JP2012207072A - Anti-static polyolefin-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin-based resin molded article whose anti-static performance and whose stability of the performance are excellent in spite of the small amount of content of an anti-static agent, and a polyolefin-based resin composition with which the molded article can be obtained.SOLUTION: In the polyolefin-based resin composition, at least a compound represented by general formula (1) is blended by 0.001-1 pts.mass to 100 pts.mass of a polyorefin-based resin. The molded article is obtained by molding the composition. In the general formula (1), Rdenotes a 9 to 21C alkyl group; and Rdenotes a hydrogen atom or a methyl group.

Description

  The present invention relates to a polyolefin resin composition and a molded product thereof, and particularly relates to a polyolefin resin composition excellent in antistatic property and storage stability and a molded product thereof.

  Polyolefin resins are widely used in various molded products such as films, sheets, and structural parts because they have excellent molding processability, heat resistance, mechanical properties, and the like, and have an advantage of low specific gravity. Moreover, since it has the property of being excellent in electrical insulation, it is frequently used for components of electrical products. However, since the polyolefin resin is too insulating, there is a problem that it is charged by friction or the like, and the charged polyolefin resin attracts surrounding dust and dust, and thus the appearance of the resin molded product is impaired. Arise. In addition, among electronic products, for example, a precision device such as a computer may not be able to work normally due to charging. Furthermore, there is a problem caused by electric shock that not only gives an unpleasant feeling to a person when an electric shock occurs from the resin to the human body, but also may cause an explosion accident in the presence of flammable gas or dust.

  In order to solve such a problem, the polyolefin resin has been conventionally treated to prevent charging. The most common antistatic treatment method is a method of adding an antistatic agent to a polyolefin resin. As such antistatic agents, there are a coating type that is applied to the surface of a resin molded body, and a kneading type that is added when processing and molding a resin. In addition, since a large amount of organic material is applied to the surface, there is a problem that the material touching the surface is contaminated.

  From such a viewpoint, conventionally, a kneading type antistatic agent and a composition thereof have been mainly studied. For example, a surfactant such as glycerin fatty acid ester is kneaded and used, a polyalkylene glycol derivative having a structure similar to a phenol resin (Patent Documents 1 and 2), or a polyetheresteramide antistatic agent (Patent Document 3). And 4) have been proposed. Furthermore, the use of ethylene oxide adducts of aliphatic amines, fatty alcohols, and fatty acid esters of polyhydric alcohols has also been proposed (Patent Document 5). However, when these are used, a sufficient antistatic effect cannot be obtained unless the addition amount is large, and the antistatic effect and sustainability are insufficient.

  On the other hand, an imidazoline compound has also been proposed as an antistatic agent (Patent Document 6). However, in the case of this compound, the performance cannot be obtained unless the styrene resin is used in combination with an alkane sulfonate. The knowledge of the present invention cannot be obtained from the literature.

JP 2000-34330 A JP 2002-60734 A Japanese Patent No. 3227118 Japanese Patent No. 3427261 JP-A-8-199157 JP-A-6-49303

Accordingly, a first object of the present invention is to provide a polyolefin resin composition capable of forming a polyolefin resin molded article having excellent antistatic performance despite its low content of antistatic component. is there.
A second object of the present invention is to provide a polyolefin-based resin molded article that is less likely to cause a drop in commercial value due to surface contamination due to static electricity or dust adhesion.

但し、式（１）中のＲ^１は炭素原子数９〜２１のアルキル基を表し、Ｒ^２は水素原子又はメチル基を表す。 As a result of intensive studies to solve the above problems, the present inventors have found an antistatic agent capable of imparting sufficient antistatic performance to a polyolefin-based resin molded product, although the amount used is small, and this The invention has been completed.
That is, the present invention comprises a polyolefin resin composition comprising at least 0.001 to 1 part by mass of the following component (A) with respect to 100 parts by mass of a polyolefin resin, and the composition: A molded body formed by molding;
(A) Component: Compound represented by the following general formula (1)

However, ^{R 1} in the formula (1) represents an alkyl group having 9 to 21 carbon atoms, ^{R 2} represents a hydrogen atom or a methyl group.

  According to the present invention, an excellent antistatic effect can be obtained with the addition of a small amount of antistatic agent, so that the antistatic agent does not exude excessively on the surface of the resin molded body, and the periphery that touches the surface of the resin molded body. A polyolefin-based resin composition that is not contaminated with organic substances can be provided.

  Hereinafter, the present invention will be described in detail. First, the polyolefin resin used in the present invention will be described.

  Examples of the polyolefin resin used in the polyolefin resin composition of the present invention include polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, syndiotactic polypropylene, hemiiso Α-olefin polymers such as tactic polypropylene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / Α-olefin copolymer such as propylene block or random copolymer.

  In the present invention, an α-olefin / propylene block or a random (co) polymer, or a mixture of these with another α-olefin polymer can be used. Among these, in the present invention, it is particularly preferable to use polypropylene, an ethylene / propylene block, or a random copolymer.

但し、式（１）中のＲ^１は炭素原子数の９〜２１のアルキル基を表し、Ｒ^２は水素原子又はメチル基を表す。 Next, the component (A) represented by the following general formula (1) used in the present invention will be described.

However, ^{R 1} in the formula (1) represents an alkyl group having 9 to 21 carbon atoms, ^{R 2} represents a hydrogen atom or a methyl group.

Specific examples of the compound represented by the general formula (1) include the following compound Nos. Although 1-10 are mentioned, this invention is not limited to these compounds.

  The blending amount of the component (A) in the polyolefin resin composition of the present invention is 0.001 to 1 part by mass, preferably 0.01 to 0.5 part by mass with respect to 100 parts by mass of the polyolefin resin. Parts, more preferably 0.05 to 0.4 parts by mass. The component (A) may be a single compound or a combination of two or more.

  The method of blending the component (A) into the polyolefin resin is not particularly limited, and a commonly used method can be appropriately selected and used. For example, it may be blended by kneading with a roll, kneading with a bumper, mixing / kneading with an extruder or a kneader.

  In addition, the compound represented by the general formula (1) which is the component (A) of the present invention may be added to the thermoplastic resin as it is, or may be added after impregnating the carrier if necessary. When the carrier is impregnated, it may be heated and mixed as it is, or, if necessary, a method of diluting with an organic solvent, impregnating the carrier, and then removing the solvent.

  As the carrier, those conventionally known as fillers and fillers for synthetic resins, or flame retardants and light stabilizers that are solid at room temperature can be used. Examples of such a carrier include calcium silicate powder, silica powder, talc powder, alumina powder, titanium oxide powder, or those obtained by chemically modifying the surface of these carriers, and solids among flame retardants and antioxidants described later. And the like. In the present invention, among these carriers, a carrier whose surface is chemically modified is preferable, and a silica powder whose surface is chemically modified is particularly preferable. These carriers preferably have an average particle size of 0.1 to 100 μm, particularly preferably 0.5 to 50 μm.

  If necessary, the polyolefin resin composition of the present invention contains a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, etc. It can be further added to stabilize the resin composition.

  Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-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-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) Nol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tertiary) 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-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Ditertiarybutyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] methane, thiodiethyleneglycol Bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3 3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methyl) Benzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] And ndecane and triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

  The amount of these phenolic antioxidants added is preferably 0.001 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, 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) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 6-ditert-butylphenyl) fluorophosphite; tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol, phosphite of 2,4,6-tritert-butylphenol and the like. The addition amount of these phosphorus antioxidants is preferably 0.001 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate; and pentaerythritol tetra (β-alkylmercaptopropionic acid). Examples include esters. The amount of these thioether-based antioxidants added is preferably 0.001 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chloro Benzotriazole, 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- (2 such as' -methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole '-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl- Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy- Substituted oxanilides such as 4′-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenylacrylate And cyanoacrylates such as methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 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, 2- (2-hydroxy-4-propoxy-5-methylphenyl) And triaryltriazines such as -4,6-bis (2,4-ditert-butylphenyl) -s-triazine. The addition amount of these ultraviolet absorbers is preferably 0.001 to 30 parts by mass, particularly preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  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) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-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 / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl- 4-piperidylamino) Xanthane / 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-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-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-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2 6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] hindered amine compounds such as aminoundecanoic the like. The amount of these hindered amine light stabilizers added is preferably 0.001 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polyolefin resin.

  In addition, it is preferable to add a known neutralizing agent to the polyolefin resin composition of the present invention as necessary in order to neutralize the residual catalyst in the polyolefin resin. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or fatty acids such as ethylene bis (stearamide), ethylene bis (12-hydroxystearamide), and stearamide. Examples include amide compounds. These neutralizing agents may be used alone or in combination.

  If necessary, at least one selected from the group consisting of alkali metal or alkaline earth metal salts, surfactants and (polymer) antistatic agents may be added to the polyolefin resin composition of the present invention. Thereby, the antistatic property of the polyolefin resin composition can be further improved.

  Examples of the alkali metal or alkaline earth metal salt include monocarboxylic acid or dicarboxylic acid having 1 to 20 carbon atoms (for example, formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), and sulfonic acid having 1 to 20 carbon atoms. (For example, methanesulfonic acid, p-toluenesulfonic acid, etc.), salts of organic acids such as thiocyanic acid with alkali metals or alkaline earth metals; hydrohalic acids (for example, hydrochloric acid, hydrobromic acid, etc.), bromide Preferred examples include salts of inorganic acids such as hydrogen acid, perchloric acid, sulfuric acid and phosphoric acid. Among these, in the present invention, it is preferable to use halides such as lithium chloride, sodium chloride and potassium chloride, acetates such as potassium acetate, and perchlorates such as potassium perchlorate. The addition amount of these alkali metal or alkaline earth metal salts in the polyolefin resin composition is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 100 parts by mass of the thermoplastic resin. It is preferable that it is -2 mass parts.

  As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used. Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyethylene oxide, fatty acid esters of glycerin And polyhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, and the like.

  Examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates, and alkyl sulfonates. Sulfonates such as paraffin sulfonates; phosphate ester salts such as higher alcohol phosphates, and the like, and cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. It is done. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines.

The above surfactants may be used alone or in combination of two or more, but in the present invention, it is preferable to use an anionic surfactant, and in particular, alkylbenzene sulfonate, alkyl It is preferable to use sulfonates such as sulfonates and paraffin sulfonates.
The addition amount of the surfactant in the polyolefin resin composition is preferably 0.001 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. .

As said polymer antistatic agent, polymer type antistatic agents, such as well-known polyether ester amide, can be used, for example. Examples of these polyether ester amides include polyether ester amides composed of polyoxyalkylene adducts of bisphenol A described in JP-A-7-10989. Moreover, in this invention, the block polymer which has a repeating structure whose coupling unit of a polyolefin block and a hydrophilic polymer block is 2-50 can be used. Examples of such a block polymer include those described in US Pat. No. 6,552,131.
The addition amount of the other polymer antistatic agent in the polyolefin resin composition of the present invention is preferably 0 to 40 parts by mass, particularly 5 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is preferable that

In the polyolefin-based fat composition of the present invention, a compatibilizing agent can be further added as necessary in order to improve the compatibility between the component of the present invention and other components and the polyolefin-based resin. As such a compatibilizing agent, a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group, for example, A polymer described in JP-A-3-258850, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or a block polymer having a polyolefin part and an aromatic vinyl polymer part Etc.
The amount of the compatibilizing agent added in the polyolefin resin of the present invention is preferably 0.1 to 15 parts by mass, particularly 1 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. preferable.

  In the polyolefin resin composition of the present invention, an aromatic carboxylic acid metal salt, an alicyclic alkyl carboxylic acid metal salt, aluminum p-tert-butylbenzoate, an aromatic phosphate metal salt, di Nucleating agents such as benzylidene sorbitols; metal soap, hydrotalcite, triazine ring-containing compound, metal hydroxide, phosphate ester flame retardant, condensed phosphate ester flame retardant, phosphate flame retardant, inorganic phosphorus flame retardant Flame retardants, (poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, other organic flame retardant aids; fillers Pigment, lubricant, foaming agent and the like may be further added.

  Examples of the triazine ring-containing compound include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimeramine and the like can be mentioned.

  Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.

  Examples of the phosphate ester flame retardant include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl Phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t -Butylphenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (isopropylphosphate) Le) diphenyl phosphate, tris - (isopropylphenyl) phosphate and the like.

  Examples of the condensed phosphate ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.

  Examples of the (poly) phosphate flame retardant include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate. .

Examples of the other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface-treated products thereof. As a commercial item, for example, TIPAQUE
R-680 (titanium oxide: trade name made by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: trade name made by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: Kyowa Chemical Industry Co., Ltd.) Product name), Alkamizer 4 (zinc-modified hydrotalcite: product name manufactured by Kyowa Chemical Industry Co., Ltd.), and the like.

  Examples of the other organic flame retardant aids include pentaerythritol.

  In addition, in the polyolefin resin composition of the present invention, additives that are usually used for synthetic resins, for example, a crosslinking agent, an antifogging agent, a plate-out preventing agent, a surface treatment agent, a plasticizer, and a lubricant, are used as necessary. , Flame retardants, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, etc., in a range that does not impair the effects of the present invention And can be blended.

  By molding the polyolefin resin composition of the present invention, the polyolefin resin molded body of the present invention having excellent antistatic performance and durability can be obtained. The molding method is not particularly limited, and examples thereof include extrusion molding, calendering molding, injection molding, roll molding, compression molding, blow molding, and the like, such as resin plates, sheets, films, fibers, and irregular shaped products. It is possible to manufacture a molded article having a shape of

  The polyolefin-based resin composition of the present invention and the molded product thereof are electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, It can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, and musical instruments.

  Specific uses of the polyolefin resin composition of the present invention and molded articles thereof include printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers). ), Office equipment such as calculators, electronic notebooks, cards, holders, stationery and OA equipment; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, and kotatsu; TV, VTR, video AV equipment such as cameras, radio cassettes, tape recorders, mini-discs, CD players, speakers, liquid crystal displays; connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulating materials, LED encapsulating materials, electric wires, cables, transformers , Deflection yokes, distribution boards, clocks and other electrical and electronic parts and communication equipment; Interior and exterior materials for vehicles: Films for plate making, adhesive films, bottles, food containers, food packaging films, pharmaceutical / pharmaceutical wrap films, product packaging films, agricultural films, agricultural sheets, greenhouse films, etc. Used for.

  The polyolefin-based resin composition of the present invention and the molded product thereof are further provided with a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover, Mattress cover, airbag, insulation material, suspension hand, suspension band, electric wire coating material, electrical insulation material, paint, coating material, upholstery material, flooring material, corner wall, carpet, wallpaper, wall covering material, exterior material, Interior materials, roofing materials, deck materials, wall materials, pillar materials, flooring materials, fence materials, frames and repetitive shapes, windows and door shapes, slabs, glazing, terraces, balconies, soundproofing plates, heat insulating plates, window materials Automobiles, vehicles, ships, aircraft, buildings, housing and building materials and civil engineering materials; clothing, curtains, sheets, non-woven fabrics, plywood, synthetic fiber boards, carpets, doormats, sheets, buckets, ho Vinegar, container, glasses, bags, cases, goggles, skis, rackets, tents, of musical instruments, household goods or sports equipment, are used in various applications and the like.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the following examples and the like, “%” and “ppm” are based on mass unless otherwise specified.
[Examples 1 to 16, Comparative Examples 1 to 4]
As the component (A), the following compound No. 1, no. 2, Compound No. 6 and compound no. Using the compound of No. 7, a polyolefin resin composition having the composition shown in Tables 1 and 2 below was prepared. Using the obtained polyolefin resin composition, a test piece was prepared under the following conditions, and performance evaluation was performed under the following conditions. The results are shown in Tables 1-4. For comparison, the following comparative compound-1 and glycerin monostearate (trade name Riquemar S-100, manufactured by Riken Vitamin Co., Ltd.) were used.

<Test specimen preparation condition-1>
The polypropylene resin composition blended based on the blending amount described in Table 1 is granulated under the conditions of 230 ° C. and 6 kg / hour using a Ikekai-made twin screw extruder (PCM 30, 60 mesh included), Pellets were obtained.
The obtained pellets were molded using a horizontal injection molding machine (NEX80: Nissei Plastics Industries) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C., and a test piece of 100 mm × 100 mm × 3 mm Got.

<Test specimen preparation condition-2>
The linear low-density polyethylene resin composition blended based on the blending amount described in Table 2 was subjected to conditions of 190 ° C. and 6 kg / hour using a twin screw extruder (PCM30, 60 mesh) made by Ikegai Co., Ltd. To obtain pellets.
The obtained pellets were molded using a horizontal injection molding machine (NEX80: Nissei Plastic Industry's trade name) under processing conditions of a resin temperature of 190 ° C. and a mold temperature of 40 ° C., and a 100 mm × 100 mm × 3 mm test piece Got.

<Surface specific resistance value (SR value)>
About the obtained test piece, it preserve | saved on the conditions of 50% of humidity at 25 degreeC or 80 degreeC immediately after shaping | molding process. After storage for 1 day (24 hours), the surface resistivity (Ω / □) was measured under the same atmosphere using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 100 V and an applied time of 1 minute. . The measurement was performed for 5 points, and the average values are shown in Tables 1 to 4.

＊１：商品名ノバテックＰＰ ＭＡ３ 日本ポリプロ（株）製
＊２：テトラキス［３−（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオニルオキシメチル］メタン（アデカスタブＡＯ−６０ （株）ＡＤＥＫＡ製）
＊３：トリス（２，４−ジ第三ブチルフェニル）ホスファイト（アデカスタブ２１１２ （株）ＡＤＥＫＡ）
＊４：ステアリン酸カルシウム
＊５：商品名リケマールS-100 理研ビタミン（株）製

* 1: Product name Novatec PP MA3 manufactured by Nippon Polypro Co., Ltd. * 2: Tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Adekastab AO-60 ADEKA Corporation) Made)
* 3: Tris (2,4-ditert-butylphenyl) phosphite (ADK STAB 2112 ADEKA)
* 4: Calcium stearate * 5: Brand name Riquemar S-100 manufactured by Riken Vitamin Co., Ltd.

＊１：商品名ノバテックＰＰ ＭＡ３ 日本ポリプロ（株）製
＊２：テトラキス［３−（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオニルオキシメチル］メタン（アデカスタブＡＯ−６０ （株）ＡＤＥＫＡ製）
＊３：トリス（２，４−ジ第三ブチルフェニル）ホスファイト（アデカスタブ２１１２ （株）ＡＤＥＫＡ）
＊４：ステアリン酸カルシウム
＊５：商品名リケマールS-100 理研ビタミン（株）製

* 1: Product name Novatec PP MA3 manufactured by Nippon Polypro Co., Ltd. * 2: Tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Adekastab AO-60 ADEKA Corporation) Made)
* 3: Tris (2,4-ditert-butylphenyl) phosphite (ADK STAB 2112 ADEKA)
* 4: Calcium stearate * 5: Brand name Riquemar S-100 manufactured by Riken Vitamin Co., Ltd.

＊１：商品名ＰＥＳ−１２０ 日本ユニカー（株）製
＊２：テトラキス［３−（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオニルオキシメチル］メタン（アデカスタブＡＯ−６０ （株）ＡＤＥＫＡ製）
＊３：トリス（２，４−ジ第三ブチルフェニル）ホスファイト（アデカスタブ２１１２ （株）ＡＤＥＫＡ）
＊４：ステアリン酸カルシウム
＊５：商品名リケマールS-100 理研ビタミン（株）製

* 1: Trade name PES-120 manufactured by Nippon Unicar Co., Ltd. * 2: Tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Adeka Stub AO-60 ADEKA Corporation) Made)
* 3: Tris (2,4-ditert-butylphenyl) phosphite (ADK STAB 2112 ADEKA)
* 4: Calcium stearate * 5: Brand name Riquemar S-100 manufactured by Riken Vitamin Co., Ltd.

＊１：商品名ＰＥＳ−１２０ 日本ユニカー（株）製
＊２：テトラキス［３−（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオニルオキシメチル］メタン（アデカスタブＡＯ−６０ （株）ＡＤＥＫＡ製）
＊３：トリス（２，４−ジ第三ブチルフェニル）ホスファイト（アデカスタブ２１１２ （株）ＡＤＥＫＡ）
＊４：ステアリン酸カルシウム
＊５：商品名リケマールS-100 理研ビタミン（株）製

* 1: Trade name PES-120 manufactured by Nippon Unicar Co., Ltd. * 2: Tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Adeka Stub AO-60 ADEKA Corporation) Made)
* 3: Tris (2,4-ditert-butylphenyl) phosphite (ADK STAB 2112 ADEKA)
* 4: Calcium stearate * 5: Brand name Riquemar S-100 manufactured by Riken Vitamin Co., Ltd.

  As is clear from the results of Tables 1 to 4, the surface specific resistance value of the molded product of the present invention is orders of magnitude smaller than the surface specific resistance value of the molded product of the comparative example, and this difference is high in storage temperature. It was confirmed that the image appears more remarkably. From this, it was confirmed that the molded product of the present invention is superior in the stability of the surface resistivity of the comparative molded product.

  The polyolefin-based resin composition of the present invention and the molded product thereof are electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, Since it can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, and musical instruments, it is extremely useful industrially.

Claims (4)

A polyolefin resin composition comprising 0.001 to 1 part by mass of the following component (A) based on 100 parts by mass of a polyolefin resin;
(A) Component: Compound represented by the following general formula (1)

However, ^{R 1} in the formula (1) represents an alkyl group having 9 to 21 carbon atoms, ^{R 2} represents a hydrogen atom or a methyl group. The polyolefin resin composition according to claim 1, wherein the compound represented by the general formula (1) is at least one selected from the group consisting of the compounds of the following compounds No. 1 to 10;

  The polyolefin resin composition according to claim 1 or 2, wherein the polyolefin resin is any one of polypropylene, an ethylene / propylene block, or a random copolymer.   A molded article comprising the polyolefin-based resin composition according to any one of claims 1 to 3.