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    • 专利摘要:
    COMPOSITION OF FLAME RETARDANT POLYOLEFIN RESIN, AND, HOUSING OR COMPONENT OF AN ELECTRIC AUTOMOTIVE VEHICLE, MACHINE, AND ELECTRIC AND ELECTRONIC EQUIPMENT. The present invention provides a polyolefin resin composition with sufficient flame retardancy to meet UL94 5VA standard without using a halogen flame retardant which produces a harmful gas during combustion, and specifically provides a flame retardant polyolefin resin composition containing, as flame retardant components of the polyolefin resin, (A) a (poly)phosphoric acid compound expressed by the general formula (1) and (B) a (poly)phosphate compound expressed by the general formula (3), and preferably ( C) zinc oxide and (D) an anti-drip agent, and which meets UL94 5VA standard. It should be noted that the details of general formula (1) and general formula (3) are as described in the report.
    公开号:BR112014009263B1
    申请号:R112014009263-0
    申请日:2012-11-22
    公开日:2021-07-13
    发明作者:Hatanaka Tomoyuki；Iwasaki；Yamazaki
    申请人:Adeka Corporation；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [0001] The present invention relates to a flame retardant polyolefin resin composition and particularly to a flame retardant polyolefin resin composition conforming to UL94 5VA, which is the UL standard for flame retardancy. BACKGROUND ART
    [0002] Polyolefin resins are advantageous for their excellence in molding processability, dynamic properties, low specific density, and the like, and thus have been used widely as inexpensive general purpose resins and in the form of a molded article for applications such as machines, electrical and electronic equipment, materials for interior or exterior of automobiles with OA equipment, and electric motor vehicle. Among these products, with respect to electrical and electronic equipment, and OA equipment, and the like, it is necessary that the molded articles have high flame retardancy especially in the case where the articles will be used as casings (chassis, bodies, exteriors, covers, etc.) or components of such products.
    [0003] Specifically, compliance with the UL standard of Underwritters Laboratories is required, and compliance with, especially, the UL94 5VA standard has recently been required primarily for large mobile equipment, large stationary equipment, equipment using high voltage, and the like.
    [0004] As for molded articles from self-extinguishing resins such as polycarbonate resin, those meeting the UL94 5VA standard have thus been proposed (see Patent Literature 1 and 2).
    [0005] However, conventionally, polyolefin resins are difficult to conform to the UL94 5VA standard, and even if this standard were met, a problem is noted in using a halogen-based flame retardant that produces a harmful gas during combustion. Furthermore, depending on the charge of the flame retardant, the problem that the inherent physical properties of resin is adversely affected has been noted. LIST OF QUOTES
    [0006] Patent Literature Patent Literature 1: JP 9-12859 The Patent Literature 2: US Patent Report number 6838502 SUMMARY OF THE INVENTION TECHNICAL PROBLEM
    [0007] Consequently, the present invention relates to a flame retardant polyolefin resin composition that does not use halogen based flame retardant that produces a harmful gas during combustion and meeting the UL94 5VA standard. SOLUTION TO THE PROBLEM
    [0008] The present inventor has intensively researched in order to solve the above-described problems and thus realized the present invention.
    [0009] That is, the present invention, a flame retardant polyolefin resin composition containing the following components (A) and (B) as flame retardant components for a polyolefin resin and meeting the UL94 5VA standard, one component ( A): a (poly)phosphate compound represented by the following general formula (1) a component (B): a (poly)phosphate compound represented by the following general formula (3). [Chemical formula 1]
    where n represents a number from 1 to 100, X1 represents ammonia or a triazine derivative represented by the following general formula (2), and p represents a number satisfying 0 < p < n + 2, [Chemical formula 2]
    wherein Z1 and Z2 may be either the same or different and are each a group selected from the group consisting of a group -NR5R6 [wherein R5 and R6 may be either the same or different and are each a hydrogen atom, a linear alkyl group or branched having 1 to 6 carbon atoms, or a methylol group], a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group, and a vinyl group, [Chemical formula 3]
    wherein r represents a number from 1 to 100, Y1 represents [R1R2N(CH2)mNR3R4], piperazine, or a diamine having a piperazine ring, wherein R1, R2, R3, and R4 each represents a hydrogen atom or a group linear or branched alkyl having 1 to 5 carbon atoms and R1, R2, R3, and R4 may be either the same or different, m represents an integer from 1 to 10, and q represents a number satisfying 0 < q < r + 2 .
    [0010] The present invention also provides the aforementioned flame retardant polyolefin resin composition, wherein the total content of components (A) and (B) is 15 to 50% by mass.
    [0011] The present invention also provides the aforementioned flame retardant polyolefin resin composition further containing zinc oxide as a component (C).
    [0012] The present invention also provides the aforementioned flame retardant polyolefin resin composition further containing an anti-drip agent as a component (D).
    [0013] The present invention also provides the aforementioned flame retardant polyolefin resin composition, wherein component (D) is polytetrafluoroethylene.
    [0014] The present invention also provides the aforementioned flame retardant polyolefin resin composition using as component (A) a melamine pyrophosphate of the general formula (1) wherein n is 2, p is 2, and X1 is a melamine of the general formula (2) wherein Z1 and Z2 are each -NH2.
    [0015] The present invention also provides the aforementioned flame retardant polyolefin resin composition using as component (B) a piperazine polyphosphate of the general formula (3) wherein q is 1 and Y1 is piperazine.
    [0016] The present invention also provides the aforementioned flame retardant polyolefin resin composition wherein the piperazine polyphosphate is a piperazine pyrophosphate.
    [0017] The present invention also provides the aforementioned flame retardant polyolefin resin composition meeting UL94 5VA standard at a thickness of 3.2mm or less.
    [0018] The present invention also provides the aforementioned flame retardant polyolefin resin composition meeting UL94 5VA standard at a thickness of 1.6mm or less.
    [0019] The present invention also provides a frame or component of an electric motor vehicle, machines, and electrical and electronic equipment obtained from the composition of flame retardant polyolefin resin. ADVANTAGEOUS EFFECTS OF THE INVENTION
    [0020] According to the present invention, it is possible to provide a flame retardant polyolefin resin composition that does not produce a harmful gas during combustion and meets the UL94 5VA standard. DESCRIPTION OF ACHIEVEMENTS
    [0021] The flame retardant polyolefin resin composition of the present invention is described in detail below based on the preferred embodiments.
    [0022] First, the polyolefin resin to be used for the flame retardant polyolefin resin composition of the present invention is described.
    [0023] Examples of the polyolefin resin to be used for the flame retardant polyolefin resin composition of the present invention include o-olefin polymers such as low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, polybutene, cycloolefin polymers, steric block polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, and poly-4-methyl-1-pentene, and copolymers of α-olefin such as block or random ethylene/propylene copolymers, ethylene-methyl methacrylate copolymers, and ethylene-vinyl acetate copolymers.
    [0024] In the present invention, a mixture of a polymer based on propylene, such as polypropylene, a block or random ethylene/propylene copolymer, an α-olefin other than the block or random ethylene/propylene copolymer, and another polymer a -Olefin can be used as the polyolefin resin.
    [0025] As the polyolefin resin, polypropylene is preferably used from the standpoint of flame retardancy.
    [0026] In the following, component (A) to be used in the flame retardant polyolefin resin composition of the present invention is described.
    [0027] The (poly)phosphate compound represented by the general formula (1) to be used as the component (A) in the flame retardant polyolefin resin composition of the present invention is a phosphoric acid salt with ammonia or a triazine derivative represented by the general formula (2).
    [0028] Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by Z1 and Z2 in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-ethyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, and decyl, and examples of the linear or branched alkoxy group having from 1 to 10 carbon atoms include groups derived from these alkyl groups. Examples of the linear or branched alkyl group having from 1 to 6 carbon atoms represented by R5 and R6 in the group -NR5R6 which may be represented by Z1 and Z2 include alkyl groups having from 1 to 6 carbon atoms of the above-listed alkyl groups.
    [0029] Specific examples of the triazine derivative include melamine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3, 5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy- 1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino- 6-mercapto-1,3,5-triazine, and 2-amino-4,6-dimercapto-1,3,5-triazine.
    [0030] Among the (poly)phosphate compounds represented by the general formula (1), a (poly)phosphoric acid salt with melamine or an ammonium (poly)phosphate compound is preferably used as the component (A).
    [0031] Examples of the salt of (poly)phosphoric acid with melamine include melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate, and among these, melamine pyrophosphate, represented by the general formula (1) where n is 2, p is 2, and X1 is melamine, is particularly preferred from the standpoint of flame retardancy. The salt of (poly)phosphoric acid with melamine, for example, in the case of melamine pyrophosphate, can be obtained by reacting sodium pyrophosphate with melamine in an arbitrary reaction ratio with the addition of hydrochloric acid, followed by neutralization with hydroxide of sodium.
    [0032] Ammonium (poly)phosphate compound is ammonium (poly)phosphate alone or a compound including ammonium (poly)phosphate as the major component. As the isolated ammonium (poly)phosphate, commercial products such as Exolit-422 and Exolit-700 produced by Clariant International Ltd., Phos-Chek-P/30 and Phos-Chek-P/40 produced by Monsanto Company can be used, SUMISAFE-P produced by Sumitomo Chemical Co., Ltd., and TERRAJU-S10 and TERRAJU-S20 produced by Chisso Corporation.
    [0033] Examples of the compound including ammonium (poly)phosphate as the main component include ammonium (poly)phosphate which is coated or microencapsulated with a thermosetting resin, ammonium (poly)phosphate whose surface is coated with a melamine monomer , an organic compound containing nitrogen, or the like, (poly)ammonium phosphate treated with a surfactant or silicone, and (poly)ammonium phosphate that has been desolubilized by the addition of melamine or the like during the production of the same. Examples of commercial products of such compounds include Exolit-462 produced by Clariant International Ltd., SUMISAFE PM produced by Sumitomo Chemical Co., Ltd., and TERRAJU-C60, TERRAJU-C70 and TERRAJU-C80 produced by Chisso Corporation.
    [0034] In the following, component (B) to be used in the flame retardant polyolefin resin composition of the present invention is described. The (poly)phosphate compound represented by the general formula (3) to be used as the component (B) in the flame retardant polyolefin resin composition of the present invention is a (poly)phosphoric acid salt with a diamine represented by Y1. The diamine represented by Y1 is R1R2N(CH2)mNR3R4, piperazine, or a diamine containing a piperazine ring.
    [0035] Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R1 to R4 include those having 1 to 5 carbon atoms of the alkyl groups provided as specific examples of the alkyl group represented by Z1 and Z2. Examples of the diamine containing a piperazine ring include compounds resulting from substitution with an alkyl group (preferably having from 1 to 5 carbon atoms) at least a 2-, 3-, 5-, and 6-position piperazine; and compounds resulting from replacement of the amino group located at the 1- and/or 4-position of piperazine with an alkyl group (preferably having from 1 to 5 carbon atoms) substituted with an amino group.
    Specific examples of the diamine represented by Y1 in the general formula (3) include N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethylethylenediamine , N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylene diamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, and 1 ,4-bis(3-aminopropyl)piperazine, and commercial products can be used as all of these compounds.
    [0037] Among the (poly)phosphate compounds represented by the general formula (3), salts of (poly)phosphoric acid with piperazine, i.e., piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate are preferred as the component (B ). Among these, a piperazine polyphosphate, represented by the general formula (3) where q is 1 and Y1 is piperazine, especially piperazine pyrophosphate, is preferred from the standpoint of flame retardancy.
    [0038] The salt of (poly)phosphoric acid with piperazine, for example, in the case of piperazine pyrophosphate, can be easily obtained in the form of a precipitate having low solubility in water by reaction of piperazine with pyrophosphoric acid in water or aqueous solution of methanol. In using a piperazine polyphosphate, a salt obtained from piperazine and polyphosphoric acid consisting of a mixture of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, and other polyphosphoric acid can be used. In this case, the composition of (poly)phosphoric acid, which is a raw material, is not particularly limited.
    [0039] In the flame retardant polyolefin resin composition of the present invention, the content of component (A) is preferably from 1 to 40% by mass from the standpoint of flame retardancy, more preferably from 3 to 30% by mass , even more preferably from 6 to 20% by mass, and most preferably from 8 to 18% by mass.
    [0040] The content of component (B) is preferably from 1 to 50% by mass from the standpoint of flame retardancy, more preferably from 5 to 40% by mass, even more preferably from 8 to 30% by mass, and most preferably from 12 to 25% by mass.
    [0041] In the flame retardant polyolefin resin composition of the present invention, the total content of components (A) and (B), which are flame retardant components, is preferably 15 to 50% by mass, more preferably 20 to 40% by mass, even more preferably from 30 to 40% by mass, and most preferably from 32 to 38% by mass. If the total content is less than 15% by mass, sufficient flame retardant effect cannot be obtained, while if it is greater than 50% by mass, the resin properties may deteriorate.
    [0042] From the point of view of flame retardancy, the ratio of content (mass basis) of component (A) to component (B) is preferably (A)/(B) = 20/80 to 50/50, more preferably (A)/(B) = 30/70 to 50/50, and even more preferably (A)/(B) = 35/65 to 45/55.
    [0043] Preferably, the flame retardant polyolefin resin composition of the present invention further contains zinc oxide which is a flame retardant component as a component (C). Zinc oxide may have been surface treated. Commercial products such as zinc oxide type 1 (produced by Mitsui Mining &Smelting Co., Ltd.), partially coated type zinc oxide (produced by Mitsui Mining &Smelting Co., Ltd.), NANO FINE 50 (zinc oxide from ultrafine particle with an average particle diameter of 0.02 µm; produced by Sakai Chemical Industry Co., Ltd.), and NANO FINE K (silicate coated ultrafine particle zinc oxide having an average particle diameter of 0.02 μm; produced by Sakai Chemical Industry Col, Ltd.) can be used as zinc oxide. The zinc oxide content as composition (C) is more preferably from 0.5 to 10% by mass, and more preferably from 1.2 to 5% by mass.
    [0044] Preferably, the flame retardant polyolefin resin composition of the present invention further contains an anti-drip agent as a component (D). Examples of the anti-drip agent include fluorine-containing anti-drip agents, silicone rubbers, and layered silicates.
    [0045] Examples of the layered silicates include smectite clay minerals such as montmorillonite, saponite, hectorite, beidelite, stynsite, and nontronite; vermiculite, halloysite, swellable mica, and talc; those in which an organic cation, a quaternary ammonium cation, or a phosphonium cation has been interspersed between the layers can be used.
    [0046] Among the anti-drip agents of component (D), fluorine-containing anti-drip agents are preferred; specific examples of fluorine-containing anti-drip agents include fluoro resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, and alkali metal perfluoroalkane sulfonate compounds or alkaline earth metal perfluoroalkane sulfonate compounds like sodium perfluoromethane sulfonate, potassium perfluoro-n-butane sulfonate, potassium perfluoro-tert-butane sulfonate, sodium perfluorooctane sulfonate, and calcium perfluoro-2-ethylhexane sulfonate. Among the aforementioned fluorine-containing anti-drip agents, polytetrafluoroethylene is most preferred from the standpoint of anti-drip property.
    [0047] The anti-collapsing agent content of component (D) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and even more preferably 0.1 to 1% in large scale. If the content is less than 0.01% by mass, the anti-drip effect is not sufficient, while if it is greater than 5% by mass, the resin properties may deteriorate.
    [0048] The flame retardant polyolefin resin composition to be used for the present invention can be prepared only by incorporating components (A) and (B) described above into a polyolefin resin, it is still preferable to incorporate component (C) ) described above and/or component (D). The timing of incorporating components (A) to (D) in the polyolefin resin is not particularly limited; for example, two or more components selected from component groups (A) to (D) may be combined into one portion above and then incorporated into the polyolefin resin or alternatively each component may be separately incorporated into the polyolefin resin. In the case of blending in one portion, each component can be mixed after being crushed respectively or can be crushed after being mixed.
    [0049] Silicone oil can be incorporated into the flame retardant polyolefin resin composition of the present invention in order to inhibit secondary aggregation during incorporation and improve water resistance. Examples of the silicone oil include dimethyl silicone oil in which the polysiloxane side chains and end chains are all methyl groups, methylphenyl silicone oil in which some of the polysiloxane side chains are phenyl groups, hydrogen methyl silicone oil in that some of the polysiloxane side chains are hydrogen, and copolymers thereof, and modified amine, modified epoxy, modified alicyclic epoxy, modified carboxyl, modified carbinol, modified mercapto, modified polyether, modified long chain alkyl, modified fluoroalkyl, high-ester modified fatty acid content, modified high fatty acid amide, and modified silanol, modified diol, modified phenol, and/or modified aralkyl-silicone oils prepared by introducing organic groups into some of the side and/or end chains of the oils silicone can also be used.
    [0050] Specific examples of silicone oil include KF-96 (produced by Shin-Etsu Chemical Co., Ltd.), KF-965 (produced by Shin-Etsu Chemical Co., Ltd.) and KF-968 (produced by Shin -Etsu Chemical Co., Ltd.) as dimethyl-silicone oil; KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.), HMS-151 (manufactured by Gelest, Inc.), HMS-071 ( produced by Gelest, Inc.), HMS-301 (produced by Gelest, Inc.), and DMS-H21 (produced by Gelest, Inc.) as hydrogen-methyl-silicone oil or silicone oil having a hydrogen-methyl structure -polysiloxane; KF-50 (produced by Shin-Etsu Chemical Co., Ltd.), KF-53 (produced by Shin-Etsu Chemical Co., Ltd.), KF-54 (produced by Shin-Etsu Chemical Co., Ltd.), and KF-56 (produced by Shin-Etsu Chemical Co., Ltd.) as examples of methylphenyl silicone oil; X-22-343 (produced by Shin-Etsu Chemical Co., Ltd.), X-22-2000 (produced by Shin-Etsu Chemical Co., Ltd.), KF-101 (produced by Shin-Etsu Chemical Co., Ltd.), Ltd.), KF-102 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd.) as examples of a modified epoxy product; X-22-3701E (produced by Shin-Etsu Chemical Co., Ltd.) as an example of a modified carboxyl product; X-22-4039 (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) as examples of a modified carbinol product; and KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an amine modified product.
    [0051] A silane coupling agent can be incorporated into the flame retardant polyolefin resin composition of the present invention. The silane coupling agent is a compound having a hydrolytic group together with an organic functional group and is represented, for example, by a general formula A-(CH2)k-Si(OR)3. A is an organic functional group, k represents a number from 1 to 3, and R represents a methyl group or an ethyl group. Examples of the organic group of A include an epoxy group, a vinyl group, a methacryl group, an amino group, a mercapto group, etc. As the silane coupling agent to be used for the present invention, those having an epoxy group are particularly preferred.
    [0052] Furthermore, preferably, a lubricant is, as necessary, incorporated into the flame retardant polyolefin resin composition of the present invention. Examples of such a lubricant include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, low molecular weight polyethylene, and polyethylene wax; halogenated hydrocarbon lubricants; fatty acid lubricants with high fatty acid content, and fatty oxy acid; fatty acid amide lubricants such as fatty acid amide and bis fatty acid amide; ester lubricants such as alcohol lower fatty acid esters, polyalcohol fatty acid esters such as glyceride, polyglycol fatty acid esters and fatty acid alcohol esters (ester wax); metal soaps, fatty alcohols, polyhydric alcohols, polyglycol, polyglycerol, partial esters made from fatty acids and polyhydric alcohols, partial ester lubricants made from fatty acids and polyglycols or polyglycerols, (meth)acrylic ester acid copolymers , silicone oil, and mineral oil.
    [0053] The loading of the lubricant in the present invention is preferably from 0.01 to 5% by mass, and more preferably from 0.1 to 1% by mass.
    [0054] Preferably, the flame retardant polyolefin resin composition of the present invention is stabilized, as needed, by the incorporation of a phenolic antioxidant, a phosphorus-based antioxidant, a thioether antioxidant, an ultraviolet absorber, a stabilizer of hindered amine light, an anti-aging agent, or the like.
    [0055] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'- methylenebis(4-methyl-6-tert-butylphenol), 2,2-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2, 2-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy) -5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5- di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4- methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, (3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, tetrakis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)methyl propionate] methane, bis[(3,5-di-tert-but thiodiethylene glycol yl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4-acid acid) glycol ester hydroxy-3-tert-butylphenyl)butyric], bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3 isocyanurate ,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl], 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5- -methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].
    [0056] The loading of such an antioxidant is preferably 0.001 to 5% by mass, and more preferably 0.05 to 3% by mass.
    [0057] Examples of the phosphorus-based antioxidant include trisnonylphenylphosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di(decyl) monophenylphosphite, di(tridecyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenoldiphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert- butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylenediphosphonate , 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, 2.2 '-methylenebis(4,6-di-tert-butylphenyl)-octadecylphosphite, 2,2'-ethylidenebis(4,6-di-te rc-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis tert-butylbenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, and a 2-ethyl-2-butylpropylene glycol phosphite with 2,4,6-tri-tert-butylphenol. The loading of such phosphorus-based antioxidant is preferably from 0.001 to 5% by mass, and more preferably from 0.05 to 3% by mass.
    [0058] Examples of the thioether antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra(β-alkylmercaptopropionic) acid esters. The loading of such thioether antioxidant is preferably 0.001 to 5% by mass, and more preferably 0.05 to 3% by mass.
    [0059] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4- methoxybenzophenone); 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy- 3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) ) benzotriazole; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di- tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxapilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4, 6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. The charge of the ultraviolet absorber is preferably 0.001 to 5% by mass, and more preferably 0.05 to 3% by mass.
    Examples of the hindered amine light stabilizer include hindered amine compounds like 2,2,6,6,-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-stearate piperidyl, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl sebacate), bis(1,2,2,6,6) sebacate - pentamethyl-4-piperidyl), bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis tetracarboxylate (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butane, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6) tetracarboxylate ,6-tetramethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl) tetracarboxylate -1,2,3,4-butane, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4) malonate -hydroxy benzyl), a polycondensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate, a polycondensate of 1,6-bis(2,2,6,6 -tetramethyl-4-piperidylamino) hex year/2,4-dichloro-6-morpholino-s-triazine, a polycondensate of 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino) hexane/2,4-dichloro-6-tert -octylamino-s-triazine, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin -6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl) - 4-piperidyl)amino)-s-triazi n-6-i I]-1,5,8,12-tetraazadodecane, 1,6,11 -tris[2,4-bis(N-butyl-N -(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-( 1,2,2,6,6-pentamethyl-4-piperidyl(I)amino)-s-triazin-6-yl]aminoundecane. The loading of such hindered amine light stabilizer is preferably 0.001 to 5% by mass, and more preferably 0.05 to 3% by mass.
    [0061] Examples of the antiaging agent include naphthylamines, diphenylamines, p-phenyldiamines, quinolines, hydroquinone derivatives, monophenols, thiobisphenols, hindered phenols, and phosphite esters. The loading of such an antiaging agent is preferably from 0.001 to 5% by mass, and more preferably from 0.05 to 3% by mass.
    [0062] In the flame retardant polyolefin resin composition of the present invention, a reinforcing agent may be incorporated as an optional component to such an extent that the effects of the present invention are not harmed. Fibrous, plate-like, granular, or powdery reinforcing agents to be used generally for synthetic resin reinforcing can be used as the reinforcing agent. Specific examples thereof include inorganic fibrous reinforcing agents such as fiberglass, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate hair crystals, aluminum borate hair crystals, magnesium hair crystals, silicon capillary crystals, wollastonite, sepiolite, asbestos, slag fiber, zonolite, elastadite, gypsum fiber, silica fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and fiber of boron; organic fibrous reinforcing agents such as polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, manila hemp, cane, wood pulp, waste paper, waste paper and wool; plate-like and granular reinforcing agents such as glass flakes, non-swellable mica, graphite, metal endsheet, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine powder silicic acid, feldspathic powder , potassium titanate, shirasu flask, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite and white clay. Strengthening agents can be coated or sizing treated with a thermoplastic resin such as an ethylene/vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or alternatively they can be treated with a coupling agent such as amino silane and epoxy silane .
    [0063] In the flame retardant polyolefin resin composition of the present invention, a crystal nucleating agent can further be incorporated as an optional component to such an extent that the effects of the present invention are not harmed. As the crystal nucleating agent, one that has generally been used as a crystal nucleating agent for polymers can be used as appropriate; in the present invention, either an inorganic crystal nucleating agent or an organic crystal nucleating agent can be used.
    [0064] Specific examples of the inorganic crystal nucleating agent may include metal salts such as kaolinite, synthesized mica, clay, zeolite, silica, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and phenyl phosphonate. These inorganic crystal nucleating agents may have been modified with an organic substance in order to improve dispersibility in the composition.
    [0065] Specific examples of the organic nucleating agent may include metal salts of organic carboxylic acids such as sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate , potassium terephthalate, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, stearate of calcium, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, β-naphthalate sodium, and sodium cyclohexanecarboxylate, salts of organic sulfonic acids such as sodium p-toluenesulfonate and sodium sulfoisophthalate, carboxylic amides such as stearamide, ethylenebislauramide, palmitamide, hydroxystearamide, erucamide, and tris(tert-butyramide) of trimesic acid, benzylidenesorbitol and its derivatives, metal salts of phosphorus compounds such as -2,2'-methylenebis(4,6-di-tert-butylphenyl) sodium phosphate, and 2,2-methylbis(4,6-di-tert-butylphenyl) sodium.
    [0066] In the flame retardant polyolefin resin composition of the present invention, a plasticizer may be incorporated as an optional component to such an extent that the effects of the present invention are not harmed. As the plasticizer, those generally used as plasticizers for polymers can be used as appropriate, and examples thereof may include polyester plasticizers, glycerin plasticizers, multivalent carboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.
    [0067] Specific examples of polyester plasticizers may include polyesters composed of acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and resin rosin, and diol components such as propylene glycol, 1,3 - butanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, and diethylene glycol, and polyesters composed of a hydroxycarboxylic acid such as polycaprolactone. These polyesters can be terminated with monofunctional carboxylic acids or monofunctional alcohols, or can be terminated with epoxy compounds.
    [0068] Specific examples of glycerin plasticizers may include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonstearate, glycerin diacetomonooleate, and glycerin monoacetomonolaurate.
    [0069] Specific examples of the multivalent carboxylic acid ester plasticizer may include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate; trimellitate such as tributyl trimellitate, trioctyl trimellitate, and trihexyl trimellitate; adipates such as diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, and benzyl butyl diglycol adipate; citrates such as acetyl triethyl citrate and acetyl tributyl citrate; azelates such as di-2-ethylhexyl azelate; sebacates such as dibutyl sebacate and di-2-ethylhexyl sebacate.
    [0070] Specific examples of polyalkylene glycol plasticizers may include polyethylene glycol, polypropylene glycol, a block copolymer of poly(ethylene oxide-propylene oxide) and/or random copolymer; polytetramethylene glycol; polyalkylene glycols such as ethylene oxide addition polymers of bisphenols, propylene oxide addition polymers of bisphenols, and tetrahydrofuran addition polymers of bisphenols; or terminal-blocked compounds thereof such as terminal epoxy modified compounds, terminal ester modified compounds, and terminal ether modified compounds.
    [0071] The above-mentioned epoxy plasticizer generally indicates epoxy triglyceride composed of alkyl epoxy stearate and soybean oil, etc.; in the present invention, so-called epoxy resins mainly prepared from raw materials, bisphenol A and epichlorohydrin, can also be used.
    [0072] Specific examples of other plasticizers may include benzoates of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, and triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, aliphatic carboxylic acid esters such as butyl oleate , oxyacid esters such as methyl acetylricinolate and butyl acetylricinolate, pentaerythritol, sorbitols, polyacrylates, and paraffins.
    [0073] When a plasticizer is used in the present invention, only one of the plasticizers can be used or alternatively two or more of the plasticizers can be used in combination.
    [0074] For the flame retardant polyolefin resin composition of the present invention, one or more organic or inorganic flame retardants or a non-halogen containing flame retardant aid may further be used as necessary to such an extent that the effects of the present invention are not harmed. Examples of the flame retardant and the flame retardant auxiliary include triazine ring containing compounds, metal hydroxides, phosphoric acid ester flame retardants, condensed phosphoric acid ester flame retardants, phosphate flame retardants, flame retardants containing inorganic phosphorus, dialkyl phosphinates, silicone flame retardants, metal oxides, boric acid compounds, swellable graphite, other inorganic flame retardant auxiliaries, pentaerythritol, and other organic flame retardants.
    [0075] Examples of the triazine ring-containing compound include melamine, amelin, benzoguanamide, acetoguanamine, phthalodiguanamine, melamine cyanurate, butylenediguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimethylamine, trimethylenedimethylamine, tetramethylenedimethylamine, hexamethylenedimelamine, and 1,3-methylamine.
    [0076] Examples of metal hydroxides include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and Kisuma 5A (the registered trademark of magnesium hydroxide produced by Kyowa Chemical Industry Co., Ltd) .
    [0077] Examples of phosphoric acid ester flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, taxoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate , trixylenyl phosphate, octyldiphenyl phosphate, xylenyldiphenyl phosphate, triisopropylphenyl phosphate, 2-ethylhexyldiphenyl phosphate, tert-butylphenyldiphenyl phosphate, bis(tert-butylphenyl)phenyl phosphate, tris-(tert-butylphenyl) phosphate isopropylphenyldiphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, and tris-(isopropylphenyl) phosphate.
    [0078] Examples of the condensed phosphoric acid ester flame retardants include 1,3-phenylene bis(diphenylphosphate), 1,3-phenylene bis(dixylenylphosphate), and bisphenol A bis(diphenylphosphate).
    [0079] Examples of the flame retardant containing inorganic phosphorus include red phosphorus.
    [0080] Examples of the dialkyl phosphinates include aluminum diethyl phosphinate and zinc diethyl phosphinate.
    [0081] Examples of the other inorganic flame retardant auxiliaries include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and hydrotalcite, and their surface treated products. Specifically, various commercial products such as TIPAQUE R-680 (the registered trademark of titanium oxide produced by Ishihara Sangyo Kaisha, Ltd.), Kyowa MAG 150 (the registered trademark of magnesium oxide produced by Kyowa Chemical Industry Co.,) can be used Ltd), DHT-4A (hydrotalcite produced by Kyowa Chemical Industry Co., Ltd), and Alkamiser 4 (the registered trademark of modified zinc hydrotalcite produced by Kyowa Chemical Industry Co., Ltd).
    [0082] In the flame retardant polyolefin resin composition of the present invention, additives commonly used for synthetic resins such as crosslinking agents, antistatic agents, metal soaps, fillers, mist inhibitors, plaque deposition inhibitors, treatment agents Surface agents, fluorescent agents, antifungal agents, sterilizers, foaming agents, metal deactivators, mold release agents, pigments, and processing aids may be incorporated as necessary to such an extent that the effects of the present invention are not impaired.
    [0083] In case of incorporating optional components other than the above-described components (A) to (D) in the flame retardant polyolefin resin composition of the present invention, the charge thereof is not particularly limited as long as the effects of the present invention are not are harmed, preferably being 40% by mass in total.
    [0084] By molding the flame retardant polyolefin resin composition of the present invention, molded articles conforming to the UL94 5VA standard can be obtained. The molding method is not particularly limited and examples thereof include extrusion, calendering, injection molding, lamination, compression molding, and blow molding, and molded articles of various shapes such as resin plates, sheets, films, and profiles.
    [0085] According to the flame retardant polyolefin resin composition of the present invention, it is possible, to conform to UL94 5VA, to preferably use a thickness of 3.2 mm or less, and more preferably a thickness of 1, 6mm or less.
    [0086] The flame retardant polyolefin resin composition of the present invention can be used for such applications as housings (chassis, bodies, exteriors, covers) or electric motor vehicle components, machinery, electrical and electronic equipment, and OA equipment, and automotive interior or exterior materials and can be used for applications where the UL94 5VA standard is required.
    [0087] Specific examples include OA equipment such as printers, personal computers, word processors, keyboards, personal digital assistants (PDA-Persona/Digital Assistant), telephone apparatus, copy machines, fax machines, and ECR (electronic cash registers) ); household appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, iron and kotatsu; audio and visual equipment such as television, video recorders, video cameras, radio-cassette players, tape recorders, mini-discs, CD players, speakers, and liquid crystal displays, and housings and components thereof . Other examples include electrical and electronic components and communication devices such as connectors, relays, capacitors, switches, printed boards, coils, semiconductor sealing materials, LED sealing materials, electrical wire, cables, transformers, deflection coils, distribution, and watches. The composition is preferably also used for high voltage equipment housing applications, hybrid vehicles, and electric motor vehicle applications. EXAMPLES
    [0088] The present invention will be described in detail by way of examples and comparative examples. The present invention, however, is not limited in any way by the examples. [Examples 1 to 15] Production and Evaluation of Flame Retardant Polyolefin Resin Compositions
    [0089] The flame retardant polyolefin resin compositions were prepared incorporating the components listed in Table 1 or Table 2. Each of the resulting resin compositions was extruded at 220°C to produce granulates, and then injection molding was performed using the granulates under the conditions of a mold temperature of 50°C and a resin temperature of 220°C, giving a bar sample having dimensions of 127mm x 13mm x 1.6mm and a bar sample having dimensions 127mm x 13mm x 3.2mm. On the other hand, press molding was carried out at 220°C using the same granulates, giving a plate sample having dimensions 150mm x 150mm x 1.6mm and a plate sample having dimensions 150mm x 150mm x 3.2 mm. [Comparative Examples 1 to 9] Production and Evaluation of Flame Retardant Polyolefin Resin Compositions
    [0090] Comparative flame retardant polyolefin resin compositions were prepared in the same manner as in Examples 1 to 15 except that the components listed in table 3 were used, and then comparative samples were prepared from the resulting resin compositions.
    [0091] Component (A) and component (B) listed in tables 1 to 3 were produced by the following methods. [Production Example 1] Component (A): melamine pyrophosphate
    [0092] Produced by the reaction of pyrophosphoric acid and melamine in a molar ratio of 1:2. [Production example 2] Component (B): piperazine pyrophosphate
    [0093] Produced by reaction of pyrophosphoric acid and piperazine in a molar ratio of 1:1.
    [0094] For the samples obtained in the examples or comparative examples, the flame retardancy test, the heat deflection temperature test (HDT), and the Izod impact strength test described below were performed. The results are shown in table 1 to table 3. The formulations shown in table 1 through table 3 are all expressed on a mass basis. <Flame Retardance Test>
    [0095] For the 1.6mm samples and 3.2mm samples prepared as above, a bar test and a plate test were performed as flame retardancy assessments in accordance with UL94 5V flame retardancy standard. flame. 5VA is greater than 5VB in flame retardancy, and the case where neither 5VA nor 5VB was achieved is called non-5V. <Thermal deflection temperature (HDT)>
    [0096] Using the granules prepared as above, injection molding was carried out under conditions of a mold temperature of 50°C and a resin temperature of 220°C to prepare a sized sample of 80 x 10 x 4 mm, whose thermal deflection temperature (°C) was then measured according to ISO75 (load: 0.45 MPa). <Charpy impact resistance>
    [0097] Impact resistance was examined under ambient temperature conditions in accordance with ISO179. [Table 1]
    : Polypropylene, melt flow rate = 8 g/10 min 2: Tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (ADK STAB AO-60 produced by ADEKA CORPORATION) * 3: Tris(2,4-di-tert-butylphenyl)phosphite (ADK STAB 2112 produced by ADEKA CORPORATION) *4: Calcium stearate *5: Glycerin monostearate [Table 21
    : Polypropylene, melt flow rate = 8 g/10 min 2: Tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (ADK STAB AO-60 produced by ADEKA CORPORATION) * 3: Tris(2,4-di-tert-butylphenyl)phosphite (ADK STAB 2112 produced by ADEKA CORPORATION) * 4: Calcium stearate * 5: Glycerin monostearate [Table 3]

    : Polypropylene, melt flow rate = 8 g/10 min *2: Tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (ADK STAB AO-60 produced by ADEKA CORPORATION) *3: Tris(2,4-di-tert-butylphenyl)phosphite (ADK STAB 2112 produced by ADEKA CORPORATION) *4: Calcium stearate *5: Glycerin monostearate
    权利要求:
    Claims (6)
    [0001]
    1. Flame retardant polyolefin resin composition characterized by comprising the following components (A) and (B) as flame retardant components for a polyolefin resin and meeting UL94 5VA standard at a thickness of 1.6mm or less, the flame retardant polyolefin resin composition further comprising the following anti-drip agent, the total content of components (A) and (B) in the flame retardant polyolefin resin composition being 32 to 38% by mass, the ratio of content (mass basis) of component (A) to component (B) being (A)/(B) = 35/65 to 50/50, anti-drip agent content being 0.1 to 1 % by mass: a component (A): a (poly)phosphate compound represented by the following general formula (1) a component (B): a (poly)phosphate compound represented by the following general formula (3) anti-drip agent: polytetrafluoroethylene
    [0002]
    2. Flame retardant polyolefin resin composition according to claim 1, characterized in that it further comprises zinc oxide as a component (C).
    [0003]
    3. Flame retardant polyolefin resin composition according to any one of claims 1 or 2, characterized in that it uses as component (A) a melamine pyrophosphate of the general formula (1) wherein n is 2, p is 2 , and X1 is a melamine of the general formula (2) where Z1 and Z2 are each -NH2.
    [0004]
    4. Flame retardant polyolefin resin composition according to any one of claims 1 to 3, characterized in that it uses as component (B) a piperazine polyphosphate of the general formula (3) wherein q is 1 and Y1 is piperazine .
    [0005]
    5. Flame retardant polyolefin resin composition according to claim 4, characterized by the fact that piperazine polyphosphate is piperazine pyrophosphate.
    [0006]
    6. Housing or component of an electric motor vehicle, machine, or electrical and electronic equipment, characterized in that they are obtained from the flame retardant polyolefin resin composition according to any one of claims 1 to 5.
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    同族专利:
    公开号 | 公开日
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    EP2789653A1|2014-10-15|
    JP5793068B2|2015-10-14|
    BR112014009263A2|2017-04-18|
    US20140288217A1|2014-09-25|
    EP2789653A4|2015-07-22|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-27| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-13| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011267220A|JP5793068B2|2011-12-06|2011-12-06|Flame retardant polyolefin resin composition|
    JP2011-267220|2011-12-06|
    PCT/JP2012/080265|WO2013084725A1|2011-12-06|2012-11-22|Flame retardant polyolefin resin composition|
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