JP2017002101A - Fire retardant polyolefin resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin composition having fire retardancy, no concern about odor derived from fire retardant and capable of manufacturing a molded article having deodorant effect to ammonia or hydrogen sulfide.SOLUTION: There is provided a fire retardant polyolefin resin composition containing (A) a polyolefin resin, (B) an organic halogen fire retardant, (C) antimony oxide, (D) zinc oxide and (E) silicon oxide with content of the (B) component of 1 to 50 pts.wt. based on 100 pts.wt. of the (A) component, content of the (C) component of 0.5 to 10 pts.wt. based on 100 pts.wt. of the (A) component, content of the (D) component of 0.13 to 1.9 pts.wt. based on 100 pts.wt. of the (A) component, and content of the (E) component of 0.37 to 5.1 pts.wt. based on 100 pts.wt. of the (A) component.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant polyolefin resin composition.

  Synthetic resins such as polyolefin, polystyrene, polyamide, polyester, polyether, polycarbonate, phenol resin, and epoxy resin are used in a wide range of fields as molding materials. However, since these resins are flammable, safety against fire is required. In particular, polyolefins used for automobile parts, home appliance parts, building materials, etc. are ignited and burnt easily, so that various flame retardants are blended to make them highly flame retardant.

  The flame retardant includes halogen-based flame retardants and non-halogen-based flame retardants. Particularly, polyolefins have extremely low flame retardant properties, so that decabromodiphenyl oxide, brominated bisphenol A derivatives having a high flame retardant effect, Halogen flame retardants such as brominated bisphenol S derivatives and brominated isocyanurate derivatives are used.

However, halogen-based flame retardants have a strong odor, and resin compositions containing halogen-based flame retardants have been used in living spaces such as toilets and kitchens and in automobiles, in recent years, in order to improve living standards and to provide a comfortable living environment. There was a problem that could not be used for space applications.
In addition, materials that deodorize life odors such as hydrogen sulfide and ammonia are beginning to be demanded, and the development of such materials is also demanded.

  Here, as a means for deodorizing a resin composition containing a flame retardant or a means for deodorizing hydrogen sulfide, etc., chemical deodorization by preparation of a deodorant used in a deodorant spray, a fragrance, etc. Is mentioned. Specific means for chemical deodorization include inorganic deodorants represented by metal oxides such as titanium oxide and zinc oxide, organic deodorants represented by nitrogen-containing compounds such as phthalocyanine, and rosemary. Natural compound-based deodorants represented by plant extracts such as extracts can be mentioned as examples, and a method for imparting a deodorizing function by kneading these deodorants into a plastic material resin is known ( Patent Documents 1-3).

JP-A-2005-42060 JP-A-9-170177 JP 2002-029003 A

  An object of the present invention is to provide a polyolefin resin composition that has flame retardancy, does not mind the odor derived from a flame retardant, and can produce a molded product having a deodorizing effect on ammonia and hydrogen sulfide. It is.

According to the present invention, the following flame retardant polyolefin resin composition is provided.
1. A flame retardant polyolefin-based resin composition containing the following components (A) to (E) in the following content.
[component]
(A) Polyolefin resin (B) Organic halogen flame retardant (C) Antimony oxide (D) Zinc oxide (E) Silicon oxide [content]
(B) Component content is 1 to 50 parts by weight per 100 parts by weight of component (A) Component (C) is 0.5 to 10 parts by weight per 100 parts by weight of component (A) (D ) Component content is 0.13 to 1.9 parts by weight with respect to 100 parts by weight of component (A) Component (E) is 0.37 to 5.1 parts with respect to 100 parts by weight of component (A) Part by weight The (B) organic halogen flame retardant is selected from tetrabromobisphenol A flame retardant, tetrabromobisphenol S flame retardant, tris (brominated neopentyl) phosphate, brominated alkyl cyanurate, and brominated alkyl isocyanurate. 2. The flame-retardant polyolefin resin composition according to 1, which is at least one kind.
3. 3. The flame retardant polyolefin resin composition according to 1 or 2, which is produced by adding a mixture of the (D) zinc oxide and (E) silicon oxide.
4). The flame-retardant polyolefin resin composition according to any one of 1 to 3, wherein the content of the (C) antimony oxide is 3 to 7 parts by weight with respect to 100 parts by weight of the component (A).
5. The flame retardant polyolefin resin composition according to any one of 1 to 4, wherein the (B) organic halogen flame retardant includes both a tetrabromobisphenol A flame retardant and a tetrabromobisphenol S flame retardant.
6). A molded product obtained by molding the flame-retardant polyolefin resin composition according to any one of 1 to 5.

  According to the present invention, there is provided a flame retardant polyolefin resin composition that has flame retardancy, does not mind the odor derived from a flame retardant, and can produce a molded product having a deodorizing effect on ammonia and hydrogen sulfide. Can be provided.

The flame retardant polyolefin resin composition of the present invention contains the following components (A) to (E) in the following content.
[component]
(A) Polyolefin resin (B) Organic halogen flame retardant (C) Antimony oxide (D) Zinc oxide (E) Silicon oxide [content]
(B) Component content is 1 to 50 parts by weight per 100 parts by weight of component (A) Component (C) is 0.5 to 10 parts by weight per 100 parts by weight of component (A) (D ) Component content is 0.13 to 1.9 parts by weight with respect to 100 parts by weight of component (A) Component (E) is 0.37 to 5.1 parts with respect to 100 parts by weight of component (A) Parts by weight

The flame-retardant polyolefin-based resin composition of the present invention having the above composition (hereinafter sometimes simply referred to as “the composition of the present invention”) exhibits high flame retardancy and has no odor derived from a flame retardant, It is a composition having a deodorizing effect on ammonia and hydrogen sulfide, which are typical malodorous components of life odor.
Hereinafter, each component of the composition of the present invention will be described.

(A) Polyolefin resin Polyolefin resin is a polymer containing monomer units derived from olefins.
Examples of polyolefin resins include polyethylene resins, ethylene-carboxylic acid alkenyl ester copolymer resins, ethylene-unsaturated carboxylic acid alkyl ester copolymer resins, polypropylene resins, polybutene resins, and poly (4-methyl- 1-pentene) resin and the like are exemplified. These may be used individually by 1 type and may be used in combination of 2 or more type.
Of the above-mentioned polyolefin resins, polyethylene resins or polypropylene resins are preferred.

When the polyolefin resin is a polypropylene resin, the polypropylene resin can be composed of one or more selected from a homopolymer of propylene, a copolymer containing propylene as a main component, and the like.
The copolymer having propylene as a main component is not particularly limited. For example, a random copolymer of propylene and one or more α-olefins other than propylene, and propylene and one or two. Examples thereof include block copolymers with α-olefins other than propylene.
Examples of α-olefins other than propylene include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned.
Here, “mainly propylene” in the “copolymer having propylene as a main component” means that the propylene-derived structure occupies most in the copolymer.

  The propylene homopolymer is preferably a propylene homopolymer having a melt mass flow rate of 0.1 to 200 g / 10 min at 230 ° C. from the viewpoint of light weight and moldability. Further, from the viewpoint of the rigidity and impact resistance of the resin composition, the melt mass flow rate at 230 ° C. is more preferably 0.2 to 60 g / 10 min or less.

  The propylene-based copolymer is preferably a propylene copolymer having a melt mass flow rate of 0.1 to 200 g / 10 min at 230 ° C. from the viewpoint of light weight and moldability. Further, from the viewpoint of the rigidity and impact resistance of the resin composition, the melt mass flow rate at 230 ° C. is more preferably 0.2 to 60 g / 10 min or less.

When the polyolefin-based resin is a polyethylene-based resin, the polyethylene-based resin can be composed of one or more selected from an ethylene homopolymer, a copolymer having ethylene as a main component, and the like.
The copolymer containing ethylene as a main component is not particularly limited. For example, a random copolymer of ethylene and one or more α-olefins other than ethylene, and ethylene and one or two. Examples thereof include block copolymers with α-olefins other than ethylene.
Examples of α-olefins other than ethylene include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned.
Here, “ethylene-based” in the “copolymer having ethylene as a main component” means that the ethylene-derived structure is the most occupied in the copolymer.

Examples of the ethylene homopolymer include low density polyethylene, linear low density polyethylene, linear low density polyethylene, and high density polyethylene. From the viewpoint of light weight and moldability, the density is 0.910. An ethylene homopolymer having a melt mass flow rate of 0.01 to 200 g / 10 min at 190 ° C. is preferably −0.965 g / cm ³ . The melt mass flow rate at 190 ° C. is more preferably 0.01 to 60 g / 10 min or less.
When the melt mass flow rate at 190 ° C. of the ethylene homopolymer is within the above range, there is no possibility of causing problems in the fluidity of the resulting resin composition and the surface appearance of the molded body.

From the viewpoint of light weight and moldability, the ethylene-based copolymer is preferably an ethylene copolymer having a melt mass flow rate of 0.01 to 200 g / 10 min at 190 ° C., and a melt at 190 ° C. An ethylene copolymer having a mass flow rate of 0.01 to 60 g / 10 min is more preferable.
When the melt mass flow rate at 190 ° C. of the copolymer containing ethylene as a main component is within the above range, there is no possibility that the fluidity of the resulting resin composition and the surface appearance of the molded product will be defective.

(B) Organic halogen flame retardant An organic halogen flame retardant means an organic flame retardant containing halogen, and preferably contains bromine and chlorine. That is, the organic halogen flame retardant is preferably an organic flame retardant containing bromine or chlorine. More preferably, the organic halogen flame retardant is an organic flame retardant containing bromine.

Examples of organic halogen flame retardants include hexabromobenzene, pentabromobenzene, pentabromotoluene, tetrabromotoluene, tetrabromoxylene, tribromoxylene, tetrabromophenol, tetrabromoresorcin, tribromopyrogalol, brominated biphenyl, Brominated aromatic compounds such as brominated diphenyl ether, brominated diphenylthioether, brominated naphthalene derivatives; hexachlorobenzene, pentachlorobenzene, pentachlorotoluene, tetrachlorotoluene, tetrachloroxylene, trichloroxylene, pentachlorophenol, tetra Chlorinated aromatic compounds such as chlorresorcin, trichloropyrogal, chlorinated diphenyl ether, chlorinated diphenyl thioether, chlorinated naphthalene derivatives; tetra Chlorinated aliphatic compounds such as lorlobromobutane, pentachloropentane, hexachlorohexane, pentachloroheptane, chlorinated paraffin; chlorinated bisphenol A, brominated bisphenol A (brominated aromatic ether), chlorinated bisphenol A Halogenated bisphenol A derivatives such as (chlorinated aromatic ether); brominated bisphenol S, chlorinated bisphenol S, brominated bisphenol S (brominated aromatic ether), chlorinated bisphenol S (chlorinated aromatic ether), etc. Halogenated bisphenol S derivatives; brominated alkyl cyanurates such as tris (dibromopropyl) cyanurate, bis (dibromopentyl) cyanurate; tris (dibromopropyl) isocyanurate, bis (dibromopropyl) isocyanurate, tris Brominated alkyl isocyanurates such as tetrabromopentyl) isocyanurate; Chlorinated alkyl cyanurates such as tris (dichloropropyl) cyanurate, bis (dichloropropyl) cyanurate, tris (tetrachloropentyl) cyanurate; Tris (dichloropropyl) ) Chlorinated alkyl isocyanurates such as isocyanurate, bis (dichloropropyl) isocyanurate, tris (tetrachloropentyl) isocyanurate; tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate, tris [2 , 2-bis (bromomethyl) propyl] phosphate, tris (brominated neopentyl) phosphate such as tris (2-bromomethyl-2-methylpropyl) phosphate, and the like.
These organic halogen flame retardants may be used alone or in combination of two or more.

  The halogenated bisphenol A derivatives are bis (dibromopropyl ether) -tetrabromobisphenol A, bis (dibromoethyl ether) -tetrabromobisphenol A, bis (dibromobutyl ether) -tetrabromobisphenol A, bis (tribromobutyl ether)- A tetrabromobisphenol A flame retardant which is a tetrabromobisphenol A derivative such as tetrabromobisphenol A or bis (tetrabromobutyl ether) -tetrabromobisphenol A is preferred.

  The halogenated bisphenol S derivatives are bis (dibromopropyl ether) -tetrabromobisphenol S, bis (dibromoethyl ether) -tetrabromobisphenol S, bis (dibromobutyl ether) -tetrabromobisphenol S, bis (tribromobutyl ether)- A tetrabromobisphenol S flame retardant which is a tetrabromobisphenol S derivative such as tetrabromobisphenol S and bis (tetrabromobutyl ether) -tetrabromobisphenol S is preferred.

  Among the above organic halogen flame retardants, since the flame retardant effect is remarkable, tetrabromobisphenol A flame retardant, tetrabromobisphenol S flame retardant, tris (brominated neopentyl) phosphate, brominated alkyl cyanurate, And one or more selected from brominated alkyl isocyanurates.

More preferably, the organic halogen flame retardant includes both a tetrabromobisphenol A flame retardant and a tetrabromobisphenol S flame retardant.
When the composition of the present invention contains both a tetrabromobisphenol A flame retardant and a tetrabromobisphenol S flame retardant as a flame retardant, a molded product having excellent heat resistance can be obtained.

The content of the organic halogen flame retardant is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin. is there.
When the content of the organic halogen flame retardant is less than 1 part by weight with respect to 100 parts by weight of the (A) polyolefin resin, there is a possibility that sufficient flame retardancy may not be obtained. On the other hand, when the content of the organic halogen flame retardant is more than 50 parts by weight with respect to 100 parts by weight of the polyolefin, there is a possibility that the mechanical properties of the obtained molded product may be lowered and the specific gravity may be increased, and the composition stability may be increased. There is a risk that the manual kneading operation becomes difficult.

When the organic halogen flame retardant is a tetrabromobisphenol A flame retardant and a tetrabromobisphenol S flame retardant, the tetrabromobisphenol A flame retardant is 1 to 25 weights per 100 parts by weight of the polyolefin resin (A). Part and tetrabromobisphenol S flame retardant are preferably contained in an amount of 1 to 25 parts by weight.
When the organohalogen flame retardant is a tetrabromobisphenol A flame retardant and a tetrabromobisphenol S flame retardant, and the content of these flame retardants is in the above range, a molded product having excellent heat resistance can be obtained.
(A) More preferably, 3 to 15 parts by weight of tetrabromobisphenol A flame retardant and 2 to 10 parts by weight of tetrabromobisphenol S flame retardant are contained per 100 parts by weight of polyolefin resin. Most preferably, 3 to 9 parts by weight of tetrabromobisphenol A flame retardant and 2 to 9 parts by weight of tetrabromobisphenol S flame retardant are contained per 100 parts by weight of polyolefin resin. In addition, it is most preferable that the tetrabromobisphenol A flame retardant and the tetrabromobisphenol S flame retardant contain 5 to 15 parts by weight in total with respect to 100 parts by weight of the (A) polyolefin resin.
When the organohalogen flame retardant is a tetrabromobisphenol A flame retardant and a tetrabromobisphenol S flame retardant, and the content of these flame retardants is in the above range, a molded product having further excellent heat resistance can be obtained.

(C) Antimony oxide Antimony oxide functions as a flame retardant aid in the composition of the present invention, and is generally available such as antimony trioxide (Sb ₂ O ₃ ) and antimony pentoxide (Sb ₂ O ₅ ). If there is, it can be used without any particular limitation. These antimony oxides may be used alone or in combination of two or more.
Here, antimony trioxide is most preferred. Antimony trioxide can have the highest flame retardancy.
The average particle diameter of the antimony oxide is preferably 0.01 μm to 5 μm, more preferably 0.1 μm to 3 μm.

Content of antimony oxide is 0.5-10 weight part with respect to 100 weight part of (A) polyolefin resin, 3-7 weight part is preferable, and 3-6 weight part is more preferable.
When the content of antimony oxide is less than 0.5 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin, a sufficient synergistic effect with the flame retardant may not be obtained and the flame retardant effect may be reduced. . On the other hand, when the content of antimony oxide is more than 10 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin, the flame retardant effect is not improved, and the mechanical properties may be lowered. Economical.

(D) Zinc oxide and (E) Silicon oxide Zinc oxide and silicon oxide function as a deodorant in the composition of the present invention, and any of ordinary powders can be used.
The average particle diameter of zinc oxide is preferably 1 μm to 100 μm, and more preferably 1 μm to 10 μm.
The average particle size of silicon oxide is preferably 1 μm to 100 μm, and more preferably 1 μm to 10 μm.
The silicon oxide is preferably silicon dioxide.
Moreover, it is preferable that the raw material to be added is a mixture of zinc oxide and silicon oxide.

The zinc oxide and silicon oxide in the composition may be an amorphous composite of zinc oxide and silicon oxide in which they are complexed with each other, and quaternary ammonium ions further complexed with quaternary ammonium ions, It may be an amorphous composite of zinc oxide and silicon oxide. Further, it may be an amorphous composite of zinc oxide and silicon oxide in which zinc oxide and silicon oxide used as raw materials are combined with each other, and further includes a quaternary ammonium ion, an oxide formed by further combining a quaternary ammonium ion. It may be an amorphous composite of zinc and silicon oxide.
The quaternary ammonium ion is a monovalent cation in which four carbon bonds are directly connected to a nitrogen atom. For example, an alkyltrimethylammonium ion, a dialkyldimethylethylammonium ion, an alkyldimethylethylammonium ion, an alkyldimethyl Examples include benzylammonium ion, alkylpyridinium ion, alkylquinolium ion, alkylamidopropyldimethylbenzylammonium ion, and benzyldimethyl p- (1,1,3,3-tetramethylbutylphenoxy) ethylammonium ion.

  When the zinc oxide and silicon oxide in the composition are an amorphous composite of quaternary ammonium ion, zinc oxide and silicon oxide, the quaternary ammonium ion is a gelatinous substance (oxidized oxide of zinc oxide and silicon oxide). Amorphous composite of zinc and silicon oxide) is incorporated in the form of ions or silicate in the gel skeleton to form a composite.

  An amorphous composite of zinc oxide and silicon oxide can be obtained by reacting an aqueous silicate solution with an aqueous zinc salt solution. An amorphous composite of quaternary ammonium ions, zinc oxide and silicon oxide can be obtained by reacting an aqueous silicate solution and an aqueous zinc salt solution in an aqueous solution system containing quaternary ammonium ions.

The preparation of the amorphous composite preferably includes a hydrogen ion concentration (pH) adjustment step using a metal salt aqueous solution that generates a metal hydroxide in a weakly acidic to neutral region. The adjustment can be performed by mixing a silicate aqueous solution, a zinc salt aqueous solution, and a metal salt aqueous solution that generates a metal hydroxide in a weakly acidic to neutral region.
Here, the weakly acidic to neutral region is in the range of pH 5 to 7, and preferably in the range of pH 6 to 7. Examples of the metal salt contained in the metal salt aqueous solution that generates a metal hydroxide in a weakly acidic to neutral region include polyaluminum chloride (PAC), aluminum chloride, titanyl sulfate, zirconium sulfate, zirconium oxychloride, tin chloride, sulfuric acid. Examples include magnesium and aluminum sulfate.

Content of zinc oxide is 0.13-1.9 weight part with respect to 100 weight part of (A) polyolefin resin, and 0.25-1.5 weight part is preferable.
If the content of zinc oxide is less than 0.13 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin, there is a possibility that sufficient deodorizing performance may not be obtained.
On the other hand, if the content of zinc oxide exceeds 1.9 parts by weight with respect to 100 parts by weight of (A) polyolefin resin, flame retardancy and heat resistance may be reduced.
Content of silicon oxide is 0.37-5.1 weight part with respect to 100 weight part of (A) polyolefin resin, and it is preferable that it is 0.6-3.7 weight part.
If the content of silicon oxide is less than 0.37 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin, there is a possibility that sufficient deodorizing performance may not be obtained.
On the other hand, when the content of silicon oxide exceeds 5.1 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin, flame retardancy and heat resistance may be reduced.
The total content of zinc oxide and silicon oxide is preferably 0.5 to 7 parts by weight, more preferably 0.8 to 5 parts by weight, based on 100 parts by weight of the (A) polyolefin resin.
If the total content of zinc oxide and silicon oxide is 0.5 parts by weight or more with respect to 100 parts by weight of the (A) polyolefin resin, the deodorizing performance is higher. On the other hand, if the total content of zinc oxide and silicon oxide is 7 parts by weight or less with respect to 100 parts by weight of (A) polyolefin resin, higher flame retardancy and higher heat resistance can be obtained.

The composition of the present invention may contain (A) a polyolefin resin, (B) an organic halogen flame retardant, (C) antimony oxide, (D) zinc oxide, and (E) silicon oxide. (A ′) Other resin component, (F) Antioxidant, (G) Ultraviolet absorber, (H) Lubricant, (I) Softener, (J) Antistatic agent, (K) One or more selected from metal deactivators, (L) antibacterial / antifungal agents, (M) pigments, and (N) crystal nucleating agents may be included.
Hereinafter, these optional components will be described.

(A ′) Other resin component In addition to the above-mentioned (A) polyolefin resin, one or more other resin components selected from vinyl resins, diene rubbers, and thermoplastic elastomers may be further added.
Examples of the vinyl resin include (meth) acrylic resin [1 selected from (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Species or (co) polymers of two or more monomers, etc.) and styrene resins [polystyrene, AS resin, ABS resin, styrene-butadiene resin, styrene-maleic anhydride resin, styrene-acrylic ester resin, HIPS, etc. ] Etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the diene rubber include butadiene rubber, butyl rubber, chloroprene rubber, isoprene rubber, nitrile rubber [acrylonitrile-butadiene copolymer and the like] and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the thermoplastic elastomer include styrene-butadiene block copolymer (SBR), styrene-butadiene-styrene triblock copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-isoprene. Examples thereof include rubber (SIR) and derivatives obtained by hydrogenating these. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of other resin components is not particularly limited as long as the effects of the present invention are not impaired. For example, the content of other resin components is 20 parts by weight or less with respect to 100 parts by weight of (A) polyolefin resin.

(F) Antioxidant The antioxidant is not particularly limited, and examples thereof include phenol-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the phenolic antioxidant include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditertiary). Butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylene bis [(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-butyl) Phenol), 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- Di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol 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 ] Undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] Etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the phosphorus antioxidant include trisnonylphenyl phosphite, 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-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) Intererythritol 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- Tert-butylphenyl) -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 and 2,4,6-tritert-butylphenol phosphite, tris (2,4-ditert-butylphenyl) phosphite, etc. Can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; pentaerythritol tetra (β-alkylmercaptopropionic acid) Examples include esters, etc. These may be used alone or in combination of two or more.

  0.1-5 weight part is preferable with respect to 100 weight part of (A) polyolefin resin, and, as for content of antioxidant, 0.1-3 weight part is more preferable.

Of these antioxidants, the composition of the present invention preferably contains both a phenolic antioxidant and a phosphorus antioxidant. In this case, the phenolic antioxidant is preferably pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and the phosphorus antioxidant is tris (2,4- ditert-butylphenyl) phosphite is preferred.
The content of the phenolic antioxidant is preferably 0.05 to 3 parts by weight, more preferably 0.08 to 2 parts by weight, based on 100 parts by weight of the (A) polyolefin resin. 0.08 to 0.5 parts by weight is more preferable, and 0.08 to 0.3 parts by weight is most preferable. Further, the content of the phosphorus-based antioxidant is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyolefin resin. 0.1 to 1 part by weight is more preferable, and 0.1 to 0.4 part by weight is most preferable.
Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and tris (2,4-ditert-butylphenyl) phosphite are commercially available as AO60 and ADK STAB 2112 respectively. (Both made by ADEKA Corporation).

(G) Ultraviolet Absorber The ultraviolet absorber included in the resin composition of the present invention includes not only an ultraviolet absorber that is a component that absorbs ultraviolet rays that promotes deterioration of the resin component, but also radicals that promote deterioration of the resin component. A light stabilizer such as a hindered amine light stabilizer (HALS) which is a component to be incorporated is also included.
Note that the ultraviolet absorber and the light stabilizer may be used alone or in combination.

Although it does not specifically limit as a ultraviolet absorber, A benzophenone compound, a triazole compound, a benzoate compound etc. are mentioned.
Specific examples of UV stabilizers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 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′-methylenebis (4- 2- (2′-hydroxyphenyl) benzotriazole such as trioctyl-6- (benzotriazolyl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole Phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, 2,4-ditertiaryamylphenyl-3,5-ditertiary Benzoates such as butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxanilide Substituted oxanilides such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl Cyanoacrylates such as ru-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s- Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2, And triaryltriazines such as 4-ditertiarybutylphenyl) -s-triazine. These may be used individually by 1 type and may be used in combination of 2 or more type.

HALS is not particularly limited, and examples thereof include an NH type hindered amine compound, an N-methyl type hindered amine compound, and an N-O-R type hindered amine compound.
Specific examples of HALS 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 (N-methyl-2,2,6,6-tetramethyl-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-butane Tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-teto Methyl-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 (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxy Benzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetra Methyl-4-piperidylamino) hexane / 2,4-dichloro-6-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-tetra Methyl-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-pen And hindered amine compounds such as tamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 4 parts by weight, and 0.05 to 3 parts per 100 parts by weight of the (A) polyolefin resin. Part by weight is more preferred.

(H) Lubricant The lubricant is not particularly limited, and examples thereof include fatty acid amide-based lubricants, fatty acid ester-based lubricants, fatty acid-based lubricants, and fatty acid metal salt-based lubricants. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the fatty acid amide lubricant include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene biserucic acid amide, and ethylene bislauryl. Examples include acid amides. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of the fatty acid ester lubricant include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, myristin. Isopropyl acid, isopropyl palmitate, octyl palmitate, octyl palm fatty acid octyl stearate, beef tallow fatty acid octyl ester, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, linear C28-30 Unbranched saturated monocarboxylic acid (hereinafter abbreviated as montanic acid) and ethylene glycol ester, montanic acid and glycerin ester, montanic acid and butylene glycol ester, montanic acid and trimethylol Ester of tan, ester of montanic acid and trimethylolpropane, ester of montanic acid and pentaerythritol, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, sorbitan trioleate, poly Examples thereof include oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

Among the above fatty acid lubricants, specific examples of saturated fatty acids include lauric acid (dodecanoic acid), isodecanoic acid, tridecylic acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecane). Acid), stearic acid (octadecanoic acid), isostearic acid, tuberculostearic acid (nonadecanoic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), cerotic Examples include acid (hexadocosanoic acid), montanic acid (octadocosanoic acid), and mellic acid, and particularly lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, and montanic acid.
Among the fatty acid lubricants, unsaturated fatty acids include myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-octadecenoic acid), ricinol Acid (octadecadienoic acid), vaccenic acid (cis-11-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), elestearic acid (9,11) , 13-octadecatrienoic acid), gadoleic acid (icosanoic acid), erucic acid (docosanoic acid), nervonic acid (tetradocosanoic acid), and the like.
One of these fatty acid-based lubricants may be used alone, or two or more thereof may be used in combination.

  Examples of the fatty acid metal salt lubricant include lithium salts, calcium salts, magnesium salts, and aluminum salts of fatty acids of the above fatty acid lubricants. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the lubricant is not particularly limited as long as it does not impair the effects of the present invention.

(I) Softener The softener is not particularly limited, and examples thereof include liquid paraffin, mineral oil softener (process oil), and mineral oil softener for non-aromatic rubber (process oil). These may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the softening agent is not particularly limited as long as the effect of the present invention is not impaired.

(J) Antistatic agent Although it does not specifically limit as an antistatic agent, Fatty acid partial ester, such as cationic antistatic agent, anionic antistatic agent, nonionic antistatic agent, amphoteric antistatic agent, glycerol fatty acid monoester Kind. These may be used alone or in combination of two or more.

  Specific examples of the antistatic agent include alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalkonium salt, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methyl Ammonium mesosulfate, (3-laurylamidopropyl) trimethylammonium methylsulfate, stearoamidopropyldimethyl-2-hydroxyethylammonium nitrate, stearoamidopropyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, Alkyl sulfonate, alkyl benzene sulfonate, alkyl diphenyl ether sodium disulfonate, alkyl nitrate ester salt, alkyl phosphate ester salt, alkyl phosphate amine salt, stear Acid monoglyceride, pentaerythritol fatty acid ester, sorbitan monopalmitate, sorbitan monostearate, diglycerin fatty acid ester, alkyldiethanolamine, alkyldiethanolamine fatty acid monoester, alkyldiethanolamide, polyoxyethylene dodecyl ether, polyoxyethylene alkylphenyl ether, Examples thereof include polyethylene glycol monolaurate, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyether block copolymer, cetyl betaine, and hydroxyethyl imidazoline sulfate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the antistatic agent is not particularly limited as long as it does not impair the effects of the present invention.

(K) Metal deactivator Although it does not specifically limit as a metal deactivator, A hydrazine type metal deactivator, a nitrogen compound type metal deactivator, a phosphite type metal deactivator, etc. are mentioned. It is done. These may be used alone or in combination of two or more.
Examples of hydrazine-based metal deactivators include N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (2-phenoxypropionylhydrazide) isophthalate, Examples include decanedicarboxylic acid disalicyloylbidrazide, oxalic acid bisbenzylidenehydrazide, and the like.
Nitrogen-based metal deactivators include N, N′-bis {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyl] ethyl} oxamide, 3- (N -Salicyloyl) amino-1,2,4, -triazole, acid amide metal deactivator, melamine and the like.
Phosphite-based metal deactivators include tris [2-t-butyl-4-thio (2′-methyl-4′-hydroxy-5-t-butyl) phenyl-5-methyl] phosphite, etc. Is mentioned.
These metal deactivators may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the metal deactivator is not particularly limited as long as it does not impair the effects of the present invention.

(L) Antibacterial / antifungal agents Antibacterial / antifungal agents include, but are not limited to, organic compound antibacterial / antifungal agents, natural organic antibacterial / antifungal agents, inorganic antibacterial / antifungal agents, and the like. . These may be used individually by 1 type and may be used in combination of 2 or more type.
Organic compound antibacterial / antifungal agents include thiabendazole, 2-n-octyl-4-isothiazolin-3-one, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, N- (fluorocyclomethylthio)- Phthalimide, bis (1-hydroxy-2 (IH) pyridinethionate-O, S) zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 10,10′-oxybisphenoxyarsine Etc.
Examples of natural organic antibacterial and antifungal agents include allyl isothiocyanate.
Inorganic antibacterial / antifungal agents include silver-supported silica gel, silver-supported zeolite, silver ions-supported hydroxyapatite, silver ions-supported water glass, silver ions-supported zirconium phosphate, and silver ions. Examples include supported ammonium polyphosphate, zeolite supporting silver and copper ions, and zeolite supporting zinc.
One of these antibacterial / antifungal agents may be used alone, or two or more thereof may be used in combination.

  The content of the antibacterial / antifungal agent is not particularly limited as long as it does not impair the effects of the present invention.

(M) Pigment The pigment is not particularly limited, and examples thereof include inorganic pigments and organic pigments.
Specific examples of inorganic pigments include titanium oxide, bengara, alumina white, yellow iron oxide, cadmium red, vermilion, yellow lead, molybdate orange, gypsum, barium sulfate, calcium carbonate, white lead, ultramarine, manganese violet, cobalt violet. , Emerald green, bitumen, carbon black, aluminum powder, zinc powder and the like.
Examples of organic pigments include azo pigments, acidic dye lakes, basic dye lakes, and condensed polycyclic pigments.
These pigments may be used alone or in combination of two or more.

  The content of the pigment is not particularly limited as long as the effect of the present invention is not impaired.

(N) Crystal nucleating agent The crystal nucleating agent is not particularly limited, and examples include sorbitols, phosphorus-based nucleating agents, rosins, and petroleum resins.
Examples of the crystal nucleating agent include sorbitols such as alkyl-substituted benzylidene sorbitol (for example, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, 1,3- o-methylbenzylidene 2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di- (p-ethylbenzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-dimethyl) Benzylidene) sorbitol, etc.), phosphorus nucleating agents (for example, sodium bis (4-t-butylphenyl) phosphate, sodium 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, organic Phosphate-based composite products, etc.), sodium benzoate, aluminum pt-butylbenzoate, sodium montanate, calcium montanate, aluminum oxide Chloride, kaolin clay, talc, rosin, petroleum resins, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the crystal nucleating agent is not particularly limited as long as it does not impair the effects of the present invention.

The flame-retardant polyolefin resin composition of the present invention can be produced by a known method.
For example, each raw material mentioned above can be mix | blended and melt-kneaded, and it can prepare as a pellet with a pelletizer. The compounding and kneading at this time are premixed with a commonly used equipment such as a ribbon blender or a drum tumbler, and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder. This method can be performed by a method using a machine and a conider.
The heating temperature at the time of kneading is usually in the range of 150 to 280 ° C. and may be appropriately selected.

  The flame-retardant polyolefin resin composition of the present invention is the above-described melt-kneading molding machine, or using the obtained pellet as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, Various molded products can be manufactured by a vacuum molding method, a foam molding method, or the like. In particular, by the melt kneading method, a pellet-shaped molding raw material can be produced, and then the pellet can be used suitably for production of an injection molded product by injection molding and extrusion molded product by extrusion molding. Further, it may be formed into an extruded sheet by extrusion molding and then thermoformed to form a molded body.

  The molded body obtained from the flame retardant polyolefin resin composition of the present invention has flame retardancy, does not mind the odor derived from the flame retardant, and has a deodorizing effect on ammonia and hydrogen sulfide, It can be used for sanitary products such as toilets, kitchens, bathrooms, etc., and household appliances such as electric pots, tableware dryers, dishwashers, microwave ovens, garbage disposal machines.

  In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples.

The materials used in Examples and Comparative Examples and the symbols in Table 1 corresponding to these materials are shown below.
[(A) Polypropylene resin]
Resin A: Polypropylene (J-700GP manufactured by Prime Polymer Co., Ltd., density = 0.905 g / cm ³ , MFR = 6.8 g / 10 min (230 ° C., 2.16 kg))
Resin B: Polyethylene (manufactured by Prime Polymer 1300J, density = 0.961 g / cm ³ , MFR = 12 g / 10 min (190 ° C., 2.16 kg))

[(B) Organic halogen flame retardant]
Flame retardant A: Tetrabromobisphenol S-bis (2,3-dibromopropyl) ether (manufactured by Maruhishi Oil Chemical Co., Ltd., Nonnen PR-2 (trade name))
Flame retardant B: Tetrabromobisphenol A-bis (2,3-dibromopropyl) ether (manufactured by Shogoku Kaikai Co., Ltd., XZ-6800 (trade name))
Flame retardant C: Tris (tribromoneopentyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., CR-900 (trade name))
Flame retardant D: Tris (2,3-dibromopropyl) isocyanurate (Daiichi Kogyo Seiyaku, Piroguard SR-750 (trade name))

[(C) Antimony oxide]
Antimony trioxide (Nippon Seika Co., Ltd. Antimony trioxide PATOX-KF, average particle size 0.8μm)
[(D) Zinc oxide and (E) Silicon oxide]
Powder mixture of particles with an average particle diameter of 2 to 3 μm consisting of a mixture ratio of 60% silicon dioxide, 22% zinc oxide, and water (residue) (Luke Industrial Shukurenzu GF KD-211)

[(F) Antioxidant]
Inhibitor A: Phenolic antioxidant (AO80, manufactured by ADEKA)
Inhibitor B: Phenolic antioxidant (Adeka manufactured by ADEKA)
Inhibitor C: Phosphorous antioxidant (ADEKA STAB 2112 from ADEKA)

Example 1-18 and Comparative Example 1-7
Each component shown in Table 1 was added in the amount shown in Table 1, and premixed with a Henschel mixer or tumbler. The obtained preliminary mixture was kneaded at 160 ° C. to 240 ° C. using a twin-screw kneader (trade name PCM45I manufactured by Ikekai Steel Co., Ltd.) to prepare a composition, and pelletized using a strand cut.
The obtained composition pellets were injection molded using an injection molding machine (Nex110II manufactured by Nissei Plastic Industry Co., Ltd., EC100 manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 190 to 210 ° C and a mold temperature of 50 ° C. A piece was made.
The characteristics of the test piece were evaluated by the following evaluation methods. The results are shown in Table 1.

(1) Flame retardancy evaluation (UL94 test)
Using a flame retardant evaluation tester (manufactured by Atlas, HVUL plastic UL combustion test chamber), a vertical combustion test was performed according to UL94 for 1/16 inch thickness of the test piece. Specifically, the five test pieces were given a combustion rank in accordance with the UL-94V standard from the first and second combustion times and the presence or absence of cotton ignition.
Here, the combustion rank V-0 is the highest, and the evaluation of combustibility decreases as V-1 and V-2 are obtained. Moreover, what does not correspond to any of the ranks of V-0 to V-2 was set to not-V.

(2) Deodorization evaluation (2-1) Deodorization test of ammonia and hydrogen sulfide Put a test piece (8cm x 8cm x 0.3cm) into a bag (25cm x 40cm), seal with heat seal, and enclose 3L of air. The target gas was added so that the initial gas concentration was set (ammonia: 100 ppm, hydrogen sulfide: 20 ppm). The gas concentration was measured with a gas detector tube (manufactured by Gastec Co., Ltd.) at every elapsed time (after 6 hours and after 24 hours).

(2-2) Odor test of flame retardant 200 g of pellets and 500 mL of water at 100 ° C. were placed in a 1 L beaker, covered with aluminum foil, and allowed to stand for 1 minute. Then, scoop up the pellets with perforated balls, smell the odor, 5 points: no odor, 4 points: almost no odor, 3 points: slightly odor, 2 points: slightly odor, 1 point: strong odor Evaluation criteria It was evaluated with.

(3) Evaluation of heat resistance A test piece (8 cm × 8 cm × 0.3 cm) was placed in a thermostatic bath at 150 ° C., and the time for generating cracks on the surface was measured.

（表中、成分（Ａ）〜（Ｆ）の配合量は全て重量部である）

(In the table, the amounts of components (A) to (F) are all parts by weight)

Comparing Examples 1 to 3 and 8 to 14 with Comparative Example 1 containing no flame retardant, it can be seen that Examples 1 to 3 and 8 to 14 are excellent in flame retardancy.
When Examples 1-3 and 8-14 are compared with Comparative Example 2 that does not contain antimony trioxide, it can be seen that Examples 1-3 and 8-14 are excellent in flame retardancy. In addition, although the heat resistance of Examples 1-3 and 8-14 falls a little compared with the comparative examples 1 and 2, in order to obtain high flame retardance, it is an acceptable range.
Comparing Examples 1 to 3 and 8 to 14 with Comparative Examples 3 and 7 not containing zinc oxide and silicon dioxide, it can be seen that Examples 1 to 3 and 8 to 14 are excellent in deodorizing properties. However, it is not necessary to contain zinc oxide and silicon oxide, and it can be seen that if the contents of zinc oxide and silicon dioxide are excessive as in Comparative Example 4, the heat resistance is significantly reduced.
Examples 4 to 7 and 15 to 18 are equivalent to or superior to those of Examples 1 to 3 in terms of flame retardancy, deodorant properties, and flame retardant odor, and Comparative Example 1 containing no flame retardant. Compared to Comparative Example 2 containing no antimony trioxide, the heat resistance is excellent. Usually, heat resistance is lowered by adding a flame retardant or antimony trioxide, but Examples 4-7 and 15-18 are surprising that heat resistance is improved by using flame retardant A and flame retardant B together. I found the effect that should be done.
The heat resistances of Examples 4 to 7 and 15 to 18 are the same as those of Comparative Examples 5 and 6 in which flame retardant A and flame retardant B are used in combination. From the viewpoint of deodorization, zinc oxide and dioxide dioxide are used. It turns out that the deodorizing property of Examples 4-7 and 15-18 containing silicon is remarkably superior compared with the comparative examples 5 and 6 which do not contain these.

Claims (6)

A flame retardant polyolefin-based resin composition containing the following components (A) to (E) in the following content.
[component]
(A) Polyolefin resin (B) Organic halogen flame retardant (C) Antimony oxide (D) Zinc oxide (E) Silicon oxide [content]
(B) Component content is 1 to 50 parts by weight per 100 parts by weight of component (A) Component (C) is 0.5 to 10 parts by weight per 100 parts by weight of component (A) (D ) Component content is 0.13 to 1.9 parts by weight with respect to 100 parts by weight of component (A) Component (E) is 0.37 to 5.1 parts with respect to 100 parts by weight of component (A) Parts by weight   The (B) organic halogen flame retardant is selected from tetrabromobisphenol A flame retardant, tetrabromobisphenol S flame retardant, tris (brominated neopentyl) phosphate, brominated alkyl cyanurate, and brominated alkyl isocyanurate. The flame retardant polyolefin resin composition according to claim 1, wherein the flame retardant polyolefin resin composition is one or more.   The flame retardant polyolefin resin composition according to claim 1 or 2, wherein the flame retardant polyolefin resin composition is produced by adding a mixture of (D) zinc oxide and (E) silicon oxide.   The flame-retardant polyolefin resin composition according to any one of claims 1 to 3, wherein the content of the (C) antimony oxide is 3 to 7 parts by weight with respect to 100 parts by weight of the component (A).   The flame retardant polyolefin resin composition according to any one of claims 1 to 4, wherein the (B) organic halogen flame retardant includes both a tetrabromobisphenol A flame retardant and a tetrabromobisphenol S flame retardant.   The molded product which shape | molded the flame-retardant polyolefin-type resin composition in any one of Claims 1-5.