JP2007119543A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which comprises a polyolefin resin and a metal hydroxide, has an improved copper-staining resistant property, and is therefore suitable as an electric wire-coating material. <P>SOLUTION: This resin composition comprises (a) 100 pts.mass of a polyolefin-based resin, (b) 10 to 350 pts.mass of magnesium hydroxide and/or aluminum hydroxide, (c) 0.001 to 10 pts.mass of N,N-bis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionyl]hydrazine, (d) 0.001 to 10 pts.mass of a salicylamide compound represented by the general formula (I) (R is H, a 1 to 12C alkyl or a 1 to 12C alkoxy), and (e) 0.001 to 5 pts.mass of at least one selected from higher fatty acid amide compounds and higher fatty acid monoglycerides. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition, and more specifically, a polyolefin-based resin to which harmful gas containing magnesium hydroxide and / or aluminum hydroxide, a specific hydrazide compound, a specific salicylic acid amide compound and a specific lubricant is added. The present invention relates to a resin composition suitable as an electric wire coating material because it does not occur and deterioration due to heavy metals such as copper is suppressed.

  Electronic computers, OA equipment, electric wires for industrial equipment such as vehicles, consumer electronic equipment such as audio, video and personal computers, indoor wiring, etc. have high flame resistance without generating harmful gases during combustion. Is now required. Accordingly, it has been demanded that these electric wires have high flame retardancy without generating harmful gas during combustion. As a flame retardant method that meets such demands, a method of adding a large amount of magnesium hydroxide, which is a non-halogen flame retardant, to a thermoplastic resin such as polyolefin is known.

  However, a resin composition that is made flame retardant by adding a large amount of magnesium hydroxide to a thermoplastic resin such as polyolefin, has mechanical properties, thermal stability, and heat aging when applied to insulated wires and tubes. It is known that the property (thermal stability at a relatively low temperature) and the like are significantly reduced.

  Moreover, based on the idea that the decrease in thermal stability is caused by contact with trace amounts of heavy metals contained in inorganic fillers or copper wires, in order to prevent such harmful effects caused by heavy metals, Agents such as melamine, guanamine, benzoguanamine, 3-salicyloylaminotriazole, N, N′-dibenzylidene (oxalic dihydrazide), N-salicyloyl-N′salicylidenehydrazine, bissalicyloylhydrazine, bis [Β- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionyl] hydrazine, bis (salicyloylhydrazide) dodecanedioate, bis [β- (3,5-ditertiarybutyl-4-hydroxy [Phenyl) propionyloxyethyl] oxalic acid diamide and the like have been used.

  However, when a metal deactivator was used alone, it was not satisfactory in practical use.

  For example, Patent Document 1 discloses an ethylene polymer, an organic halogenated flame retardant having an oxygen index of 23 or more, 3-salicyloylamino-1,2,4-triazole, and N, N′-bis [3- A heat-resistant and flame-retardant insulated wire containing a compound such as (3,5-di-t-alkyl-4-hydroxyphenyl) propionyl] hydrazine and hydrotalcite has been proposed. Specific two hindered piperidine compounds, and N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine or N-salicyloylamino Electron beam crosslinking comprising a resin composition containing -1,2,4-triazole, hindered phenol antioxidant, thio antioxidant and metal soap A transparent heat-resistant tube is proposed, and in Patent Document 3, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [3- (3,5 A polyolefin insulated wire formed by adding a heavy metal deactivator such as -di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and hydrotalcite and extruding it onto a conductor has been proposed. In polyolefin, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] Add a heavy metal deactivator such as hydrazine and one or a mixture selected from magnesium hydroxide, aluminum hydroxide, calcium hydroxide Polyolefin insulated wires formed by extrusion coating on the body have been proposed, but these patent documents do not describe the use of higher fatty acid amide compounds or higher fatty acid monoglycerides, and specific heavy metals. There is no suggestion of having a remarkable effect by combining inactivating agents.

  For this reason, there has been a demand for the development of a resin composition that can provide a wire coating material that does not generate harmful gases and has excellent heat aging resistance.

JP-A-5-2927 JP-A-6-176649 Japanese Patent Laid-Open No. 7-73748 Japanese Patent Laid-Open No. 7-320548

  Accordingly, an object of the present invention is to provide a resin composition suitable as a wire coating material by improving the copper contamination of a resin composition comprising a polyolefin resin and a metal hydroxide.

  As a result of intensive studies, the present inventors add a specific hydrazide compound, a specific salicylic acid amide compound and a higher fatty acid amide compound or a higher fatty acid monoglyceride to a resin composition comprising a polyolefin resin and a metal hydroxide. It was found that the resin composition obtained by this can achieve the above object.

  The present invention has been made on the basis of the above knowledge. (A) 100 parts by mass of a polyolefin-based resin, (b) 10 to 350 parts by mass of magnesium hydroxide and / or aluminum hydroxide, (c) N, N-bis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyl] hydrazine 0.001 to 10 parts by mass, (d) salicylic acid amide compound 0.001 to 10 represented by the following general formula (I) It provides a resin composition characterized by containing 0.001 to 5 parts by mass of part by mass and (e) at least one selected from higher fatty acid amide compounds and higher fatty acid monoglycerides.

  The resin composition of the present invention does not generate harmful gases and has excellent heat aging resistance when in contact with heavy metals such as copper, and is particularly suitable for use as a wire coating material.

  Hereinafter, the resin composition of the present invention will be described in detail.

  The polyolefin resin which is the component (a) used in the present invention is a polymer containing ethylene or propylene as a main component. Ethylene polymers include ethylene homopolymers such as high pressure polyethylene, linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE); ethylene-α-olefin copolymers, ethylene-vinyl acetate copolymers (EVA), ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer (EEA), Examples include ethylene-ethyl methacrylate copolymers and ethylene-vinyl alcohol copolymers. As propylene-based polymers, a known α-olefin stereoregular catalyst such as a Ziegler-Natta type catalyst is usually used. Mainly propylene homopolymer obtained by polymerization or propylene A random copolymer of propylene and other α-olefins such as ethylene, butene-1,4-methylpentene-1, hexene-1, heptene-1, octene-1, and the like. Examples thereof include a propylene homopolymer, an ethylene-propylene copolymer, a propylene-butene-1 copolymer, and an ethylene-propylene-butene-1 terpolymer.

  Among these polyolefin resins, an ethylene polymer, in particular, an ethylene homopolymer or an ethylene homopolymer and an ethylene-vinyl acetate copolymer (EVA) blend is excellent in various mechanical properties. Since a resin composition is obtained, it is preferable.

The magnesium hydroxide or aluminum hydroxide as the component (b) in the present invention can be any as long as it is generally used as a flame retardant, but the average particle size is preferably 0.1 to 15 μm, more preferably Has a specific surface area according to the BET method of preferably 1 to 20 m ² / g, more preferably 3 to 8 m ² / g. Commercially available magnesium hydroxide is surface-treated with a surfactant such as sodium stearate and sodium lauryl sulfonate in advance to improve dispersibility and fluidity, and these commercially available products can also be used. .
In particular, magnesium hydroxide is preferable because it has a higher decomposition temperature than aluminum hydroxide, and is less likely to cause foaming during the production of a molded product.

  The amount of magnesium hydroxide or aluminum hydroxide used is 10 to 350 parts by weight, preferably 80 to 300 parts by weight, with respect to 100 parts by weight of the polyolefin-based resin. In the case of using more than 350 parts by mass, the fluidity is lowered in the processing of the molded product, and the rigidity, dimensional stability, impact strength, etc. of the molded product are decreased. .

  N, N-bis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyl] hydrazine used as component (c) in the present invention is Irganox MD1024 (Ciba Specialty Chemicals). (Commercially available) can be used.

  The usage-amount of the said hydrazide compound is 0.001-10 mass parts with respect to 100 mass parts of polyolefin resin, Preferably it is 0.01-5 mass parts, More preferably, it is 0.01-1 mass part. If the amount used is less than 0.001 part by mass, the effect is not sufficiently exerted, and if it is more than 10 parts by mass, there are disadvantages such as a decrease in insulation or blooming.

  In the salicylic acid amide compound represented by the above general formula (I), which is the component (d) used in the present invention, in the general formula (I), as the alkyl group having 1 to 12 carbon atoms represented by R, , Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, hexyl, heptyl, octyl, isooctyl, sec-octyl, 2-ethylhexyl, nonyl, isononyl, decyl Straight chain or branched alkyl groups such as R 1 and C 1-12 alkoxy groups represented by R include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonyloxy, Examples thereof include linear or branched groups such as decyloxy.

  Examples of the salicylic acid amide compound include N- (1,2,4-triazol-3-yl) salicylamide, N- (1,2,4-triazol-3-yl) -3-methylsartylamide, N -(1,2,4-triazol-3-yl) -5-methylsalicylamide, N- (1,2,4-triazol-3-yl) -5-tert-octylsalicylamide, N- (1, 2,4-triazol-3-yl) -4-methoxysalicylamide and the like, and in particular, N- (1,2,4-triazol-3-yl) sartylamide is preferable. CDA-1 (Asahi Denka Kogyo Co., Ltd.) is listed. These salicylic acid amide compounds can be used singly or in combination of two or more.

  The usage-amount of the said salicylic acid amide compound is 0.001-10 mass parts with respect to 100 mass parts of polyolefin resin, Preferably it is 0.01-5 mass parts, More preferably, it is 0.01-1 mass part. If the amount used is less than 0.001 part by mass, the effect is not sufficiently exerted, and if it is more than 10 parts by mass, there are disadvantages such as a decrease in insulation or blooming.

  In the higher fatty acid amide compound or higher fatty acid monoglyceride which is the component (e) used in the present invention, examples of the higher fatty acid include lauric acid, myristic acid, parimtic acid, stearic acid, oleic acid, 12-hydroxystearic acid, Examples thereof include aliphatic carboxylic acids having 12 or more carbon atoms, such as linoleic acid, ricinoleic acid, behenic acid, erucic acid, and montanic acid. Also, a mixture mainly composed of these higher aliphatic carboxylic acids, such as soybean oil fatty acid, Fatty acids from natural fats and oils such as beef tallow fatty acid, rapeseed oil fatty acid, linseed oil fatty acid and castor oil fatty acid may be used.

  The higher fatty acid amide compounds used in the present invention include higher fatty acid (alkyl or alkenyl) amides and alkylene bis (higher fatty acid amides) represented by the following general formula (II).

Therefore, the higher fatty acid amide compounds used in the present invention include lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, erucic acid amide, montalic acid amide, stearyl erlic acid amide, oleyl. Palmitic acid amide, methylene bis (stearic acid amide), ethylene bis (myristic acid amide), ethylene bis (palmitic acid amide), ethylene bis (stearic acid amide), etc. preferable.
The higher fatty acid molyglyceride used in the present invention is mainly composed of the higher fatty acid and glycerol monoester compound. The commercially available higher fatty acid monoglyceride contains diglyceride and triglyceride in addition to monoglyceride, but in the present invention, it can be used as it is without any purification as long as it contains about 50% by mass or more of the monoglyceride component.

  The amount of these higher fatty acid amide compounds or higher fatty acid monoglycerides used is 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, with respect to 100 parts by mass of the polyolefin resin. If the amount used is less than 0.001 part by mass, the effect is not sufficiently obtained, and if it exceeds 5 parts by mass, the physical properties may be adversely affected, which is not preferable.

  These higher fatty acid amide compounds or higher fatty acid monoglycerides are known as lubricants for synthetic resins, but other lubricants such as waxes, higher fatty acids, higher fatty acid metal salts, higher fatty acids and monohydric alcohols. Esters or higher fatty acid triglycerides show little improvement in terms of thermal stability, and the effects of the higher fatty acid amide compounds or higher fatty acid monoglycerides used in the present invention are extremely specific.

  It is preferable that the resin composition of the present invention contains (f) a polyol compound because the initial physical properties of the resin can be improved. Examples of the polyol compound include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol stearic acid half ester, bis (dipentaerythritol) adipate, and glycerin. Among them, dipentaerythritol is preferable because it provides particularly excellent physical properties.

  The amount of the polyol compound used is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. When the amount used is less than 0.001 part by mass, the effect is hardly seen, and when it exceeds 5 parts by mass, not only is there no effect due to the increase, but also plate-out occurs during processing. May cause adverse effects.

  In addition, a known plasticizer can be used to improve the processability of the resin composition of the present invention and the physical properties of the molded product. Examples of the known plasticizer include dibutyl phthalate, butyl hexyl phthalate, and diheptyl phthalate. , Phthalate plasticizers such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyl diglycol) adipate; Phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, tri Phosphate plasticizers such as octyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1, 3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc., and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipine Polyester plasticizer using acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and if necessary monohydric alcohol, monocarboxylic acid as a stopper; other, tetrahydride Phthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenylene polycarboxylic acid plasticizer An agent or the like can be blended.

  Further, the resin composition of the present invention further includes various additives used as usual additives for olefinic resin fats, such as phosphorus, phenolic or sulfur antioxidants, ultraviolet absorbers, hindered amines. System light stabilizers, organosilicon compounds, and the like can also be blended.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, bird Uril trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl) -4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4 , 6-Diamylphenyl)]-isopropylidene diphenyl phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5- Methylphenol) diphosphite, hexa (tride) 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- Examples thereof include 10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4,6-di) Tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3) -Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris ( 3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trime Tylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4- Hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3- Tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane], triethylene glycol bis [β -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic acid esters.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 ′-(2 2-methacryloyloxyethoxyethoxy) benzophenone, 2-hydroxybenzophenones such as 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tertiary) Butyl-5-methylphenyl) -5-chlorobenzotriazole, -(2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7-9mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy -3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxy) 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of phenyl) benzotriazole; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-Hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5 Triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-acryloyloxyethoxy) 2- (2-hydroxyphenyl) -1,3,5-triazines such as phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy Substituted oxanilides such as cis-4′-dodecyloxanilide; cyano such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Examples thereof include acrylates.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2 6,6-tetramethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditertiary Butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2, 6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro- -Morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine Polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-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-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- ( 2,2,6,6-tetramethyl-4-piperidyl) amino-s-tri Gin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazine -6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxy] Carbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.

  Examples of the organosilicon compound include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethoxymethylsilane, and γ-methacryloxypropyldimethylchlorosilane. Etc. can be illustrated.

  In addition, the resin composition of the present invention further includes additives that are usually used for polyolefin resins as necessary, for example, fillers, colorants, crosslinking agents, antistatic agents, plate-out preventing agents, surface treating agents. , Lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents, and the like.

  Further, the resin composition of the present invention can be used regardless of the processing method. For example, calendering, roll processing, extrusion molding, melt rolling, pressure molding, paste processing, powder processing It can be suitably used for molding processing, foam molding processing and the like.

  The resin composition of the present invention comprises a building material such as a wall material, a floor material, a window frame, and wallpaper; a wire covering material; an automotive interior and exterior material; an agricultural material such as a house and a tunnel; and a fish food packaging material such as a wrap and a tray. It can be used as miscellaneous goods such as paints, hoses, pipes, sheets and toys, but is particularly suitable for use as a wire covering material for electric wires and cables.

When the wire coating material is produced using the resin composition of the present invention, a single screw extruder, a multi screw extruder, a Banbury mixer, a roll, a kneader, a heatable Henschel mixer type high-speed fluid mixer, etc. can be used. Yes, a wire coating material can be produced by melt-kneading various blended components at a temperature equal to or higher than the melting point of the thermoplastic resin.
As the use of the resin composition of the present invention, it is effective in application to insulated wires (including cables) and insulated tubes because it itself has excellent flame retardancy and heat aging resistance and high initial tensile strength and electrical characteristics. It is useful for various molded parts in fields where high flame retardancy is required.
In particular, in order to produce an insulated wire from the resin composition of the present invention, a technique such as extrusion coating is applied on the core conductor to form a coating layer made of the resin composition of the present invention, and then an electron beam or the like. Manufactured by ionizing radiation. In order to produce an insulating tube, particularly a heat-shrinkable insulating tube, the resin composition of the present invention is formed into a tube shape, then irradiated with an ionizing ray such as an electron beam, and then heated above the softening point of the tube. Manufactured by expanding in the radial direction by applying an internal pressure in a state and cooling and fixing.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by the following Example.

Example 1
The following formulation was pre-kneaded with a Banbury mixer, rolled for 10 minutes at 140 ° C. and 20 rpm, and the resulting sheet was pressed at 170 ° C. for 5 minutes to prepare a press sheet. A prescribed test piece was prepared from the press sheet and evaluated as follows.
Using the obtained test piece, a tensile test was performed according to JIS K 7118, and the breaking strength (MPa) and the elongation (%) were measured. In addition, a tensile test was similarly performed on a test piece which had been subjected to accelerated deterioration for 216 hours using a sunshine weatherometer with rain at 63 ° C.
In addition, the following compound was mixed using a Banbury mixer, and the mixture was mixed with a 40 mm extruder using a 40 mm extruder with a thickness of about 0 on the outer periphery of a conductor obtained by twisting seven tin-plated copper wires having an outer diameter of 0.32 mm. An insulated wire was prepared by coating to 5 mm.
The obtained insulated wire was put in a 120 ° C. gear oven, and the crack generation time (hour) was measured to evaluate [heat aging resistance].
The results are shown in [Table 1] and [Table 2].

(Composition) Mass parts Linear low density polyethylene resin 100
(Novatech LL UF240)
Magnesium hydroxide (Kisuma 5A) 100
Tetrakis (3-4-hydroxy-3,5-ditertiary 0.5
Butylphenyl) propionyloxymethyl) methane bis (2,2,6,6-tetramethyl-4-0.2
Piperidyl) sebacate 2- (2-hydroxy-3,5-ditert-butyl 0.2
Phenyl) -5-chlorobenzotriazole ethylenebis (stearic acid amide) 0.3
Test compounds [Table 1] and [Table 2] [Table 1] and [Table 2]

Example 2
A tensile test (original) and a heat aging resistance test were conducted in the same manner as in Example 1 using the following blend.
The results are shown in [Table 3].

(Blend) Mass parts Linear low density polyethylene resin 80
(Novatech LL UF240)
Ethylene-vinyl acetate copolymer 20
(Nihon Unicar; PES-400)
Magnesium hydroxide (Kisuma A) 100
Tetrakis (3-4-hydroxy-3,5-ditertiary 0.5
Butylphenyl) propionyloxymethyl) methane bis (2,2,6,6-tetramethyl-4-0.2
Piperidyl) sebacate 2- (2-hydroxy-3,5-ditert-butyl 0.2
Phenyl) -5-chlorobenzotriazole N, N-bis [3- (3,5-ditert-butyl-4-hydro 0.1
Xylphenyl) propionyl] hydrazine N- (1,2,4-triazol-3-yl) sartylamide 0.1
Dipentaerythritol 0.1
Test compound [Table 3] [Table 3]

As is clear from the above examples and comparative examples, when a hydrazide compound is not used for a resin composition comprising a polyolefin resin, a metal hydroxide, etc., heat aging resistance is insufficient due to copper contamination. , N, N-bis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyl] hydrazine alone is improved to some extent, but the improvement effect is still insufficient. Similarly, when only the salicylic acid amide compound is used, it is completely insufficient.
Further, even when the salicylic acid amide compound and the hydrazide compound are combined, a sufficient synergistic effect cannot be obtained except when the salicylic acid amide compound of the present invention and the hydrazide compound of the present invention are combined.
Even when the salicylic acid amide compound of the present invention and the hydrazide compound of the present invention are combined, the effect is not sufficient when the higher fatty acid amide compound or higher fatty acid monoglyceride is not used.

  In contrast, N, N-bis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyl] hydrazine and a resin composition comprising a polyolefin-based resin, a metal hydroxide, and the like When a salicylic acid amide compound is combined and a higher fatty acid amide compound or a higher fatty acid monoglyceride is used, a synergistic effect is exhibited and heat aging resistance is significantly improved by copper contamination. Furthermore, physical properties can be improved by using dipentaerythritol in combination.

Claims (9)

(A) 100 parts by mass of a polyolefin-based resin, (b) 10 to 350 parts by mass of magnesium hydroxide and / or aluminum hydroxide, (c) N, N-bis [3- (3,5-ditert-butyl-4 -Hydroxyphenyl) propionyl] hydrazine 0.001 to 10 parts by mass, (d) 0.001 to 10 parts by mass of a salicylic acid amide compound represented by the following general formula (I), and (e) a higher fatty acid amide compound and a higher fatty acid monoglyceride A resin composition comprising 0.001 to 5 parts by mass of at least one member selected from the group consisting of:

  The resin composition according to claim 1, wherein the component (a) is an ethylene polymer.   (B) The resin composition of Claim 1 or 2 whose compounding quantity of a component is 80-300 mass parts.   (B) A component is magnesium hydroxide, The resin composition in any one of Claims 1-3.   The resin composition according to any one of claims 1 to 4, wherein the component (d) is N- (1,2,4-triazol-3-yl) salicylamide.   (E) Component is ethylenebis (stearic acid amide), The resin composition in any one of Claims 1-5.   Furthermore, the resin composition in any one of Claims 1-6 formed by containing 0.001-5 mass parts of (f) at least 1 type of a polyol compound.   The resin composition according to claim 7, wherein the component (f) is dipentaerythritol. The resin composition according to any one of claims 1 to 8, which is used for electric wire coating.