which is not generally necessary is particularly preferable. An extruder, a Banbury mixer, a roller, a kneader, and the like can be given as examples. The order of mixing the components that operate them batchwise or continuously is not particularly limited.
  • PC (1) Bisphenol A polycarbonate (trademark; Lexan, manufactured by Nippon Gee Plastics Co., Ltd.), intrinsic viscosity measured in methylene chloride at 25C 0.56 dl / g
  • PC (2) Bisphenol A polycarbonate (trademark; Lexan, manufactured by Nippon G. Plastics Co., Ltd.), intrinsic viscosity measured in methylene chloride at 25 ° C. 0.5 ctl / g
  • PC (3) polycarbonate of bisphenol A (trademark; Lexan, manufactured by Nippon G. Plastics Co., Ltd.), intrinsic viscosity measured in methylene chloride at 25 ° C. 0.44 dl / g
  • PC (4) Bisphenol A polycarbonate (trademark; Lexan, manufactured by Nippon G. Plastics Co., Ltd.) in methylene chloride, intrinsic viscosity measured at 25.48 dl / g
  • C PE C copolyester carbonate produced as follows: 7.2 g (31 mmol) of dodecane diacid (DDDA) and 2.7 gt ⁇ 8 mmol of NaOH tablets were mixed with 180 m of water. 1) to produce a DDDA dinatrium salt / Next, into a 2000 ml molton flask equipped with a sample outlet on the bottom and five ports on the top, a stirring blade, pH measurement end, Bisphenol A71 (31 1 mmol), Triethylamine C ml. [) -Cumylphenol 2.0 s was added to this polymerization flask equipped with a Claisen adapter with an injection tube and a dry ice condenser.
  • Metaprene S—201 Trademark, methyl methacrylate-petit / real acrylate-dimethylsiloxane copolymer, manufactured by Mitsubishi Rayon Co., Ltd.
  • CR733S Trademark, phenylresorcinol polyphosphate, manufactured by Dai-A Chemical Co., Ltd.
  • Teflon 30J business model, polytetrafluoroethylene, Mitsui Dubonflow Mouth Chemical Co., Ltd.
  • test rods Five test rods were tested at a 1/16 inch thickness according to the test method specified in Underwriters Laboratories Inc.'s Bulletin 94 "Combustion Test for Material Classification" (hereinafter UL-94). According to this test method, the test material was evaluated to one of UL-94 V-0, VI-I and V-II based on the results of five samples.
  • the criteria for each V grade for UL-4 are as follows:
  • V-0 The average flame holding time after removing the ignition flame is 5 seconds or less, and all samples do not drop the fine flame igniting the absorbent cotton.
  • V-I The average flame holding time after removing the ignition flame is 25 seconds or less, and all samples do not drop the fine flame igniting the absorbent cotton.
  • V—I I The average flame holding time after removing the ignition flame is 25 seconds or less, and these samples drop a fine flame that ignites absorbent cotton.
  • UL-94 stipulates that all test bars must pass a particular V rating before they can be classified. If this condition is not fulfilled ..
  • the five test bars are given the grade of the worst test bar.-For example, one test bar is classified as V—I 1. In that case, the grade for all five test bars is V-II.
  • the Izod impact strength was measured at 23 ° C with a thickness of 1'8 inch and a notch according to ASTM D256, and the melt index (MI) was measured at a temperature of 260 and 5 ° C according to ASTH D1238. It was measured under the condition of kg load. Flame retardancy was evaluated as in Example 1.
  • Teflon 30J 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0, 5 0.5 0.5 0,5 0.5 0.5 0.5 0.5
  • the polycarbonate-based resin composition of the present invention makes use of its excellent flame retardancy and / or impact resistance at low temperature, and is used for interior and exterior parts of automobiles, housing of OA equipment, housing of home electric appliances. It can be used in various fields such as applications.

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

Abstract

L'invention se rapporte à une composition à base de résine de polycarbonate, qui possède d'excellentes caractéristiques du point de vue de son pouvoir ignifuge et/ou de sa résistance aux chocs à basse température. La composition ayant un excellent pouvoir ignifuge comprend 1 à 100 parties en poids d'une résine de polycarbonate et/ou un carbonate de copolyester ayant un segment aliphatique et 99 à 0 parties en poids d'une résine SAN, et elle contient en outre 0,5 à 40 parties en poids de chacun des deux constituants à base de caoutchouc suivants, à savoir une résine ABS et un copolymère greffé de caoutchouc composite, préparés par greffe d'un monomère vinylique sur un caoutchouc composite constitué par du polyorganosiloxane et du polyalkyl(méth)acrylate, ainsi que 1 à 30 parties en poids d'un composé d'ester phosphorique comme agent ignifuge. Cette composition possède un pouvoir ignifuge excellent à tel point qu'un moulage à paroi fine à base de cette composition peut passer le test V ou 5V de l'UL94. La composition ayant une excellente résistance aux chocs à basse température comprend 1 à 99 parties en poids d'une résine de polycarbonate et/ou d'un carbonate de copolyester ayant un segment aliphatique et 99 à 1 parties en poids d'une résine SAN, et elle contient en outre 0,5 à 40 parties en poids de chacun des deux constituants à base de caoutchouc mentionnés ci-dessus. Cette résistance aux chocs est particulièrement remarquable à basses températures.
PCT/JP1993/000533 1992-04-24 1993-04-23 Composition a base de resine de polycarbonate WO1993022382A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP12981892 1992-04-24
JP4/129818 1992-04-24
JP35815192A JP2977690B2 (ja) 1992-04-24 1992-12-25 耐衝撃性樹脂組成物
JP35815292 1992-12-25
JP4/358151 1992-12-25
JP4/358152 1992-12-25

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0663425A2 (fr) * 1994-01-12 1995-07-19 General Electric Company Composition de copolycarbonate résistante aux chocs
WO1998008900A1 (fr) * 1996-08-30 1998-03-05 Basf Aktiengesellschaft Matieres de moulage comprenant un melange de polycarbonate et un caoutchouc de siloxane a structure reticulaire
WO2000012609A1 (fr) * 1998-08-31 2000-03-09 General Electric Company Melanges de polymeres ignifugeants et leur procede de fabrication
US6174942B1 (en) 1999-01-22 2001-01-16 General Electric Company Flame retardant polymer blends, and method for making
US6204313B1 (en) 1999-01-22 2001-03-20 General Electric Company Flame retardant polymer blends, and method for making
US6228912B1 (en) 1999-01-22 2001-05-08 General Electric Company Flame retardant resin compositions containing phosphoramides and method for making
US6348527B1 (en) * 1998-08-13 2002-02-19 Idemitsu Petrochemical Co., Ltd. Thermoplastic resin composition based on a combination of polycarbonate and styrenic resins
US6388046B1 (en) 1998-08-31 2002-05-14 General Electric Company Flame retardant resin compositions containing phosphoramides, and method for making
US6433046B1 (en) 1999-01-22 2002-08-13 General Electric Company Flame retardant resin compositions containing phosphoramides, and method of making
US6569929B2 (en) 1999-01-22 2003-05-27 General Electric Company Method to prepare phosphoramides, and resin compositions containing them
KR100483890B1 (ko) * 1997-12-26 2005-07-21 주식회사 코오롱 열가소성난연수지조성물
US7303810B2 (en) 2001-03-05 2007-12-04 3Form, Inc. Fire-resistant architectural resin materials
US7550057B1 (en) 2004-04-09 2009-06-23 3Form, Inc. Architectural laminate panel with embedded compressible objects and methods for making the same
CN106977891A (zh) * 2017-03-17 2017-07-25 中山市通彩化工科技有限公司 一种耐低温无卤阻燃聚碳酸酯组合物及其用途
CN107082877A (zh) * 2017-03-17 2017-08-22 中山市通彩化工科技有限公司 一种制备非透明型聚硅氧烷‑聚碳酸酯无规共聚物的方法

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JPS54148834A (en) * 1978-04-20 1979-11-21 Gen Electric Polycarbonate composition
JPS6479257A (en) * 1987-09-21 1989-03-24 Mitsubishi Rayon Co Thermoplastic resin composition
JPH0269557A (ja) * 1988-07-19 1990-03-08 Bayer Ag 難燃性熱可塑性ポリカーボネート成形用配合物

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPS54148834A (en) * 1978-04-20 1979-11-21 Gen Electric Polycarbonate composition
JPS6479257A (en) * 1987-09-21 1989-03-24 Mitsubishi Rayon Co Thermoplastic resin composition
JPH0269557A (ja) * 1988-07-19 1990-03-08 Bayer Ag 難燃性熱可塑性ポリカーボネート成形用配合物

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0663425A3 (fr) * 1994-01-12 1995-09-13 General Electric Company Composition de copolycarbonate résistante aux chocs
US5602201A (en) * 1994-01-12 1997-02-11 General Electric Company Impact resistant resin composition
EP0663425A2 (fr) * 1994-01-12 1995-07-19 General Electric Company Composition de copolycarbonate résistante aux chocs
CN1061067C (zh) * 1994-01-12 2001-01-24 通用电气公司 耐冲击树脂组合物
WO1998008900A1 (fr) * 1996-08-30 1998-03-05 Basf Aktiengesellschaft Matieres de moulage comprenant un melange de polycarbonate et un caoutchouc de siloxane a structure reticulaire
US6232397B1 (en) 1996-08-30 2001-05-15 Basf Aktiengesellschaft Molding compounds consisting of a polycarbonate mixture and a siloxane reticular rubber
KR100483890B1 (ko) * 1997-12-26 2005-07-21 주식회사 코오롱 열가소성난연수지조성물
US6348527B1 (en) * 1998-08-13 2002-02-19 Idemitsu Petrochemical Co., Ltd. Thermoplastic resin composition based on a combination of polycarbonate and styrenic resins
US6388046B1 (en) 1998-08-31 2002-05-14 General Electric Company Flame retardant resin compositions containing phosphoramides, and method for making
WO2000012609A1 (fr) * 1998-08-31 2000-03-09 General Electric Company Melanges de polymeres ignifugeants et leur procede de fabrication
KR100805574B1 (ko) * 1998-08-31 2008-02-20 제너럴 일렉트릭 캄파니 난연성 중합체 블렌드 및 그의 제조 방법
US6174942B1 (en) 1999-01-22 2001-01-16 General Electric Company Flame retardant polymer blends, and method for making
US6433046B1 (en) 1999-01-22 2002-08-13 General Electric Company Flame retardant resin compositions containing phosphoramides, and method of making
US6569929B2 (en) 1999-01-22 2003-05-27 General Electric Company Method to prepare phosphoramides, and resin compositions containing them
US6228912B1 (en) 1999-01-22 2001-05-08 General Electric Company Flame retardant resin compositions containing phosphoramides and method for making
US6204313B1 (en) 1999-01-22 2001-03-20 General Electric Company Flame retardant polymer blends, and method for making
US7303810B2 (en) 2001-03-05 2007-12-04 3Form, Inc. Fire-resistant architectural resin materials
US7550057B1 (en) 2004-04-09 2009-06-23 3Form, Inc. Architectural laminate panel with embedded compressible objects and methods for making the same
CN106977891A (zh) * 2017-03-17 2017-07-25 中山市通彩化工科技有限公司 一种耐低温无卤阻燃聚碳酸酯组合物及其用途
CN107082877A (zh) * 2017-03-17 2017-08-22 中山市通彩化工科技有限公司 一种制备非透明型聚硅氧烷‑聚碳酸酯无规共聚物的方法

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