JP5580542B2 - Flame retardant styrene resin composition - Google Patents

Description

  The present invention relates to a flame-retardant styrene resin composition, and more particularly, a halogen-based flame retardant that generates a harmful gas during combustion and an inorganic system such as magnesium hydroxide and antimony trioxide that extremely impair the physical properties of the resin. The present invention relates to a flame retardant styrene resin composition excellent in resin physical properties such as flame retardancy and tensile properties, which is obtained by blending a specific phosphate flame retardant with a styrene thermoplastic elastomer without using a flame retardant.

  Conventionally, synthetic resins have been widely used for building materials, automobile parts, packaging materials, agricultural materials, housing materials for home appliances, toys and the like due to their excellent chemical and mechanical properties. However, many synthetic resins are flammable substances, and flame retardant is indispensable depending on applications. Polyvinyl chloride (hereinafter referred to as PVC) resin, which is flame retardant and excellent in wear resistance and flexibility, has been widely used as a coating resin used for electric wiring in automobiles or homes.

  However, PVC resin generates harmful and corrosive halogen gas during combustion, and there are many problems such as corrosion of equipment, suction damage during fire evacuation, and global environmental pollution. Transition to is planned.

  As an alternative synthetic resin to replace PVC resin for wire coating, thermoplastic elastomers (polyolefin-based and styrene-based resins, etc.) with excellent processability and mechanical properties are being changed, but these resins are flammable. It is necessary to add a flame retardant. Among them, hydrogenated styrene elastomer resins are attracting attention as an alternative to PVC resins because they are excellent in rubber elasticity, flexibility, cold resistance and chemical resistance and can be reduced in weight. Flame retardants are difficult, and as flame retardants, halogen flame retardants and antimony trioxide, and metal hydroxide flame retardants such as magnesium hydroxide are used. In addition to the fact that it does not make sense, there is a problem that the amount of smoke generated during combustion is significant, and a large amount of flame retardant is indispensable in order to obtain the flame retardance required for metal hydroxide flame retardants There is a problem that the mechanical properties of the resin are extremely impaired.

  Due to the above problems, attempts have been made to incorporate a non-halogen flame retardant that does not use a metal hydroxide flame retardant. For example, those using red phosphorus (patent documents 1 and 2), those using ammonium polyphosphate (patent documents 3 to 5), those using condensed phosphate esters (patent documents 6 and 7), melamine cyanurate The thing using a system flame retardant (patent document 8) is proposed.

Japanese Patent Laid-Open No. 06-102442 Japanese Patent No. 3819116 JP 2003-096247 A JP 2003-105165 A JP 2006-241405 A JP 2006-016587 A Japanese Patent No. 3797895 JP 2003-226798 A

  However, the red phosphorus has a problem of generation of a toxic gas phosphine, and the phosphate ester flame retardant has problems such as deterioration of mechanical properties or insufficient flame retardancy.

  Accordingly, an object of the present invention is to provide a flame retardant property and a tensile property without using a halogen-based flame retardant that generates a harmful gas during combustion and an inorganic flame retardant such as magnesium hydroxide and antimony trioxide that extremely impair the physical properties of the resin. An object of the present invention is to provide a flame retardant styrene resin composition having excellent resin properties such as characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have improved the mechanical properties of the styrene thermoplastic elastomer resin by blending a specific phosphate flame retardant with the styrene thermoplastic elastomer resin. The inventors have found that a flame-retardant styrene-based resin composition having excellent flame retardancy can be provided without damaging the present invention and completed the present invention.

  That is, the flame-retardant styrene-based resin composition of the present invention is composed of piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, and a mixture of two or more thereof with respect to 100 parts by mass of the styrene-based thermoplastic elastomer resin (A) component. A melamine selected from the group consisting of a salt of piperazine and an inorganic phosphorus compound (b-1) selected from the group consisting of: melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and a mixture of two or more thereof 1 to 200 parts by mass of the flame retardant (B) component, and the silicone oil (C) component to 0 part by mass of the flame retardant (B) component. 0.01 to 10 parts by mass, does not contain magnesium hydroxide and antimony trioxide, and contains only the component (A) as a resin component And, wherein the component (A) is characterized in that a hydrogenated styrene elastomer resin.

  In the flame-retardant styrene resin composition of the present invention, the blending ratio of the component (b-1) to the component (b-2) is (b-1) component: (b-2) component = 20: It is preferable that it is 80-80: 20 (mass ratio).

  Furthermore, in the flame-retardant styrene resin composition of the present invention, the hydrogenated styrene elastomer resin as the component (A) is a styrene-ethylene-butylene-styrene resin and / or a styrene-ethylene-propylene-styrene resin. It is preferable that

  Moreover, the flame-retardant styrene resin composition of the present invention further comprises at least one metal oxide (D) component selected from the group consisting of zinc oxide, titanium oxide, magnesium oxide and silicon oxide. ) It is preferable to mix 0.01 to 10 parts by mass with respect to 100 parts by mass of the component.

  By adopting the above configuration, a halogen-based flame retardant that generates harmful gases during combustion, and an inorganic flame retardant such as magnesium hydroxide and antimony trioxide that severely impairs the physical properties of the resin, and further a resin with tensile properties, etc. It has become possible to provide a flame-retardant styrene resin composition having excellent flame retardancy without impairing physical properties. Moreover, the flame retardant styrene resin composition of the present invention is useful as a resin for coating an electric wire.

  Hereinafter, the flame-retardant styrene resin composition of the present invention will be described in detail.

As the styrene-based thermoplastic elastomer resin (A) component used in the present invention, styrene-ethylene-butylene-styrene (SEBS) resin in which a double bond of butadiene or isoprene is hydrogenated, styrene-ethylene-propylene-styrene (SEPS) ) Hydrogenated styrenic elastomer resin such as resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin, etc., and these can be used alone or in multiple blends. is there. Among them, as the resin for covering the wire, a hydrogenated styrene-based elastomer resin excellent in properties such as rubber elasticity and cold resistance is preferable, and in particular, styrene-ethylene-butylene-styrene (SEBS) resin, styrene-ethylene-propylene-styrene (SEPS). ) Resins are preferred.

  In the present invention, the salt of piperazine which is the component (b-1) constituting the component (B-1) and the inorganic phosphorus compound is selected from piperazine phosphate, piperazine pyrophosphate, and piperazine polyphosphate, which are used alone or in a mixture. May be. Specific examples of preferable salts of piperazine and inorganic phosphorus compounds used in the present invention include orthophosphoric acid piperazine salts, pyrophosphoric acid piperazine salts, and polyphosphoric acid piperazine salts. However, in the case of piperazine polyphosphate salt, phosphoric acid may be a salt obtained from orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, other polyphosphoric acid and polyphosphoric acid and piperazine, and the composition of raw polyphosphoric acid is particularly limited Not.

  The compounding ratio of the piperazine and the inorganic phosphorus compound (composition ratio of the component (b-1)) is not particularly limited as long as the flame retardant effect is manifested. Preferably, the nitrogen atom of piperazine and the inorganic phosphorus compound The molar ratio of phosphorus atoms is preferably 1: 5 to 5: 1, particularly preferably 1: 2 to 2: 1.

  The salt of the piperazine and the inorganic phosphorus compound can be obtained by the following method. For example, in the case of a pyroperidic acid piperazine salt, it is easily obtained as a poorly water-soluble precipitate by reacting piperazine and pyrophosphoric acid in water or an aqueous methanol solution.

  In the present invention, the salt of the melamine and the inorganic phosphorus compound that are the component (b-2) constituting the component (B) in the present invention is selected from melamine phosphate, melamine pyrophosphate, and melamine polyphosphate, which are used alone or in a mixture. May be. Specific examples of the melamine phosphate compound preferably used in the present invention include melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate.

  The blending ratio of the melamine and the inorganic phosphorus compound (composition ratio of the component (b-2)) is not particularly limited as long as the flame retardant effect is exhibited. Preferably, the melamine nitrogen atom and the phosphorus of the inorganic phosphorus compound are used. The molar ratio of atoms is preferably 1: 5 to 5: 1, particularly preferably 1: 3 to 3: 1.

  The salt of phosphoric acid and melamine can be obtained by the following method. For example, in the case of melamine pyrophosphate, sodium pyrophosphate and melamine are reacted by adding hydrochloric acid at an arbitrary reaction ratio, and neutralized with sodium hydroxide to obtain melamine pyrophosphate.

  As a preferable blending ratio of the component (b-1) and the component (b-2), (b-1) :( b-2) = 20: 80 to 80:20 (mass ratio) is preferable. (B-1) :( b-2) = 40: 60 to 60:40 is more preferable.

  In addition, the component (b-1) and the component (b-2) used in the present invention each have an average particle size of 100 μm or less, more preferably 10 μm or less. When the average particle size of the phosphate compound is larger than 100 μm, the dispersibility with respect to the resin is deteriorated, and not only high flame retardancy may not be obtained, but also the mechanical strength of the molded resin may be lowered. is there.

  The compounding quantity of the flame retardant (B) component used for this invention is 1-200 mass parts with respect to 100 mass parts of styrene-type thermoplastic elastomer resin (A) components, and flame retardance and the mechanical physical property of resin, From the viewpoint of the balance, 10 to 150 parts by mass are preferable, and 25 to 100 parts by mass are more preferable.

The silicone oil (C) component used in the present invention preferably has a viscosity of 5 at 25 ° C.
000 mm ² / s or less, particularly preferably more preferably the following 3000 mm ² / s for good workability dispersibility or the like into the resin.

  The silicone oil preferably has a methylsiloxane structure. Silicone oils having a methylsiloxane structure include those having a dimethylpolysiloxane structure, those having both a dimethylpolysiloxane structure and a methylhydrogenpolysiloxane structure, and those having only a methylhydrogenpolysiloxane structure. There is. The silicone oil may be epoxy-modified, carboxyl-modified, carbinol-modified and / or amino-modified.

  Moreover, the addition method of silicone oil is not specifically limited, For example, it is excellent in the flame-retarding effect by which secondary aggregation was suppressed by stirring a flame retardant powder and silicone oil, heating at 100-150 degreeC, and processing. A flame retardant composition in which adverse effects on the properties are suppressed is obtained. As another addition treatment method, it is also possible to carry out treatment such as addition / mixing, mixing granulation, coating, dispersion, kneading and the like at 100 to 150 ° C. by spray drying.

The silicone oil having the dimethylpolysiloxane structure is KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd .: viscosity 3000 mm ² / s), and the one having a methyl hydrogen structure of 100% is KF-99 (Shin-Etsu Chemical). Co., Ltd .: Viscosity: 20 mm ² / s), part of which has a methyl hydrogen structure is HMS-151 (manufactured by Gelest: viscosity 25-35 mm ² / s), HMS-071 (manufactured by Gelest: viscosity 25-35 mm ² / s), HMS-301 (manufactured by Gelest: viscosity 25-35 mm ² / s), DMS-H21 (manufactured by Gelest: viscosity 100 mm ² / s), etc., and epoxy-modified products such as X -22-2000 (Shin-Etsu chemical Co., Ltd.: viscosity 190), KF-102 (Shin-Etsu chemical Co., Ltd.: viscosity 4000 mm ² / s), Carboxyl-modified, for example, X-22-4015 (Shin-Etsu Chemical Co., Ltd.: Viscosity 130 mm ² / s), carbinol-modified, for example, X-22-4015 (Shin-Etsu Chemical Co., Ltd.: Viscosity 2000 mm ² / s) A modified product such as amino-modified, for example, KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd .: viscosity 20 mm ² / s) may be used.

  The compounding quantity of the silicone oil (C) component used for this invention is 0.01-10 mass parts with respect to 100 mass parts of flame retardant (B) components, 0.1-5 mass parts is preferable. 5-3 mass parts is more preferable.

  The flame-retardant styrene resin composition of the present invention preferably contains at least one metal oxide (D) component selected from the group consisting of zinc oxide, titanium oxide, magnesium oxide and silicon oxide.

  The compounding quantity of the metal oxide (D) component used for this invention is 0.01-10 mass parts with respect to 100 mass parts of flame retardant (B) components, 0.1-5 mass parts is preferable, 0 0.5-3 parts by mass is more preferable.

  In addition to the styrene-based thermoplastic elastomer resin, other resins can be added to the flame-retardant styrene-based resin composition of the present invention. For example, α-olefin polymer such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, poly-3-methylpentene, or ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer Polymers such as polymers, ethylene-methyl acrylate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers and ethylene-propylene copolymers, polyvinyl chloride, Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride -Vinyl acetate Halogen-containing resins such as copolymers, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers and vinyl chloride-cyclohexyl maleimide copolymers, petroleum resins, coumarone resins, polyvinyl acetate, acrylic resins , Polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched Thermoplastic resins such as polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, and fibrous resin, and blends or phenols thereof Examples thereof include thermosetting resins such as resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber may be used. These synthetic resins may be used alone or in combination of two or more.

  In the flame-retardant styrene resin composition of the present invention, if necessary, an inorganic reinforcing material may be blended with the above synthetic resin to form a fiber reinforced resin. Examples of inorganic reinforcing materials include glass fiber, carbon fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, kaolin, calcined kaolin, Examples thereof include fiber-like, granular, plate-like, or needle-like inorganic reinforcing materials such as wollastonite, glass beads, glass flakes, and titanium oxide.

  Further, the flame retardant styrene resin composition of the present invention may be blended with polytetrafluoroethylene or titanium oxide as an anti-drip agent as necessary in order to prevent resin dripping (drip) during combustion. . The compounding amount of polytetrafluoroethylene or titanium oxide can be 0.01 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin. If the addition is less than 0.01, the effect as an anti-drip agent is not manifested, and even if it exceeds 5 parts by mass, the physical properties of the resin are reduced, which is not preferable.

  Furthermore, you may mix | blend a higher fatty acid compound with the flame-retardant styrene-type resin composition of this invention in order to improve resin processability. Examples thereof include higher aliphatic carboxylic acids, metal salts and ester compounds thereof, and higher fatty acid amide compounds.

  Examples of the higher aliphatic carboxylic acid include lauric acid, myristic acid, palmitic acid, stearic acid, alginic acid, behenic acid, and alkenyl succinic anhydride.

  Examples of the metal salt of the higher aliphatic carboxylic acid include zinc laurate, barium laurate, calcium stearate, zinc stearate, magnesium stearate, lithium stearate, aluminum stearate, and barium stearate.

  Examples of the higher fatty acid ester compounds include esters of mono- or polyhydric alcohols and higher aliphatic carboxylic acids. Examples include glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, higher alcohol fatty acid ester and the like. Examples of the glycerin fatty acid ester include monoglyceride, diglyceride, or a mixture of monoglyceride and diglyceride. Specifically, lauric acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride, behenic acid monoglyceride, ricinoleic acid monoglyceride, palmitic acid mono -Diglyceride or stearic acid mono-diglyceride etc. are mentioned. Examples of sorbitan fatty acid esters include lauric acid sorbitan ester, palmitic acid sorbitan ester, stearic acid sorbitan ester, oleic acid sorbitan ester, and polyglycerin fatty acid ester include stearic acid polyglyceride, oleic acid polyglyceride, and the like. Examples of the propylene glycol fatty acid ester include propylene glycol monolaurate, propylene glycol monopalmitate, propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, and the higher alcohol fatty acid ester includes stearyl stearate. Etc.

  Examples of the higher fatty acid amide compounds include lauric acid amide, myristylic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, erucic acid amide, montanic acid amide, stearyl erucic acid amide, oleyl palmitic acid amide, methylene bis (stearin). Acid amide), ethylene bis (myristyl amide), ethylene bis (stearic amide) and the like.

  The higher fatty acid compound can be used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the flame retardant component (B).

  The flame retardant styrene resin composition of the present invention is stabilized by a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, etc., if necessary. It is preferable to do.

  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] Ndecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tocophenol and the like, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the synthetic resin, More preferably, 0.05 to 5 parts by mass is used.

  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-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- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [ d, f] [1,3,2] dioxaphosphin-6-yl] oxy] propyl] phenol, 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol phosphite 0.001-10 mass parts with respect to 100 mass parts of synthetic resins, More preferably, 0.05-5 mass parts is used.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate esters). 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic 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) ) -4,6-bis (2,4-ditertiarybutylphenyl) -s-triazine and the like, and triaryltriazines, and 0.001 to 30 parts by mass relative to 100 parts by mass of the synthetic resin. Preferably, 0.05 to 10 parts by mass are used.

  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-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 -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 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-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] aminoundecane and the like, and hindered amine compounds such as 0.001 to 30 parts by mass relative to 100 parts by mass of the synthetic resin. Preferably, 0.05 to 10 parts by mass are used.

  Furthermore, the flame retardant styrene resin composition of the present invention includes a nucleating agent, other flame retardants, other metal oxides, hydrotalcites, metal deactivators, triazine ring-containing compounds as necessary. Pigments, metal soaps, antistatic agents, fillers, lubricants, anti-aggregation agents, foaming agents and the like may be added.

  Examples of the nucleating agent include metal salts of benzoic acids such as aluminum p-t-butylbenzoate and sodium benzoate, sodium bis (2,4-di-t-butylphenyl) phosphate, methylene bis (2,4 -Di-t-butylphenyl) phosphate sodium salt, bis [methylenebis (2,4-di-t-butylphenyl) phosphate] hydroxyaluminum metal salt and aromatic phosphate metal such as hydroxyaluminum A mixture of a salt and an alkali metal compound, dibenzylidene sorbitol, dibenzylidene sorbitols such as bis (methylbenzylidene sorbitol), bis (dimethylbenzylidene sorbitol), amino acid metal salts, rosin acid metal salts, etc., and 100 parts by mass of a synthetic resin 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by weight is used.

  Other flame retardants include halogen-based flame retardants such as tetrabromobisphenol A and decabromodiphenyl ether; inorganic phosphorus compounds such as red phosphorus and melamine phosphate, triphenyl phosphate, resorcinol / phenol / phosphate condensate, bisphenol Phosphorus flame retardants comprising phosphate ester compounds such as A · 2,6-xylenol and phosphoric acid condensates; inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide; nitrogen-containing compounds such as melamine cyanurate In addition, 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass is used with respect to 100 parts by mass of the synthetic resin.

  Examples of the other metal oxides include aluminum oxide, calcium oxide, magnesium oxide, zirconium oxide, barium oxide, vanadium oxide, tin dioxide, lead dioxide, antimony oxide, molybdenum oxide, cadmium oxide, and the like. 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

The hydrotalcites may be natural products or synthetic products, and may be those modified with an alkali metal such as lithium. In particular, the composition represented by the following general formula (1) is preferable and can be used regardless of the presence or absence of crystal water or the presence or absence of surface treatment.
ZnxMgyAl ₂ (OH) ₂ (x + y + 2) CO ₃ .nH ₂ O (1)
(In the formula, x is 0 to 3, y is 1 to 6, and x + y is 4 to 6. n is 0 to 10.) Although the particle size is not particularly limited, It is desirable that it is small as long as the characteristics of talcite are not lost. When the particle size is large, the dispersibility is lowered and the stabilization effect is reduced, and further, the physical properties such as mechanical strength and transparency of the obtained resin composition are lowered. 0.01-10 mass parts with respect to 100 mass parts of synthetic resins, More preferably, 0.1-5 mass parts is used.

  Examples of the heavy metal deactivator include salicylamido-1,2,4-triazol-3-yl, bissalicylic acid hydrazide, dodecandioyl bis (2- (2-hydroxybenzoyl) hydrazide), bis (3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionic acid) hydrazide and the like, and 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin. Part is used.

  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 dimelamine and the like can be mentioned, and 0.001 to 10 parts by mass, more preferably 0.05 to 100 parts by mass of the synthetic resin. ~ 5 parts by weight are used.

  The above-mentioned various blends are appropriately selected in terms of blending amount, quality, etc. according to the type of resin, processing conditions, and usage. In addition, as a method of adding to the resin, each compound is separately added to the resin, mixed with a Henschel mixer and then supplied to the processing machine, and any combination of compounds other than the resin as a mixture in advance A method of adding powder or granules into a resin, a method of adding a master pellet by blending at a high concentration in the resin, a method of adding to a resin, and an extruder having a plurality of supply ports. A known addition method such as a method of adding to the resin from the supply port is used.

  The processing method of the flame-retardant styrene-based resin composition of the present invention is not particularly limited, and a known processing method is appropriately used depending on the resin used, the presence or absence of a filler, and the like.

  The use of the flame-retardant styrene resin composition of the present invention is not particularly limited, but can be usefully used as, for example, a mechanical mechanism part, an electric / electronic part, or an automobile part. For example, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards , Tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts ; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, Houses represented by acon parts, typewriter parts, word processor parts, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning jigs, oilless bearings, stern bearings, Various bearings such as underwater bearings, motor-related parts such as motor parts, lighters and typewriters, optical equipment such as microscopes, binoculars, cameras and watches, precision machine-related parts; alternator terminals, alternator connectors, IC regulators, light meter potentiometer base, various valves such as exhaust gas valves, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, Letter main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air Flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Distributor, Starter switch, Starter relay, Transmission wire harness, Window washer nozzle, Air conditioner panel switch board, Fuel related electromagnetic valve Coil, fuse connector, horn terminal, electrical component insulation plate, step motor Terrotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, personal computer, printer, display, CRT display, fax machine, copy machine, word processor, laptop computer, DVD drive, PD drive Widely used in various applications such as storage device housings such as flexible disk drives, relays, switches, case members, transformer members, electrical and electronic equipment parts such as coil bobbins, automobile parts, machine parts, other molded products, films, filaments and fibers. Can be used. Among them, it is useful as an electric wire / cable coating resin for cords of power transmission lines, home appliances, OA equipment, and the like.

  The present invention will be described in detail by examples. However, the present invention is not limited to the following examples.

[Adjustment of flame retardant powder (component (B)]]
Piperazine pyrophosphate (nitrogen of piperazine: phosphorus atom of pyrophosphate = 1: 1) (component (b-1)) and melamine pyrophosphate (nitrogen atom of melamine: phosphorus atom of pyrophosphate = 3: 1) (Component (b-2)) 50 parts by mass is put into a jet mill (manufactured by Seishin Co., Ltd .: Co-JETSystem α-mkIII), and pulverized at room temperature with a nozzle pressure of 0.8 MPa and a supply rate of 500 g / hour. A powder (component (B)) was obtained. The flame retardant powder (component (B)) stored at 50 ° C. and a load of 0.175 kg · cm ⁻¹ for 1 week was used.

[Adjustment of flame retardant composition (B + C component)]
1 part by mass of silicone oil (component (C); methyl silicone oil: manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF-99, viscosity 20 mm ² / s) is added to 100 parts by mass of the flame retardant powder. ): FM20C / I) and stirred at 280 rpm at 120 ° C. for 10 minutes to obtain a flame retardant composition (B + C component).

[Example 1]
Styrene-ethylene-butylene-styrene (SEBS) resin (styrene thermoplastic elastomer resin (A) component; manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec H1051) per 100 parts by mass, N, N′-ethylenebisstearin 0.3 parts by mass of acid amide (lubricant), 0.1 parts by mass of tetrakis {3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate methyl} methane (phenolic antioxidant), bis ( 2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite (phosphorus antioxidant) is added to the thermoplastic elastomer resin composition obtained by blending 0.1 part by mass with the above flame retardant composition. 70.7 parts by mass of the product (B + C component) is mixed and extruded at 200 to 230 ° C. to produce pellets, which are used for injection molding at 220 ° C. A test piece having a thickness of 1.6 mm was obtained. Using the obtained test piece, the following UL-94 flame retardancy test and tensile property test were performed. The results are shown in Table 1.

[Example 2]
In addition, 0.7 parts by mass of zinc oxide (metal oxide (D) component) is added to 100 parts by mass of the component (A) in the compounding composition of Example 1, and molding similar to Example 1 is performed. Test pieces were produced under the same conditions and the same evaluation was performed. The results are shown in Table 1.

[Example 3]
The test piece was prepared under the same conditions as in Example 2 except that the flame retardant composition (B + C component) was 45.45 parts by mass and the zinc oxide (metal oxide (D) component) was 0.45 parts by mass. A similar evaluation was made. The results are shown in Table 1.

[Comparative Example 1]
Magnesium hydroxide as a flame retardant instead of the flame retardant composition (B + C component) per 100 parts by mass of styrene-ethylene-butylene-styrene (SEBS) resin (Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec H1051) Except using 60 mass parts, the synthetic resin composition was manufactured on the same mixing | blending and conditions as the previous Example, and the flame retardance was evaluated. The results are shown in Table 1.

[Comparative Example 2]
A styrene-ethylene-butylene-styrene (SEBS) resin (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec H1051), 100 parts by mass, the same as in the example without adding a flame retardant, silicone oil and metal oxide Test pieces were prepared under the conditions, and flame retardancy and tensile properties were tested. The results are shown in Table 1.

(Evaluation method)
<Flame-retardant UL-94V test>
Keep the test piece 127mm long, 12.7mm wide and 1.6mm thick vertically, burn the burner at the lower end indirectly for 10 seconds, remove the flame, and let the time when the fire ignited the test piece disappears. It was measured. Next, at the same time when the fire was extinguished, the second flame contact was performed for 10 seconds, and the time when the ignited fire extinguished was measured in the same manner as the first time. Moreover, it was also evaluated at the same time whether or not the cotton under the test piece was ignited by the falling fire type.
The combustion rank was given according to the above-mentioned UL-94V standard from the 1st and 2nd combustion time, the presence or absence of cotton ignition, and the like. The combustion rank is the highest at V-0, and the flame retardancy decreases as V-1 and V-2 below. However, those not corresponding to any of the ranks V-0 to V-2 are NR.

<Tensile property test>
The test piece was measured for tensile elongation (%), tensile strength (MPa), and tensile modulus (MPa) according to JIS K-6251.

  As is apparent from the results of Comparative Example 1 in Table 1 above, when a conventionally used magnesium hydroxide is added as a flame retardant to the styrene-based thermoplastic elastomer resin, the UL-94V standard is satisfied. Flame retardancy was not obtained. Further, from Comparative Examples 1 and 2, as for the tensile properties, when magnesium hydroxide was blended, the physical properties of the styrenic thermoplastic elastomer resin were greatly impaired. On the other hand, as is apparent from the results of Examples 1 to 3 in Table 1, the specific phosphate-based flame retardants according to the present invention, piperazine pyrophosphate and melamine pyrophosphate, are converted into styrene-based thermoplastic elastomer resins. When blended with the above, flame retardancy as high as V-0 in the UL-94V standard was obtained. Furthermore, as is clear from Examples 1 to 3 and Comparative Example 2, the tensile properties of the styrenic thermoplastic elastomer resin were not impaired as compared with the case where no flame retardant was blended.

Claims (4)

Piperazine and inorganic phosphorus compound salt selected from the group consisting of piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, and mixtures of two or more thereof with respect to 100 parts by mass of component (A) of the styrenic thermoplastic elastomer resin (A) (B-1) component, and a salt (b-2) component of melamine and an inorganic phosphorus compound selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and a mixture of two or more thereof. comprising 1 to 200 parts by mass of the flame retardant component (B), it becomes blended with 0.01 to 10 parts by mass relative to the silicone oil component (C) the flame retardant (B) 100 parts by weight of the component, magnesium hydroxide and free of antimony trioxide, the as the resin component comprises only the component (a), and the component (a), the hydrogenated styrene Heras Flame retardant styrene type resin composition which is a mer resin.   The blending ratio of the (b-1) component and the (b-2) component is (b-1) component: (b-2) component = 20: 80 to 80:20 (mass ratio). Flame retardant styrene resin composition.   The flame retardant styrene resin composition according to claim 1 or 2, wherein the hydrogenated styrene elastomer resin is a styrene-ethylene-butylene-styrene resin and / or a styrene-ethylene-propylene-styrene resin.   Furthermore, 0.01 to 10 parts by mass of at least one metal oxide (D) component selected from the group consisting of zinc oxide, titanium oxide, magnesium oxide and silicon oxide with respect to 100 parts by mass of the flame retardant (B) component. The flame-retardant styrenic resin composition according to any one of claims 1 to 3, which is blended.