WO1998049233A1 - Composition de resine de polycarbonate/polyolefine, procede de production de celle-ci et moules - Google Patents
Composition de resine de polycarbonate/polyolefine, procede de production de celle-ci et moules Download PDFInfo
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- WO1998049233A1 WO1998049233A1 PCT/JP1998/001902 JP9801902W WO9849233A1 WO 1998049233 A1 WO1998049233 A1 WO 1998049233A1 JP 9801902 W JP9801902 W JP 9801902W WO 9849233 A1 WO9849233 A1 WO 9849233A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
Definitions
- the present invention relates to a polycarbonate polyolefin resin composition, a method for producing the same, and a molded product, and in particular, has excellent slidability, mechanical strength, and flame retardancy, and is particularly suitable for OA equipment, home appliances, automobile parts, medical equipment, and the like.
- TECHNICAL FIELD The present invention relates to a polycarbonate / polyolefin resin composition suitable as a raw material of the present invention, a method for producing the same, and a molded article comprising the polycarbonate / polyolefin resin composition. Background art
- Polycarbonate (hereinafter referred to as “P (:)”) is widely used in the automotive and electrical fields due to its excellent heat resistance, impact resistance, electrical properties, and good dimensional stability.
- PC has a high melt viscosity, is inferior in organic solvent resistance, friction and abrasion characteristics, its use is limited in fields where such characteristics are required.
- a composition in which a polyolefin resin is blended with PC has been proposed (Japanese Patent Publication No. 40-13664, Japanese Patent Application Laid-Open No. Sho 59-223).
- Japanese Patent Publication No. 40-13664 Japanese Patent Application Laid-Open No. Sho 59-223
- these compositions have low compatibility between PC and polyolefin, when these compositions are molded by a molding method such as injection molding, the laminar exfoliation occurs.
- Japanese Patent Application Laid-Open No. 63-215570 discloses, in addition to PC and polyolefin, a composition comprising PC having a carboxyl group at a molecular terminal and polypropylene having an epoxy group.
- Japanese Patent Application Laid-Open No. 63-2155702 discloses, in addition to PC and polyolefin, a composition comprising PC having a hydroxyl group at the molecular terminal and polypropylene having a carboxyl group. . These compositions do not show lamellar separation, and have characteristics that combine excellent mechanical strength, organic solvent resistance, and excellent appearance (do not show lamellar separation).
- PC containing a carboxyl group or a hydroxyl group which is a constituent component of these compositions, is obtained by adding a special monomer during the polymerization process. Therefore, for example, if a person skilled in the art who does not have a PC polymerization facility carries out this method, the production is not always easy, since a large cost is required, for example, a new PC polymerization facility is required. There was no. Further, the compositions obtained by these methods are still not sufficient as compared with the original characteristic values of PC, and further improvement of the characteristic values is desired.
- fluorocarbon resins such as polytetrafluoroethylene Methods have been implemented to improve friction and wear characteristics.
- the composition obtained by adding the fluorocarbon resin to the polycarbonate resin has excellent sliding properties in addition to the excellent properties of the polycarbonate resin. Used for parts (gears, cams, etc.) that require heat resistance, impact resistance, and sliding characteristics. Fluororesin is expensive and generates toxic gas when incinerated after being discarded.Polycarbonate-based sliding material replaces polycarbonate resin Z fluororesin-based composition The development of was desired.
- polyolefins especially high-density polyethylene, low-density polyethylene, linear low-density polyethylene, etc.
- polycarbonates in terms of heat resistance, bending rigidity, flame retardancy, etc.
- the inferiority of the resin it was difficult to use it in the field where the polycarbonate fluororesin composition was used.
- Attempts have been made to mix polycarbonate and polyethylene to develop a composition that combines the excellent heat resistance, impact resistance, flame retardancy, etc. of polycarbonate resins with the excellent friction and wear properties of polyethylene. I have.
- the compatibility between polycarbonate and polyethylene is remarkably poor, and simply kneading not only tends to cause delamination, but also causes the surface to easily peel off during friction and abrasion, resulting in reduced wear characteristics. .
- a composition comprising a polycarbonate resin, a modified polyolefin, and an aminocarboxylic acid is excellent in ⁇ , compatibility, slidability, surface properties, and mechanical strength, and can solve the above problem. It was previously proposed (Japanese Patent Laid-Open No. 8-1576464). However, this composition had a problem that the flame retardancy was insufficient for some applications.
- aromatic polyester containing polycarbonate resin There is known a method of adding a brominated polycarbonate oligomer and diantimony trioxide for the purpose of improving the flame retardancy of a resin (JP-A-62-172054).
- a first object of the present invention is to combine the excellent mechanical properties of PC with the excellent moldability of polyolefin, and have excellent surface properties so that layer separation does not occur, and furthermore, flame retardancy is improved.
- An object of the present invention is to provide an excellent PC / polyolefin resin composition.
- a second object of the present invention is to provide a method for easily producing the above-mentioned PC / polyolefin resin composition using a kneader.
- a third object of the present invention is to provide a molded article obtained by melt-molding the above-mentioned PCZ polyolefin-based resin composition having excellent properties.
- the present invention provides a resin composition containing the following components (A) to (F) in a specific combination.
- R is an alkylene group having 5 or more carbon atoms, an alkylidene group, an oligomermethylene group, a phenylene group or a naphthylene group, and the phenylene group or the naphthylene group may have a substituent.
- the present invention as a first embodiment of the resin composition,
- R is an alkylene group having 5 or more carbon atoms, an alkylidene group, an oligomermethylene group, a phenylene group, or a naphthylene group, and the phenylene group or the naphthylene group may have a substituent.
- the first composition of the present invention Z polyolefin resin composition obtained by melt-kneading (Hereinafter referred to as “the first composition of the present invention”).
- composition of the present invention comprises (A) a polycarbonate resin, (C) a modified polyolefm-based resin, (D) a compound represented by the formula (d), and (F) a brominated polycarbonate oligomer.
- a resin composition obtained by melt-kneading (B) a polyolefin-based resin with diantimony oxide and / or nimonium pentoxide (hereinafter, referred to as “the second composition of the present invention”) is preferable.
- composition of the present invention comprises (A) a polycarbonate resin, (C) a modified polyolefm-based resin, (D) a compound represented by the formula (d), and (F) a brominated polycarbonate oligomer.
- a resin composition obtained by melt-kneading (B) a polyolefin-based resin and (E) a styrene-based copolymer resin with diantimony oxide and Z or antimony pentoxide (hereinafter referred to as “third invention”). Composition ”) is preferred.
- the present invention also provides a method for producing the first composition according to the present invention, wherein (C) at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, and an acid anhydride group.
- R is an alkylene group having 5 or more carbon atoms, an alkylidene group, an oligomermethylene group, a phenylene group or a naphthylene group, and the phenylene group or the naphthylene group may have a substituent.
- the compound represented by the formula is melt-kneaded, and then (A) a polycarbonate resin and (F) a brominated polycarbonate oligomer, and diantimony tetroxide or diantimony pentoxide are added to (C) and (D) ) In addition to the molten mixture It is intended to provide a method for producing a polycarbonate / polyolefin resin composition having a kneading step.
- R is an alkylene group having 5 or more carbon atoms, an alkylidene group, an oligomermethylene group, a phenylene group, or a naphthylene group, and the phenylene group or the naphthylene group may have a substituent.
- Another object of the present invention is to provide a method for producing a polycarbonate / polyolefin-based resin and a composition, which comprises a step of adding antimony to the melt-kneaded product of (C) and (D) and further melt-kneading.
- R is an alkylene group having 5 or more carbon atoms, an alkylidene group, an oligomermethylene group, a phenylene group, or a naphthylene group, and the phenylene group or the naphthylene group may have a substituent.
- Another object of the present invention is to provide a method for producing a polycarbonate Z polyolefin-based resin composition having a step of melt-kneading in addition to a product.
- the present invention provides a molded article obtained by melt-molding the resin composition.
- the first composition of the present invention contains the above-mentioned components (A), (C), (D) and (F).
- the PC resin used as the component (A) is obtained by reacting an aromatic dihydroxy compound or an aromatic hydroquine compound with a small amount of a polyhydroxy compound and phosgene, carbonic acid or a diester thereof.
- This is a thermoplastic aromatic polycarbonate polymer obtained as described above.
- bisphenol A is preferable because a composition having excellent heat resistance, mechanical properties, moldability and the like can be obtained.
- a combination of bisphenol A and tetramethylbisphenol A, and a combination of bisphenol A and tetrabromobisphenol A are preferred.
- This PC resin is made of melt flow rate (MFR) (ASTM D 1 38,
- the molecular weight of the PC-based resin is not particularly limited, but is preferably a number-average molecular weight of 100 to 100 (in terms of polystyrene), and more preferably 500 to 400. It is. If the molecular weight is smaller than this range, the resulting composition will have reduced characteristic values such as impact strength, and if it is larger than this range, the moldability will be reduced.
- the PC resin may be a mixture of a crystalline or amorphous thermoplastic resin as long as the effects of the present invention are not impaired.
- Mixing a crystalline thermoplastic resin has the advantage of improving chemical resistance and the like, and mixing an amorphous resin has the advantage of improving heat resistance.
- Crystalline or amorphous thermoplastic tree Specific examples of the fat include polyethylene terephthalate, polybutylene terephthalate, bisphenol type polyarylate, 6,6-nylon, 6-nylon, 6-10-nylon and the like.
- the amount of the resin is preferably 20% by weight or less, more preferably 10% by weight or less.
- the content of the PC resin in the first composition of the present invention is preferably 40 to 99% by weight, more preferably 60 to 95% by weight, and particularly preferably 80 to 95% by weight.
- the content of the PC-based resin is less than 40% by weight, the heat resistance and impact resistance of the obtained composition decrease, and when the content exceeds 90% by weight, the moldability of the obtained composition deteriorates. Will be.
- the content of the PC resin may be 40% by weight or less.
- the modified polyolefin resin used as the component (C) is at least one functional group selected from the group consisting of an epoxy group, a carboxyl group and an acid anhydride group. It is a modified polyolefin resin.
- a polyolefin-based resin similar to that used as the component (B) may be obtained by adding at least one functional group selected from an epoxy group, a carboxyl group, and an acid anhydride group. Those obtained by copolymerizing a saturated monomer can be used.
- unsaturated monomers containing an epoxy group include, for example, glycidyl methacrylate, butyldaricidyl malate, butyldaricidyl fumarate, propyl glycidyl malate, glycidyl atalylate, N- [4- (2,3-epoxypropo Xy) 1,5-dimethylbenzyl] acrylamide.
- glycidyl methacrylate and N- [4- (2,3-epoxypropoxy) -13,5-dimethylbenzyl] acrylamide are preferred in view of price and availability.
- Examples of the unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, and maleic acid.
- Examples of the unsaturated monomer containing an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. Among them, acrylic acid and maleic anhydride are preferred from the viewpoint of reactivity and availability.
- maleic anhydride-modified polyethylene is particularly preferred as the modified polyolefin-based resin in that the sliding properties of the resulting composition can be improved.
- the maleic anhydride-modified polyethylene has a main skeleton composed of polyethylene and maleic anhydride as the unsaturated monomer.
- the polyethylene constituting the main skeleton of the modified polyethylene is preferably a linear low-density polyethylene, a low-density polyethylene or a high-density polyethylene, particularly preferably a linear low-density polyethylene and a low-density polyethylene.
- the molecular weight of the modified polyethylene is usually preferably from 0.2 to 20 g / 10 minutes, more preferably from 0.2 to 10 gZ10 minutes, in terms of melt flow rate (MFR). is there. If modified polyethylene having an MFR smaller than this range is used, moldability may be reduced, and if modified polyethylene larger than this range is used, slidability may be reduced.
- MFR melt flow rate
- a method for preparing a modified polyolefin resin by copolymerizing an unsaturated monomer containing a functional group with a polyolefin resin may be any method, and is not particularly limited. For example, a method of melt-kneading a polyolefin-based resin and an unsaturated monomer in the presence or absence of a radical initiator using a twin-screw extruder, a Banbury mixer, a kneader-type kneader, or the like. And a method of copolymerizing an unsaturated monomer.
- the content of the unsaturated monomer in the modified polyolefin-based resin is 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight.
- the content of the unsaturated monomer is less than this range, the effect of improving the laminar exfoliation of the composition obtained is reduced, and when it is more than this range, there is a possibility that the long-term heat resistance and the like may be adversely affected.
- the content of the modified polyolefin-based resin in the first composition of the present invention is preferably 0.5 to 60% by weight, more preferably 0.5 to 30% by weight, and still more preferably 0.5 to 30% by weight. It is in the range of 20% by weight. If the content of the modified polyolefin-based resin is less than this range, the compatibility of PC in the obtained composition will be reduced to cause laminar separation, and if it is more than this range, the heat resistance and the like will be reduced. However, for the purpose of improving the heat resistance and rigidity of the polyolefin resin, 60% by weight or more may be used.
- the compound used as the component (D) is represented by the following formula (d):
- R is an alkylene group having 5 or more carbon atoms, an alkylidene group, an oligomethylene group, a phenylene group or a naphthylene group.
- the upper limit of the number of carbon atoms of R is not particularly limited, but is preferably 20 or less, more preferably 12 or less is good.
- a compound having an extremely large carbon number not only becomes industrially difficult to obtain, but also reduces the heat resistance of the obtained composition. If the carbon number of R is less than 5, it tends to evaporate and sublimate during the production of the yarn.
- alkylene group examples include a pentylene group (-C 5 ⁇ -) and a hexylene group (_C 6 H.2-).
- the alkylidene group may be any of linear, branched and alicyclic groups.
- examples of the oligomethylene group include those having a structure in which 5 to 20 ethylene groups are bonded in a linear manner.
- Examples of the phenylene group include a P-phenylene group, an m-phenylene group, and a 0-phenylene group.
- examples of the naphthylene group include a 2,6-naphthylene group, a 2,7-naphthylene group, a 1,5-naphthylene group, a 1,8-naphthylene group, and a 4,4′-diphenylene group.
- the phenylene group or the naphthylene group may have a substituent, and for example, may have a substituent such as an alkyl group, a carboxyl group, a halogen atom, an amino group, or an alkoxy group.
- the compound represented by the formula (d) include 6-aminocaproic acid, 7-aminoheptanic acid, 8-aminooctanoic acid, 11-aminoundecanoic acid, p-aminobenzoic acid, and m-amido.
- the content of the compound represented by the formula (d) in the first composition of the present invention is 0.05 to 5% by weight, preferably 0.05 to 4% by weight, and more preferably 0 to 5% by weight. 0.5 to 2% by weight.
- the content of the compound represented by the formula (d) is less than this range, the compatibility of each component of the composition is reduced and laminar separation is remarkable.
- the addition amount is more than this range, particularly (A) ) Significant decrease in molecular weight of PC resin The impact strength of the resulting composition may be reduced.
- the first composition of the present invention contains, as the component (F), a brominated polycarbonate oligomer and niantimon tetroxide and / or niantimon pentoxide.
- a composition having improved flame retardancy can be obtained without impairing the sliding characteristics, solvent resistance, mechanical strength and the like.
- the brominated polycarbonate oligomer used is a polycarbonate having a bromine atom in the molecular skeleton, and is a polymer having 2 to 100, preferably 3 to 10 repeating units.
- the brominated polycarbonate oligomer may have a strong bromine atom and may be bonded at any position in the molecular skeleton, and is not particularly limited, but preferably has a bromine atom bonded to an aromatic ring.
- the brominated polycarbonate oligomer having a molecular end sealed with an alkylphenol or the like is preferable from the viewpoint of thermal stability.
- niantimon tetroxide and niantimon pentoxide used together with the brominated polycarbonate oligomer as the component (F) may be used alone or in combination.
- diantimony trioxide which is generally widely used as a flame retardant aid, cannot be used in the present invention because it promotes the decomposition of the resin component and has an insufficient flame retardant effect.
- the proportion of the brominated polycarbonate oligomer in the component (F) to diantimony tetroxide and Z or diantimony pentoxide is not particularly limited, but from the viewpoint of improving the flame retardancy, the brominated polycarbonate oligomer / Niantimonium oxide and / or diantimony pentoxide) A ratio of 10/1 to 1/2 is preferred, a ratio of 3Z 1 to 1/1 is more preferred, and a ratio of 2/1 is particularly preferred.
- the total content of the brominated polycarbonate oligomer (F) in the first composition of the present invention and diantimony tetroxide and Z or diantimony pentoxide is not particularly limited, but the flame retardancy is not limited.
- the second composition of the present invention further comprises (B) a polyolefin-based resin in addition to the components (A), (C), (D) and (F) of the first composition. Is what you do.
- the components (A), (C), (D) and (F) are the same as those described for the first composition.
- examples of the polyolefin resin used as the component (B) include crystalline polypropylene, crystalline propylene-ethylene block copolymer and random copolymer, low-density polyethylene, and high-density polyethylene.
- examples include high-density polyethylene, linear low-density polyethylene, ultrahigh-molecular-weight polyethylene, ethylene-propylene random copolymer, and ethylene-propylene-gen copolymer.
- these polyolefin-based resins may be used alone or in combination of two or more.
- the polyolefin resin is not particularly limited, but preferably has a melt flow rate (MFR) (230 ° C, load 2.161 ⁇ 8) of 0.1 to 70 g / 10 min, particularly preferably 0.5 to 30 gZ 10 minutes. If the MFR is smaller than this range, the use of a polyolefin-based resin may result in inferior molding processability of the obtained composition. If the MFR is larger than this range, the obtained impact strength may decrease. There is it.
- MFR melt flow rate
- the content of the polyolefin resin in the second composition of the present invention is preferably 0.1 to 60% by weight, more preferably 0.2 to 55% by weight, and still more preferably 3 to 50% by weight. Particularly preferably, the content is 3 to 20% by weight. If it is larger than this range, the heat resistance of the resulting composition will be reduced. For the purpose of improving the heat resistance and flame retardancy of the polyolefin resin, the content may be 60% by weight or less.
- the third composition of the present invention further comprises (E) a styrene copolymer in addition to the components (A), (B), (C), (D) and (F) of the second composition. It contains a polymer resin.
- the components (A), (B), (C), (D) and (F) are the same as those described for the first composition and the second composition.
- the styrene-based copolymer resin used as the component (E) is a copolymer of styrene and olefin or butadiene.
- the styrenic copolymer resin may be any type of block copolymer, graft copolymer or alternating copolymer.
- Examples of the block copolymer include styrene-ethylene propylene copolymer, styrene-butadiene styrene copolymer, and styrene-ethylene butylene-styrene copolymer.
- Examples of the graft copolymer include: Polystyrene graft polypropylene, polystyrene / polyacrylonitrile graft polypropylene, polystyrene graft low density polyethylene, polystyrene / polyacrylonitrile graft low density polyethylene, and the like.
- Examples of the alternating copolymer include a styrenebutadiene copolymer and the like.
- the content of the styrenic copolymer resin in the third composition of the present invention is 0.05 to 30% by weight, preferably 0.5 to 10% by weight.
- the content of the styrenic copolymer resin is less than this range, there is no effect of addition, and when it is more than this range, the heat resistance and bending stiffness of the obtained composition decrease.
- the second and third compositions of the present invention may contain, in addition to the components (A) to (F), other thermoplastic resins and thermoplastic resins.
- Other resin components, elastomers, pigments, organic and inorganic fillers and the like may be added.
- the thermoplastic resin include polyethylene terephthalate, polybutylene terephthalate, nylon, modified PPO, liquid crystal resin, and Teflon
- examples of the resin component other than thermoplastic include silicone oil.
- examples of the inorganic filler include aramide fiber, carbon fiber, talc, My power, calcium carbonate, and potassium titanate whisker.
- appropriate amounts of general additives commonly used for thermoplastic resins, such as plasticizers and antioxidants may be added.
- (C) a modified polyolefin-based resin and (D) a compound represented by the formula (d) are melt-kneaded, and then (A) a polycarbonate resin and (F) adding a brominated polycarbonate oligomer and diantimony tetroxide and / or diantimony pentoxide to the melt-kneaded product of (C) and (D), and further comprising a step of melt-kneading It can be carried out.
- a preferred method for producing the first, second or third composition of the present invention comprises melt-kneading the component (C) and the component (D), adding the component (A) to the melt-kneaded product, (B), (E), and (F).
- the component (C) and the component (D) are melt-kneaded to react with the component (C) and the component (D) to form a compatibilized precursor.
- a resin composition having excellent compatibility of each component can be obtained. That is, when a polyolefin resin modified with at least one kind of functional group selected from a carboxyl group and an acid anhydride group is used as the component (C), the component (C) is selected from the carboxyl group and the acid anhydride group.
- (D) reacting a polyolefin resin modified with at least one kind of functional group with a compound represented by the formula (d) to obtain the following formula (H): H
- a compatibilizing precursor having a bond represented by 0 is generated, and a functional group portion of the compatibilizing precursor is generated.
- a compatibilizer By reacting (-COOH) with the polycarbonate resin, a compatibilizer can be generated.
- a polyolefin resin modified with an epoxy group is used as the component (C)
- the polyolefin resin modified with the epoxy group and the compound represented by the formula (d) are combined with the epoxy group-modified polyolefin resin. And reacting with the following formula (J):
- a compatibilizing precursor having a bond represented by C—C —— (J) HONH—R—COOH is generated, and the functional group portion (—COOH) of the compatibilizing precursor is reacted with a polycarbonate resin.
- a compatibilizer can be generated.
- the formation reaction of the compatibilizer does not proceed smoothly, and a secondary reaction occurs. It is not preferable because the strength of the obtained composition is reduced.
- the compatibilizer is formed during the melt-kneading step, the (A) PC resin and the (B) or (C) polyolefin resin component are formed. It is thought that the compatibility with the polymer is improved and the polymer alloy is achieved. Also,
- the compatibilizer produced in the process of producing the composition of the present invention is an effective compatibilizer between the PC resin and the polyolefin resin component is considered as follows. That is, one NH 2 group contained in the component (D) reacts with a carboxyl group and an acid anhydride group contained in the component (C) to form an amide bond, or reacts with an epoxy group to form an amino bond. And the component (D) is added to the component (C). As a result, the carboxyl group derived from the component (D) is introduced into the component (C) via a specific chemical bond such as an amide bond or a amino bond.
- the carboxy group introduced into the component (C) reacts with the carbonate bond in the component (A), and the polycarbonate and the polycarbonate-grafted polyolefin in which the component (C) is bonded by an ester bond; and a polycarbonate having a terminal OH group.
- C 0 2 The polycarbonate-grafted polyolefin produced here has a polycarbonate component and a polyolefin component in the same molecule, and is considered to be an effective compatibilizer for the polycarbonate Z polyolefin-based resin composition.
- the amount of the functional group in the component (C), the amount of the component (D), and the amount of the component (A) should be stoichiometrically equivalent.
- the degree of polymerization of the component (A) and the degree of polymerization of the polyolefin in the component (C) are preferably higher.
- each component for example, a single-screw extrusion Machine, twin screw extruder, kneader, brabender etc. can be applied.
- a twin-screw extruder is preferred for efficient alloying.
- the temperature of the reaction (melt kneading) is preferably at least 265 ° C and less than 380 ° C, more preferably from 270 ° C to 340 ° C.
- reaction temperature is lower than 265 ° C., sufficient compatibilization between the PC resin and the polyolefin cannot be achieved, and when the obtained resin composition is molded, laminar separation easily occurs.
- the temperature exceeds 380 ° C., the obtained resin composition is thermally decomposed, resulting in poor mechanical properties.
- some of the constituent components for example, (A) a part of a PC resin and (D) a compound represented by the formula (d) are kneaded in advance, and then the remaining components are added thereto. A kneading method may be adopted.
- a compatibilizing precursor is formed in the melt-kneading step, and this is used as a compatibilizing agent, in which (A) a polycarbonate resin and Z or (E) a styrene-based copolymer resin are blended.
- a compatibilizing agent in which (A) a polycarbonate resin and Z or (E) a styrene-based copolymer resin are blended.
- the matrix as a matrix, polyolefin particles are dispersed in the mouth phase, and the average particle size of the particles is 0.1 ⁇ m to 5 m when observed with an electron microscope, and the average aspect ratio is 5 or less. Is particularly preferable for obtaining a molded article having excellent slidability.
- the molded article of the present invention is obtained by subjecting any one of the above-mentioned compositions to melt molding by a molding method generally used for thermoplastic resins.
- a molding method for example, injection molding, hollow molding, sheet molding, lamination molding, press molding and the like can be applied.
- injection molding is preferable.
- the melting can be performed at a melting temperature of 240 to 360 ° C and a mold temperature of 40 to 130 ° C.
- the polyolefin-based resin particles dispersed from the surface of the molded article to a depth of 20 / zm have an average aspect ratio (major axis Z minor axis) of 5 or less. Is preferred. If the average aspect ratio is 5 or more, slidability will decrease. You. This is considered to be because the layer near the surface has a laminar structure, which makes it easier to peel off and increases the amount of wear.
- the polyolefin resin particles polyethylene particles are preferable.
- Preferred dispersion forms of the polyolefin-based resin particles include, for example, a compounding amount of the polycarbonate resin of 90% or more, a compounding amount of the modified polyethylene of 10% or less, and a compound of the structural unit (D). This is achieved when the blending amount of Nb is 0.05 to 2.0% by weight, etc., but is not limited because the temperature, injection speed, cooling speed, and the like during molding also vary.
- an inorganic filler such as glass fiber, carbon fiber, aramide fiber, talc, myriki, calcium carbonate, etc.
- an inorganic filler such as glass fiber, carbon fiber, aramide fiber, talc, myriki, calcium carbonate, etc.
- glass fiber, carbon fiber, aramide fiber, or the like because the improvement in bending rigidity and the improvement in sliding characteristics are expected.
- silicone oil, molybdenum compounds and the like can be added. These additives are also preferable because they can be expected to improve the sliding properties.
- general additives such as a plasticizer and an antioxidant added to the thermoplastic resin may be added in an appropriate amount. Since the molded article of the present invention has excellent slidability, it can be used as parts for office automation equipment, home electric appliances, medical equipment and the like, and is particularly suitable for parts such as gears, cams and bearings.
- PE polyethylene Linilex AM07 1 0 manufactured by Nippon Petrochemical
- MAP P Maleic anhydride-modified polypropylene Mitsubishi Kasei AP 590 P
- EP P P Epoxy-modified polypropylene Tonen Chemical's
- C-900X modified MAPE Maleic anhydride-modified polyethylene Mitsui Chemicals
- a A p-Aminobenzoic acid (manufactured by A1drich)
- Injection molding machine manufactured by Yamashiro Seiki S AV—60—52 Type 2, performed at a molding temperature of 260 ° C.
- a 1 / 16-inch specimen was prepared by injection molding and tested according to the UL-94 standard for flame retardancy evaluation. Flame retardancy improves in the order of NG, V-2, V-1, V-0.
- a friction / wear test (ring-on-ring method) was performed between a ring-shaped test piece made by injection molding and a test piece made of steel (S-45C) of similar shape.
- the test conditions were a linear velocity of 3 Om / min, a load of 2.6 kg / cm 2 , and a test time of 72 hours.
- the torque during this test is detected by the load cell, and the dynamic friction coefficient was calculated, and the specific wear was calculated from the change in weight of the test piece before and after sliding, and used as an index of slidability.
- the measurement was performed on a notched specimen according to ASTM D256.
- the measurement was performed at a temperature of 280 ° C and a load of 2.16 kg according to ASTM D1238.
- MAAE maleic anhydride-modified polyethylene
- AU 11-aminoundecanoic acid
- D helical mixer
- Example 2 the same as Example 1 except that the components (C) and (D) were used at the ratios shown in Table 1, and the components (A) and (F) were used at the ratios shown in Table 1.
- the resin composition was manufactured in the same manner as above, dried at 120 ° C for 8 hours, and then subjected to injection molding to measure the flame retardancy, sliding properties, dynamic friction coefficient and Izod impact strength. It was measured. Table 2 shows the results.
- a kneaded product was prepared in the same manner as in Example 1 using the components (C) and (D) in the proportions shown in Table 1.
- a resin composition was produced in the same manner as in Example 1. After drying at 120 ° C for 8 hours, it was subjected to injection molding to measure flame retardancy, slidability, kinetic friction coefficient and Izod impact strength, and MFR. Table 2 shows the results.
- the polycarbonate z polyolefin-based resin and composition of the present invention have both excellent mechanical properties of pc and excellent moldability of polyolefin, and have excellent surface properties without causing layer separation. It is excellent in flame retardancy. Therefore, the polycarbonate / polyolefin-based resin composition of the present invention is useful as a material for interior / exterior parts, housings, and mechanical parts (gears, cams, etc.) of automobiles, electrics, and electronic devices.
- the above-mentioned PCZ polyolefin-based resin composition can be easily produced using a kneader.
- the molded article of the present invention is a PC / polyolefin having the above-mentioned excellent properties. Since it is made of a resin composition, it has high industrial practical value as a material for internal and external parts such as automobiles, electric and electronic equipment, housings, and mechanical parts (gears, cams, etc.).
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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)
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK98917676T DK0911367T3 (da) | 1997-04-25 | 1998-04-24 | Polycarbonat/polyolefin-harpikspræparat, dets fremgangsmåde til fremstilling og genstande formstöbt derfra |
EP98917676A EP0911367B1 (en) | 1997-04-25 | 1998-04-24 | Polycarbonate/polyolefin resin composition, process for producingthe same, and moldings |
DE69824934T DE69824934T2 (de) | 1997-04-25 | 1998-04-24 | Polycarbonat-polyolefinharzzusammensetzung und verfahren zu seiner herstellung und formmassen |
AT98917676T ATE270693T1 (de) | 1997-04-25 | 1998-04-24 | Polycarbonat-polyolefinharzzusammensetzung und verfahren zu seiner herstellung und formmassen |
US09/214,006 US6231965B1 (en) | 1997-04-25 | 1998-04-24 | Polycarbonate/polyolefin resin composition, process for producing the same, and moldings |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10876797A JP3148149B2 (ja) | 1997-04-25 | 1997-04-25 | ポリカーボネート/ポリオレフィン系樹脂組成物およびその製造方法、ならびに成形体 |
JP9/108767 | 1997-04-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998049233A1 true WO1998049233A1 (fr) | 1998-11-05 |
Family
ID=14492979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/001902 WO1998049233A1 (fr) | 1997-04-25 | 1998-04-24 | Composition de resine de polycarbonate/polyolefine, procede de production de celle-ci et moules |
Country Status (9)
Country | Link |
---|---|
US (1) | US6231965B1 (ja) |
EP (1) | EP0911367B1 (ja) |
JP (1) | JP3148149B2 (ja) |
KR (1) | KR100390327B1 (ja) |
AT (1) | ATE270693T1 (ja) |
DE (1) | DE69824934T2 (ja) |
DK (1) | DK0911367T3 (ja) |
ES (1) | ES2224381T3 (ja) |
WO (1) | WO1998049233A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010005486A3 (en) * | 2008-06-30 | 2010-03-04 | Bayer Materialscience Llc | Flame retardant, optically clear thermoplastic molding composition |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6980152B2 (en) * | 2003-07-03 | 2005-12-27 | Textron Systems Corporation | Externally cued aircraft warning and defense |
US8273825B2 (en) | 2007-03-20 | 2012-09-25 | Sabic Innovative Plastics Ip B.V. | Polycarbonate/polyolefin based resin compositions and their production processes and uses |
EP2195379A1 (en) * | 2007-09-26 | 2010-06-16 | Dow Global Technologies Inc. | Improved carbonate polymer blends with reduced gloss |
KR101237741B1 (ko) * | 2010-06-30 | 2013-02-26 | 주식회사 투에이취켐 | 고유동성 및 난연성을 갖는 금속피복용 변성 폴리에틸렌 수지 조성물, 이를 이용하여 제조된 금속피복용 변성 폴리에틸렌 파우더, 및 그 제조방법 |
JP6193119B2 (ja) * | 2011-03-31 | 2017-09-06 | ニッタ株式会社 | 高耐久性を有する熱可塑性樹脂組成物 |
KR101455366B1 (ko) * | 2011-11-23 | 2014-11-04 | 에스케이이노베이션 주식회사 | 고차단성 종이 코팅용 조성물 |
KR101835942B1 (ko) | 2015-10-27 | 2018-03-08 | 롯데첨단소재(주) | 내전리방사선성 폴리카보네이트 수지 조성물 및 이를 포함하는 성형품 |
US12102458B2 (en) | 2018-01-24 | 2024-10-01 | Teijin Limited | Reusable medical box |
Citations (3)
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JPH05171011A (ja) * | 1991-12-26 | 1993-07-09 | Polyplastics Co | 難燃性ポリエステル樹脂組成物 |
JPH08157664A (ja) * | 1994-03-16 | 1996-06-18 | Kawasaki Steel Corp | ポリカーボネート/ポリオレフィン系樹脂組成物および成形体、その製造方法 |
JPH08157732A (ja) * | 1994-12-09 | 1996-06-18 | Japan Synthetic Rubber Co Ltd | 難燃性樹脂組成物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1332015C (en) * | 1987-08-17 | 1994-09-13 | Yuichi Orikasa | Thermoplastic resin composition and method for preparing the same |
KR0163021B1 (ko) * | 1988-08-22 | 1999-01-15 | 가타 야마 유타카 | 표면백화를 방지하는 난연성 올레핀 중합체 조성물 |
US5594062A (en) * | 1994-03-16 | 1997-01-14 | Kawasaki Steel Corporation | Polycarbonate/polyolefin based resin compositions and their production processes and uses |
-
1997
- 1997-04-25 JP JP10876797A patent/JP3148149B2/ja not_active Expired - Fee Related
-
1998
- 1998-04-24 DE DE69824934T patent/DE69824934T2/de not_active Expired - Fee Related
- 1998-04-24 AT AT98917676T patent/ATE270693T1/de not_active IP Right Cessation
- 1998-04-24 EP EP98917676A patent/EP0911367B1/en not_active Expired - Lifetime
- 1998-04-24 KR KR10-1998-0710493A patent/KR100390327B1/ko not_active IP Right Cessation
- 1998-04-24 ES ES98917676T patent/ES2224381T3/es not_active Expired - Lifetime
- 1998-04-24 US US09/214,006 patent/US6231965B1/en not_active Expired - Fee Related
- 1998-04-24 WO PCT/JP1998/001902 patent/WO1998049233A1/ja active IP Right Grant
- 1998-04-24 DK DK98917676T patent/DK0911367T3/da active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05171011A (ja) * | 1991-12-26 | 1993-07-09 | Polyplastics Co | 難燃性ポリエステル樹脂組成物 |
JPH08157664A (ja) * | 1994-03-16 | 1996-06-18 | Kawasaki Steel Corp | ポリカーボネート/ポリオレフィン系樹脂組成物および成形体、その製造方法 |
JPH08157732A (ja) * | 1994-12-09 | 1996-06-18 | Japan Synthetic Rubber Co Ltd | 難燃性樹脂組成物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010005486A3 (en) * | 2008-06-30 | 2010-03-04 | Bayer Materialscience Llc | Flame retardant, optically clear thermoplastic molding composition |
Also Published As
Publication number | Publication date |
---|---|
EP0911367A1 (en) | 1999-04-28 |
JPH10298420A (ja) | 1998-11-10 |
KR100390327B1 (ko) | 2004-05-20 |
DE69824934D1 (de) | 2004-08-12 |
DK0911367T3 (da) | 2004-11-22 |
EP0911367A4 (en) | 2000-08-09 |
DE69824934T2 (de) | 2005-04-07 |
US6231965B1 (en) | 2001-05-15 |
ES2224381T3 (es) | 2005-03-01 |
KR20000022089A (ko) | 2000-04-25 |
JP3148149B2 (ja) | 2001-03-19 |
ATE270693T1 (de) | 2004-07-15 |
EP0911367B1 (en) | 2004-07-07 |
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