WO2013111808A1 - Flame-retardant resin composition, molded body, laminated structure, reflective plate and lighting device - Google Patents

Flame-retardant resin composition, molded body, laminated structure, reflective plate and lighting device Download PDF

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Publication number
WO2013111808A1
WO2013111808A1 PCT/JP2013/051414 JP2013051414W WO2013111808A1 WO 2013111808 A1 WO2013111808 A1 WO 2013111808A1 JP 2013051414 W JP2013051414 W JP 2013051414W WO 2013111808 A1 WO2013111808 A1 WO 2013111808A1
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resin composition
flame
mass
retardant resin
flame retardant
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PCT/JP2013/051414
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French (fr)
Japanese (ja)
Inventor
一道 ▲真▼島
信行 重文字
悠貴 山田
真太郎 黒田
寿樹 山本
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出光ライオンコンポジット株式会社
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Publication of WO2013111808A1 publication Critical patent/WO2013111808A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/738—Thermoformability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to a flame retardant resin composition containing titanium dioxide, a molded body, a laminated structure, a reflector, and a lighting device.
  • Patent Documents 1 to 4 resin compositions containing titanium dioxide have been used for reflectors such as electric signboards, lighting fixtures, and displays that use light emitting diodes as a light source (see, for example, Patent Documents 1 to 4).
  • the resin composition described in Patent Document 1 is 45% by mass in total of titanium dioxide and inorganic filler, 5 to 42% by mass as titanium dioxide, based on polypropylene resin or resin based on polypropylene resin, As an inorganic filler, 3 to 18% by mass is contained.
  • the resin composition can be added with a flame retardant such as halogen, phosphorus, metal oxide, metal hydroxide, or the like, such as chlorine or bromine, as long as the reflectance is not impaired.
  • the resin composition described in Patent Document 2 contains 5 to 10% by mass of titanium oxide with respect to the ethylene propylene block copolymer and the high-density polyethylene. And this resin composition can mix
  • the resin composition described in Patent Document 3 comprises polypropylene polymer matrix of 31 to 70% by weight, flame retardant material of 12 to 24% by weight and reflective filler (rutile titania) particles of 15 to 30% by weight. The structure of the light-reflective material dispersed in proportion is adopted.
  • the resin composition described in Patent Document 4 has a reflective material structure in which 1 to 50 wt% of a flame retardant such as brominated aromatic compound such as decabromodiphenyl oxide or brominated imide is added to polypropylene resin. It has been.
  • An object of the present invention is to provide a flame retardant resin composition, a molded body, a laminated structure, a reflector, and a lighting device that can obtain flame retardancy while suppressing deterioration in moldability and reflectance. .
  • the flame-retardant resin composition of the present invention comprises (A) a polypropylene resin composition containing 55% by mass or more of a polypropylene resin, and (B) 5% by mass or more and 20% by mass or less of titanium dioxide. (C) 1% by mass or more and 30% by mass or less of at least one brominated flame retardant selected from the group of ethylene bispentabromodiphenyl or derivatives thereof, ethylene bistetrabromophthalimide or derivatives thereof, decabromodiphenyl ether or derivatives thereof And are mixed.
  • the flame-retardant resin composition of the present invention comprises (A) a polypropylene resin composition containing 55% by mass or more of a polypropylene resin, and (B) 5% by mass or more and 20% by mass of titanium dioxide. And (C) a flame retardant resin composition obtained by mixing 1% by mass to 30% by mass of a brominated flame retardant, wherein the brominated flame retardant is ethylene bispentabromodiphenyl, ethylene bis It contains at least one selected from the group consisting of tetrabromophthalimide and decabromodiphenyl ether.
  • the said brominated flame retardant contains at least 1 or more types chosen from the group of ethylenebispentabromodiphenyl or its derivative (s), ethylenebistetrabromophthalimide or its derivative (s). Moreover, in this invention, it is preferable that the said brominated flame retardant contains at least 1 or more types chosen from the group of ethylenebispentabromodiphenyl or its derivative (s). Furthermore, in this invention, it is preferable that the said brominated flame retardant contains ethylenebispentabromodiphenyl.
  • the flame retardant aid is at least one selected from the group consisting of antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, and silicon dioxide. It is preferable. Furthermore, in the present invention, it is preferable that the titanium dioxide is surface-treated with at least one selected from the group consisting of silicon dioxide and aluminum oxide.
  • the polypropylene resin may be a homopolymer of propylene, a random copolymer of propylene and an ⁇ -olefin other than propylene, and a block copolymer of propylene and an ⁇ -olefin other than propylene. It is preferable to have a configuration that is at least one selected from the group. Furthermore, in this invention, it is preferable to set it as the structure formed by mixing at least 1 type or more chosen from the group of a ultraviolet absorber and a light stabilizer by 0.01 mass% or more and 5 mass% or less by external mix
  • the polypropylene resin composition preferably contains a polyethylene resin.
  • the polyethylene resin has a density 0.910 g / cm 3 or more 0.965 g / cm 3 or less, or less 50 g / 10 min melt mass flow rate 0.01 g / 10 minutes or more at 190 ° C.
  • Ethylene It is preferable that at least one selected from the group consisting of a homopolymer and a copolymer of ethylene and an ⁇ -olefin other than ethylene is preferable.
  • the molded product of the present invention is formed by molding the flame retardant resin composition of the present invention.
  • the laminated structure of the present invention is characterized by having at least one layer composed of the flame retardant resin composition of the present invention. And in the laminated structure of this invention, it is preferable that the layer which consists of the said flame-retardant resin composition is set as the structure which is a surface layer.
  • the reflecting plate of the present invention is formed by molding the flame retardant resin composition of the present invention.
  • the illuminating device of the present invention includes the reflector of the present invention.
  • the resin composition containing titanium dioxide contains at least one bromine selected from the group consisting of ethylenebispentabromodiphenyl or a derivative thereof, ethylenebistetrabromophthalimide or a derivative thereof, decabromodiphenyl ether or a derivative thereof. Since a flame retardant is mixed, flame retardancy can be imparted while maintaining reflectivity and moldability.
  • the flame-retardant resin composition of the present invention is suitable for, for example, a molded body or a laminated structure such as an electric signboard or lighting device using a light emitting diode or organic EL (Electro Luminescence) as a light source, or a reflection plate of a display. Used, but not limited to this.
  • the flame-retardant resin composition of the present invention comprises (A) a polypropylene resin composition containing 55% by mass or more of a polypropylene resin, and (B) 5% by mass or more and 20% by mass or less of titanium dioxide. (C) 1% by mass or more and 30% by mass or less of at least one brominated flame retardant selected from the group of ethylene bispentabromodiphenyl or derivatives thereof, ethylene bistetrabromophthalimide or derivatives thereof, decabromodiphenyl ether or derivatives thereof And are mixed.
  • the polypropylene resin composition is a resin containing 55% by mass or more of a polypropylene resin.
  • the polypropylene resin is selected from the group of, for example, a propylene homopolymer, a random copolymer of propylene and an ⁇ -olefin other than propylene, and a block copolymer of propylene and an ⁇ -olefin other than propylene. At least one or more are preferably used. And if content of polypropylene resin becomes less than 55 mass%, since the reflectance fall by the surface smoothness of a molded object being impaired, and a heat resistant fall arise, 55 mass in a polypropylene resin composition is produced.
  • % Or more must be contained.
  • a polypropylene resin composition it is preferable to contain a polyethylene-type resin, for example. That is, the melt tension of the flame retardant resin composition can be further improved by containing a polyethylene resin. Thus, by improving the melt tension, it is possible to improve the shapeability (drawdown at the time of vacuum forming) in the molding or secondary processing of the extrusion molded body (sheet).
  • the polyethylene resin density 0.910 g / cm 3 or more 0.965 g / cm 3 or less, ethylene homopolymer or less 50 g / 10 min melt mass flow rate 0.01 g / 10 minutes or more at 190 ° C.
  • At least one selected from the group of copolymers of ethylene and ⁇ -olefins other than ethylene can be used. This is because if the density of the polyethylene resin is out of the above range, the moldability and the mechanical properties of the molded body may be deteriorated. In addition, if the melt mass flow rate at 190 ° C. is outside the above range, the reflectance may be lowered due to defects in moldability and surface appearance in terms of fluidity of the flame retardant resin composition. And a polypropylene resin composition contains 50 mass% or more with respect to the whole flame-retardant resin composition. If the amount is less than 50% by mass, there will be a problem in the formability of extrudates during molding of pellets or in the formability in secondary processing (drawdown during vacuum forming, load on processing equipment, etc.).
  • Titanium dioxide (B) Titanium dioxide (B) Any one of anatase type, rutile type and brookite type can be used as titanium dioxide, and rutile type which is the most stable structure is particularly preferable. Titanium dioxide is preferably a granular material surface-treated with at least one selected from the group consisting of inorganic compounds and organic compounds.
  • inorganic compounds include hydrous oxides, oxides, hydroxides, and siloxanes of metals such as aluminum, silicon, zirconium, titanium, antimony, tin, and cerium.
  • the organic compound include polyols and silane coupling agents.
  • titanium oxide surface-treated with silicon dioxide or aluminum oxide is preferable because it prevents deterioration of the flame-retardant resin composition after a long period of time outdoors or in the vicinity of a light source, and titanium oxide surface-treated with polyol is difficult. It is preferable at the point which the dispersibility to a fuel resin composition is excellent. Titanium dioxide preferably has an average particle size of 0.4 ⁇ m or less. This is because if the average particle size is larger than 0.4 ⁇ m, the dispersibility in the molded article is inferior and the reflectance may be lowered. And titanium dioxide is contained by 5 mass% or more and 20 mass% with respect to the whole flame-retardant resin composition.
  • brominated flame retardant at least one brominated flame retardant selected from the group of ethylene bispentabromodiphenyl or a derivative thereof, ethylene bistetrabromophthalimide or a derivative thereof, decabromodiphenyl ether or a derivative thereof is used.
  • these derivatives can be any derivatives in which some of the molecules of the compound are substituted and do not impair the function as a brominated flame retardant.
  • Brominated flame retardants are superior in long-term heat resistance compared to non-brominated flame retardants typified by phosphorus-based flame retardants and metal hydroxides, and therefore flame retardant resin compositions containing brominated flame retardants are: It can be used stably for a long time without deterioration in the vicinity of a heat source (lighting fixture such as LED).
  • a heat source lighting fixture such as LED
  • the phosphorus-based flame retardant tends to bleed out on the surface of the molded body, and the reflectance of the molded body may decrease after a long period of time.
  • metal hydroxides are inferior in acid resistance compared to brominated flame retardants, there is a risk of rapid deterioration when exposed to rain with high acidity for a long time outdoors.
  • At least one selected from the group consisting of ethylene bispentabromodiphenyl or a derivative thereof, ethylene bistetrabromophthalimide or a derivative thereof, decabromodiphenyl ether or a derivative thereof is excellent in heat resistance and is thermally decomposed during molding. Is less, and the antagonistic action with the weathering agent is small.
  • ethylenebispentabromodiphenyl has excellent long-term heat resistance and high tracking resistance after changes over time when the flame retardant resin composition is used in a reflector such as an illuminating device that is an electrical device. Is preferable.
  • a brominated flame retardant is contained at 1 mass% or more and 30 mass% or less with respect to the whole flame-retardant resin composition.
  • the content of brominated flame retardant is less than 1% by mass, the flame retardancy is inferior, and when used for lighting members, the tracking resistance is inferior and ignition may occur, and the content of brominated flame retardant is 30. This is because if the amount is more than mass%, the moldability and the mechanical properties of the molded body are lowered.
  • the flame retardant resin composition may further contain 1% by mass or more and 30% by mass or less of an internal flame retardant aid.
  • the flame retardant aid is not particularly limited.
  • At least one selected from the group consisting of antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, and silicon dioxide is ethylene bispentabromodiphenyl or a derivative thereof, ethylene bistetrabromophthalimide or a derivative thereof It is preferably used in that it exhibits a synergistic effect with decabromodiphenyl ether or a derivative thereof and improves the flame retardancy of the resin composition.
  • the content of the flame retardant auxiliary is less than 1% by mass with respect to the entire flame retardant resin composition, the flame retardancy is inferior, and when used for a lighting member or the like, the tracking resistance is inferior and ignition may occur. This is because if it exceeds 30% by mass, the moldability and the mechanical properties of the molded article may be deteriorated.
  • the flame retardant resin composition can be further mixed with at least one selected from the group consisting of ultraviolet absorbers and light stabilizers in an external formulation of 0.01% by mass to 5% by mass.
  • the ultraviolet absorber is a component that absorbs ultraviolet rays that promote deterioration of the resin component, and is not particularly limited.
  • a benzophenone compound, a triazole compound, or a benzoate compound can be used.
  • the light stabilizer is a component that takes in radicals that promote deterioration of the resin component, and is not particularly limited.
  • an NH type hindered amine compound, an N-methyl type hindered amine compound, and an NOR type A hindered amine compound can be used.
  • an ultraviolet absorber and a light stabilizer can prevent deterioration of a resin component more by mixing and using, you may use individually, respectively.
  • the compounding quantity of at least 1 sort (s) chosen from the group of a ultraviolet absorber and a light stabilizer becomes less than 0.01 mass% (0.01 mass part) of external compounding, a molded object will be in the outdoors or near a light source.
  • the surface of the molded body may deteriorate due to light after a long period of time, causing discoloration and a decrease in reflectance.
  • the amount exceeds 5% by mass (5 parts by mass), the weathering agent is added to the surface of the molded body. Since bleed may cause a decrease in surface appearance and reflectance, it is blended in the above range.
  • the flame-retardant resin composition is prepared, for example, by melting and kneading each raw material and using a pelletizer as pellets.
  • the flame-retardant resin composition in the form of pellets is molded into a predetermined shape, formed into a sheet, and laminated on the surface of a preformed substrate, or the flame-retardant resin composition is used together with other resins. Extrusion is performed to form a laminated structure having at least one layer of the flame retardant resin composition, and the laminated structure is molded to form a reflector.
  • Example 1 to 4 Comparative Examples 1 to 5
  • the raw materials used in the following Examples 1 to 4 and Comparative Examples 1 to 5 are as follows.
  • Polypropylene resin hereinafter PP
  • the above raw materials are blended in the proportions shown in Tables 1 and 2 below, melt kneaded using a twin screw extruder with a screw diameter of 30 mm set at a cylinder temperature of 260 ° C., and the strand discharged from the die is cooled by a cooling bath.
  • the flame-retardant resin composition was prepared by cutting with a pelletizer and pelletizing.
  • the test piece in each formulation was evaluated by flame retardancy, reflectance, weather resistance, and formability.
  • Flame retardancy was evaluated by a method based on JIS K6911 A method. Specifically, the combustion test piece produced by the above method was used as a sample, the flame height was set to 25 mm, the flame was tilted by 30 °, and the test piece was in contact with the test piece for 30 seconds and then burned for 180 seconds or more If flammable. If the fire extinguishes within 180 seconds and the combustion distance exceeds 25 mm and is 100 mm or less, it is self extinguishing. When the fire was extinguished within 180 seconds and the combustion distance was 25 mm or less, it was determined to be nonflammable. The results are shown in Tables 1 and 2.
  • the flat plate produced by the above-mentioned method was used as a reflectance measurement sample, and the reflectance was measured using a spectrophotometer (trade name COLOR-Eye 7000A, manufactured by GRETAGMACBETH) under the condition of a 10-degree field of view with a D65 light source. The results are shown in Tables 1 and 2.
  • the draw-down property was evaluated as the draw-down property by measuring the amount of sag when the sheet obtained by the above method was processed to 330 mm ⁇ 330 mm and indirectly heated at 450 ° C. for 30 seconds. Based on the amount of droop obtained by the above method, the drawdown property was determined according to the following criteria.
  • melt tension (unit: mN) was melted by heating to 230 ° C. using a capillary rheometer (manufactured by Toyo Seiki Seisakusho). The sample was extruded from a nozzle having a diameter of 1 mm into the atmosphere at 23 ° C. so as to have a speed of 30 mm / min, and the tension when the obtained strand was drawn at a speed of 6 m / min was measured.
  • the melt tension obtained by the above evaluation method was determined according to the following criteria.
  • Tables 1 and 2 The results are shown in Tables 1 and 2 below.
  • Comparative Examples 6 and 7 were carried out in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 5 except that the following raw materials were used. The results are shown in Table 3 below.
  • Flame Retardant-D Flame Cut 120G (trade name, manufactured by Tosoh Corporation) (Tetrabromobisphenol-A) ⁇ Flame retardant-E; Fireguard 3600 (trade name, manufactured by Teijin Chemicals Ltd.) (tetrabromobisphenol-A diglycidyl ether) ⁇ Flame retardant aid: Antimony trioxide FCP-AT3 (trade name, manufactured by Suzuhiro Chemical Co., Ltd.) ⁇ Titanium dioxide; PF-691 (trade name, manufactured by Ishihara Sangyo Co., Ltd.) UV absorber; Chemisorb 114 (trade name, manufactured by Chemipro Kasei Co., Ltd.) Light stabilizer: Tinuvin XT850 (trade name, manufactured by BASF Japan)
  • Example 5 to 8 and Comparative Examples 8 and 9 were carried out in the same manner as Examples 1 to 4 and Comparative Examples 1 to 5 except that the following raw materials were used. The results are shown in Table 4 below.
  • the present invention is suitably used for an electric signboard or lighting device using a light emitting diode or an organic EL (Electro Luminescence) as a light source, a molded body such as a reflection plate of a display, a laminated structure, or a flame retardant resin composition thereof It is done.
  • a light emitting diode or an organic EL Electro Luminescence
  • a molded body such as a reflection plate of a display, a laminated structure, or a flame retardant resin composition thereof It is done.

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  • Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

This flame-retardant resin composition is obtained by blending (A) 50% by mass or more of a polypropylene resin composition that contains 55% by mass or more of a polypropylene resin, (B) from 5% by mass to 20% by mass (inclusive) of titanium dioxide, and (C) from 1% by mass to 30% by mass (inclusive) of at least one bromine-based flame retardant that is selected from the group consisting of ethylenebispentabromodiphenyl and derivatives thereof, ethylenebistetrabromophthalimide and derivatives thereof, and decabromodiphenyl ether and derivatives thereof.

Description

難燃性樹脂組成物、成形体、積層構造体、反射板、および、照明装置Flame-retardant resin composition, molded body, laminated structure, reflector, and lighting device
　本発明は、二酸化チタンを含有する難燃性樹脂組成物、成形体、積層構造体、反射板、および照明装置に関する。 The present invention relates to a flame retardant resin composition containing titanium dioxide, a molded body, a laminated structure, a reflector, and a lighting device.
　近年、発光ダイオードなどを光源とする電飾看板、照明器具、ディスプレイなどの反射板などに、二酸化チタンを含有する樹脂組成物が用いられている（例えば、特許文献１～４参照）。
　特許文献１に記載の樹脂組成物は、ポリプロピレン系樹脂またはポリプロピレン系樹脂を主成分とする樹脂に対して、二酸化チタンおよび無機充填剤の合計で４５質量％、二酸化チタンとして５～４２質量％、無機充填剤として３～１８質量％を含有する。そして、この樹脂組成物は、反射率を損なわない範囲で、塩素や臭素などのハロゲン系、リン系、金属酸化物系、金属水酸化物系などの難燃剤を添加可能としている。
　特許文献２に記載の樹脂組成物は、エチレンプロピレンブロック共重合体と高密度ポリエチレンとに対し、酸化チタンを５～１０質量％含有する。そして、この樹脂組成物は、必要に応じて難燃剤を配合可能としている。
　特許文献３に記載の樹脂組成物は、ポリプロピレンの重合体マトリックス３１～７０重量％に、難燃性物質１２～２４重量％および反射性充填材（ルチル形チタニア）の粒子１５～３０重量％の割合で分散された光反射性物質の構成が採られている。
　特許文献４に記載の樹脂組成物は、ポリプロピレン樹脂に、デカブロモジフェニルオキシドのような臭素化芳香族化合物や臭素化イミドなどの難燃剤を１～５０wt％添加された反射性物質の構成が採られている。 In recent years, resin compositions containing titanium dioxide have been used for reflectors such as electric signboards, lighting fixtures, and displays that use light emitting diodes as a light source (see, for example, Patent Documents 1 to 4).
The resin composition described in Patent Document 1 is 45% by mass in total of titanium dioxide and inorganic filler, 5 to 42% by mass as titanium dioxide, based on polypropylene resin or resin based on polypropylene resin, As an inorganic filler, 3 to 18% by mass is contained. The resin composition can be added with a flame retardant such as halogen, phosphorus, metal oxide, metal hydroxide, or the like, such as chlorine or bromine, as long as the reflectance is not impaired.
The resin composition described in Patent Document 2 contains 5 to 10% by mass of titanium oxide with respect to the ethylene propylene block copolymer and the high-density polyethylene. And this resin composition can mix | blend a flame retardant as needed.
The resin composition described in Patent Document 3 comprises polypropylene polymer matrix of 31 to 70% by weight, flame retardant material of 12 to 24% by weight and reflective filler (rutile titania) particles of 15 to 30% by weight. The structure of the light-reflective material dispersed in proportion is adopted.
The resin composition described in Patent Document 4 has a reflective material structure in which 1 to 50 wt% of a flame retardant such as brominated aromatic compound such as decabromodiphenyl oxide or brominated imide is added to polypropylene resin. It has been.
特開２００９－２９２８６４号公報JP 2009-292864 A 特開２０１１－２６４２２号公報JP 2011-26422 A 特表２００２－５３５７３１号公報JP 2002-535731 A 特表２００４－５２３７９２号公報Japanese translation of PCT publication No. 2004-523792
　しかしながら、特許文献１，２に記載のような二酸化チタンを含有して反射率を高めた樹脂組成物では、難燃性を付与するために難燃剤を添加すると、反射率および成形性が低下してしまうおそれがある。また、特許文献３，４に記載の難燃剤を添加して難燃性を付与したものでも、十分な反射率および成形性が得られない。 However, in the resin composition containing titanium dioxide as described in Patent Documents 1 and 2 and having an increased reflectance, when a flame retardant is added to impart flame retardancy, the reflectance and moldability decrease. There is a risk that. Moreover, even if what added the flame retardant of patent documents 3 and 4 and gave flame retardance, sufficient reflectance and a moldability are not obtained.
　本発明は、成形性および反射率の低下を抑制しつつ難燃性が得られる難燃性樹脂組成物、成形体、積層構造体、反射板、および、照明装置を提供することを目的とする。 An object of the present invention is to provide a flame retardant resin composition, a molded body, a laminated structure, a reflector, and a lighting device that can obtain flame retardancy while suppressing deterioration in moldability and reflectance. .
　本発明の難燃性樹脂組成物は、（Ａ）ポリプロピレン系樹脂を５５質量％以上含有するポリプロピレン系樹脂組成物５０質量％以上と、（Ｂ）二酸化チタンを５質量％以上２０質量％以下と、（Ｃ）エチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体、デカブロモジフェニルエーテルまたはその誘導体の群から選ばれる少なくとも一種以上の臭素系難燃剤を１質量％以上３０質量％以下と、を混合してなることを特徴とする。
　また、本発明の難燃性樹脂組成物は、（Ａ）ポリプロピレン系樹脂を５５質量％以上含有するポリプロピレン系樹脂組成物５０質量％以上と、（Ｂ）二酸化チタンを５質量％以上２０質量％以下と、（Ｃ）臭素系難燃剤を１質量％以上３０質量％以下と、を混合してなる難燃性樹脂組成物であって、前記臭素系難燃剤がエチレンビスペンタブロモジフェニル、エチレンビステトラブロモフタルイミド、デカブロモジフェニルエーテルの群から選ばれる少なくとも一種以上含有することを特徴とする。
　さらに、本発明では、前記臭素系難燃剤がエチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体の群から選ばれる少なくとも一種以上含有することが好ましい。
　また、本発明では、前記臭素系難燃剤がエチレンビスペンタブロモジフェニルまたはその誘導体の群から選ばれる少なくとも一種以上含有することが好ましい。
　さらに、本発明では、前記臭素系難燃剤がエチレンビスペンタブロモジフェニルを含有することが好ましい。 The flame-retardant resin composition of the present invention comprises (A) a polypropylene resin composition containing 55% by mass or more of a polypropylene resin, and (B) 5% by mass or more and 20% by mass or less of titanium dioxide. (C) 1% by mass or more and 30% by mass or less of at least one brominated flame retardant selected from the group of ethylene bispentabromodiphenyl or derivatives thereof, ethylene bistetrabromophthalimide or derivatives thereof, decabromodiphenyl ether or derivatives thereof And are mixed.
The flame-retardant resin composition of the present invention comprises (A) a polypropylene resin composition containing 55% by mass or more of a polypropylene resin, and (B) 5% by mass or more and 20% by mass of titanium dioxide. And (C) a flame retardant resin composition obtained by mixing 1% by mass to 30% by mass of a brominated flame retardant, wherein the brominated flame retardant is ethylene bispentabromodiphenyl, ethylene bis It contains at least one selected from the group consisting of tetrabromophthalimide and decabromodiphenyl ether.
Furthermore, in this invention, it is preferable that the said brominated flame retardant contains at least 1 or more types chosen from the group of ethylenebispentabromodiphenyl or its derivative (s), ethylenebistetrabromophthalimide or its derivative (s).
Moreover, in this invention, it is preferable that the said brominated flame retardant contains at least 1 or more types chosen from the group of ethylenebispentabromodiphenyl or its derivative (s).
Furthermore, in this invention, it is preferable that the said brominated flame retardant contains ethylenebispentabromodiphenyl.
　そして、本発明では、さらに難燃助剤を内配合で１質量％以上３０質量％以下混合してなる構成とすることが好ましい。
　また、本発明では、前記難燃助剤は、三酸化アンチモンと、ホウ酸亜鉛と、ポリテトラフルオロエチレンと、金属酸化物と、二酸化珪素との群から選ばれる少なくとも一種以上である構成とすることが好ましい。
　さらに、本発明では、前記二酸化チタンは、二酸化珪素および酸化アルミニウムの群から選ばれる少なくとも一種以上で表面処理されている構成とすることが好ましい。
　また、本発明では、前記ポリプロピレン系樹脂は、プロピレンの単独重合体、プロピレンとプロピレン以外のα－オレフィンとのランダム共重合体、および、プロピレンとプロピレン以外のα－オレフィンとのブロック共重合体の群から選ばれる少なくとも一種以上である構成とすることが好ましい。
　さらに、本発明では、紫外線吸収剤および光安定剤の群から選ばれる少なくとも一種以上を、外配合で０．０１質量％以上５質量％以下混合してなる構成とすることが好ましい。
　そして、本発明では、前記ポリプロピレン系樹脂組成物は、ポリエチレン系樹脂を含有する構成とすることが好ましい。
　また、本発明では、前記ポリエチレン系樹脂は、密度０．９１０ｇ／ｃｍ３以上０．９６５ｇ／ｃｍ３以下、１９０℃でのメルトマスフローレート０．０１ｇ／１０分以上５０ｇ／１０分以下であるエチレン単独重合体、エチレンとエチレン以外のα－オレフィンとの共重合体の群から選ばれる少なくとも一種以上である構成とすることが好ましい。 And in this invention, it is preferable to set it as the structure formed by further mixing 1 mass% or more and 30 mass% or less of flame retardant adjuvant by internal mixing.
In the present invention, the flame retardant aid is at least one selected from the group consisting of antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, and silicon dioxide. It is preferable.
Furthermore, in the present invention, it is preferable that the titanium dioxide is surface-treated with at least one selected from the group consisting of silicon dioxide and aluminum oxide.
In the present invention, the polypropylene resin may be a homopolymer of propylene, a random copolymer of propylene and an α-olefin other than propylene, and a block copolymer of propylene and an α-olefin other than propylene. It is preferable to have a configuration that is at least one selected from the group.
Furthermore, in this invention, it is preferable to set it as the structure formed by mixing at least 1 type or more chosen from the group of a ultraviolet absorber and a light stabilizer by 0.01 mass% or more and 5 mass% or less by external mix | blending.
In the present invention, the polypropylene resin composition preferably contains a polyethylene resin.
In the present invention, the polyethylene resin has a density 0.910 g / cm 3 or more 0.965 g / cm 3 or less, or less 50 g / 10 min melt mass flow rate 0.01 g / 10 minutes or more at 190 ° C. Ethylene It is preferable that at least one selected from the group consisting of a homopolymer and a copolymer of ethylene and an α-olefin other than ethylene is preferable.
　本発明の成形体は、本発明の難燃性樹脂組成物を成形してなることを特徴とする。
　本発明の積層構造体は、本発明の難燃性樹脂組成物からなる層を少なくとも１層以上有していることを特徴とする。
　そして、本発明の積層構造体では、前記難燃性樹脂組成物からなる層は、表面層である構成とすることが好ましい。
　本発明の反射板は、本発明の難燃性樹脂組成物を成形してなることを特徴とする。
　本発明の照明装置は、本発明の反射板を備えたことを特徴とする。 The molded product of the present invention is formed by molding the flame retardant resin composition of the present invention.
The laminated structure of the present invention is characterized by having at least one layer composed of the flame retardant resin composition of the present invention.
And in the laminated structure of this invention, it is preferable that the layer which consists of the said flame-retardant resin composition is set as the structure which is a surface layer.
The reflecting plate of the present invention is formed by molding the flame retardant resin composition of the present invention.
The illuminating device of the present invention includes the reflector of the present invention.
　本発明によれば、二酸化チタンを含有する樹脂組成物に、エチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体、デカブロモジフェニルエーテルまたはその誘導体の群から選ばれる少なくとも一種以上の臭素系難燃剤を混合してなるので、反射率および成形性を維持しつつ難燃性を付与することができる。 According to the present invention, the resin composition containing titanium dioxide contains at least one bromine selected from the group consisting of ethylenebispentabromodiphenyl or a derivative thereof, ethylenebistetrabromophthalimide or a derivative thereof, decabromodiphenyl ether or a derivative thereof. Since a flame retardant is mixed, flame retardancy can be imparted while maintaining reflectivity and moldability.
　以下、本発明の難燃性樹脂組成物の実施形態について説明する。
　なお、本発明の難燃性樹脂組成物は、例えば発光ダイオードや有機ＥＬ（Electro Luminescence）を光源とした電飾看板または照明装置、あるいはディスプレイの反射板などの成形体や積層構造体に好適に用いられるが、この限りではない。 Hereinafter, embodiments of the flame-retardant resin composition of the present invention will be described.
The flame-retardant resin composition of the present invention is suitable for, for example, a molded body or a laminated structure such as an electric signboard or lighting device using a light emitting diode or organic EL (Electro Luminescence) as a light source, or a reflection plate of a display. Used, but not limited to this.
　［原料］
　本発明の難燃性樹脂組成物は、（Ａ）ポリプロピレン系樹脂を５５質量％以上含有するポリプロピレン系樹脂組成物５０質量％以上と、（Ｂ）二酸化チタンを５質量％以上２０質量％以下と、（Ｃ）エチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体、デカブロモジフェニルエーテルまたはその誘導体の群から選ばれる少なくとも一種以上の臭素系難燃剤を１質量％以上３０質量％以下と、が混合されたものである。 [material]
The flame-retardant resin composition of the present invention comprises (A) a polypropylene resin composition containing 55% by mass or more of a polypropylene resin, and (B) 5% by mass or more and 20% by mass or less of titanium dioxide. (C) 1% by mass or more and 30% by mass or less of at least one brominated flame retardant selected from the group of ethylene bispentabromodiphenyl or derivatives thereof, ethylene bistetrabromophthalimide or derivatives thereof, decabromodiphenyl ether or derivatives thereof And are mixed.
　　（（Ａ）ポリプロピレン系樹脂組成物）
　（Ａ）ポリプロピレン系樹脂組成物は、ポリプロピレン系樹脂を５５質量％以上含有する樹脂である。
　ポリプロピレン系樹脂としては、例えば、プロピレンの単独重合体、プロピレンとプロピレン以外のα－オレフィンとのランダム共重合体、および、プロピレンとプロピレン以外のα－オレフィンとのブロック共重合体の群から選ばれる少なくとも一種以上が、好適に用いられる。
　そして、ポリプロピレン系樹脂の含有量が５５質量％より少なくなると、成形体の表面平滑性が損なわれることによる反射率の低下、および耐熱性の低下が生じるため、ポリプロピレン系樹脂組成物中に５５質量％以上含有させることが必要である。
　また、ポリプロピレン系樹脂組成物としては、例えばポリエチレン系樹脂を含有することが好ましい。すなわち、ポリエチレン系樹脂を含有することで、難燃性樹脂組成物の溶融張力をさらに向上できる。このことにより、溶融張力を向上させることで押出成形体（シート）の成形または二次加工における賦形性（真空成形時のドローダウン）を向上できる。
　ここで、ポリエチレン系樹脂としては、密度０．９１０ｇ／ｃｍ３以上０．９６５ｇ／ｃｍ３以下、１９０℃でのメルトマスフローレート０．０１ｇ／１０分以上５０ｇ／１０分以下であるエチレン単独重合体、エチレンとエチレン以外のα－オレフィンとの共重合体の群から選ばれる少なくとも一種以上を用いることができる。ポリエチレン系樹脂の密度が上記範囲外となると、成形性や成形体の機械的物性の低下が生じるおそれがあるためである。また、１９０℃でのメルトマスフローレートが上記範囲外となると、難燃樹脂組成物の流動性の点で成形性や表面外観の不具合による反射率の低下が生じるおそれがあるためである。
　そして、ポリプロピレン系樹脂組成物は、難燃性樹脂組成物全体に対して５０質量％以上含有する。５０質量％より少なくなると、ペレット造粒時、押出成形体の成形または二次加工における賦形性（真空成形時のドローダウン・加工設備への負荷等）に問題が生じるためである。 ((A) Polypropylene resin composition)
(A) The polypropylene resin composition is a resin containing 55% by mass or more of a polypropylene resin.
The polypropylene resin is selected from the group of, for example, a propylene homopolymer, a random copolymer of propylene and an α-olefin other than propylene, and a block copolymer of propylene and an α-olefin other than propylene. At least one or more are preferably used.
And if content of polypropylene resin becomes less than 55 mass%, since the reflectance fall by the surface smoothness of a molded object being impaired, and a heat resistant fall arise, 55 mass in a polypropylene resin composition is produced. % Or more must be contained.
Moreover, as a polypropylene resin composition, it is preferable to contain a polyethylene-type resin, for example. That is, the melt tension of the flame retardant resin composition can be further improved by containing a polyethylene resin. Thus, by improving the melt tension, it is possible to improve the shapeability (drawdown at the time of vacuum forming) in the molding or secondary processing of the extrusion molded body (sheet).
Examples of the polyethylene resin, density 0.910 g / cm 3 or more 0.965 g / cm 3 or less, ethylene homopolymer or less 50 g / 10 min melt mass flow rate 0.01 g / 10 minutes or more at 190 ° C. Further, at least one selected from the group of copolymers of ethylene and α-olefins other than ethylene can be used. This is because if the density of the polyethylene resin is out of the above range, the moldability and the mechanical properties of the molded body may be deteriorated. In addition, if the melt mass flow rate at 190 ° C. is outside the above range, the reflectance may be lowered due to defects in moldability and surface appearance in terms of fluidity of the flame retardant resin composition.
And a polypropylene resin composition contains 50 mass% or more with respect to the whole flame-retardant resin composition. If the amount is less than 50% by mass, there will be a problem in the formability of extrudates during molding of pellets or in the formability in secondary processing (drawdown during vacuum forming, load on processing equipment, etc.).
　　（（Ｂ）二酸化チタン）
　（Ｂ）二酸化チタンは、アナターゼ型、ルチル型、ブルカイト型のいずれのものが利用でき、特に最も安定な構造であるルチル型が好ましい。
　二酸化チタンとしては、無機化合物および有機化合物の群から選ばれる少なくとも一種以上で表面処理された粉粒体が好ましい。
　無機化合物としては、アルミニウム、ケイ素、ジルコニウム、チタン、アンチモン、スズまたはセリウムなどの金属の含水酸化物、酸化物、水酸化物およびシロキサンなどが挙げられる。有機化合物としては、ポリオール、シランカップリング剤などが挙げられる。
　特に、二酸化珪素や酸化アルミニウムで表面処理された酸化チタンは、屋外や光源近傍で長時間経過後に難燃樹脂組成物の劣化を防止する点で好ましく、ポリオールで表面処理された酸化チタンは、難燃樹脂組成物への分散性が優れる点で好ましい。
　また、二酸化チタンは、平均粒径が０．４μｍ以下のものが好ましい。平均粒径が０．４μｍより大きいと成形体中での分散性に劣り、反射率の低下が生じるおそれがあるためである。
　そして、二酸化チタンは、難燃性樹脂組成物全体に対して５質量％以上２０質量％で含有される。二酸化チタンの含有量が５質量％より少なくなると、成形体において十分な反射率が得られず、反射体としての機能が得られなくなる。一方、二酸化チタンの含有量が２０質量％より多くなると、成形性が損なわれるなどの不都合を生じるおそれがあるためである。 ((B) Titanium dioxide)
(B) Any one of anatase type, rutile type and brookite type can be used as titanium dioxide, and rutile type which is the most stable structure is particularly preferable.
Titanium dioxide is preferably a granular material surface-treated with at least one selected from the group consisting of inorganic compounds and organic compounds.
Examples of inorganic compounds include hydrous oxides, oxides, hydroxides, and siloxanes of metals such as aluminum, silicon, zirconium, titanium, antimony, tin, and cerium. Examples of the organic compound include polyols and silane coupling agents.
In particular, titanium oxide surface-treated with silicon dioxide or aluminum oxide is preferable because it prevents deterioration of the flame-retardant resin composition after a long period of time outdoors or in the vicinity of a light source, and titanium oxide surface-treated with polyol is difficult. It is preferable at the point which the dispersibility to a fuel resin composition is excellent.
Titanium dioxide preferably has an average particle size of 0.4 μm or less. This is because if the average particle size is larger than 0.4 μm, the dispersibility in the molded article is inferior and the reflectance may be lowered.
And titanium dioxide is contained by 5 mass% or more and 20 mass% with respect to the whole flame-retardant resin composition. When the content of titanium dioxide is less than 5% by mass, sufficient reflectance cannot be obtained in the molded body, and the function as a reflector cannot be obtained. On the other hand, when the content of titanium dioxide is more than 20% by mass, there is a possibility that inconveniences such as impaired moldability may occur.
　　（（Ｃ）臭素系難燃剤）
　（Ｃ）臭素系難燃剤として、エチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体、デカブロモジフェニルエーテルまたはその誘導体の群から選ばれる少なくとも一種以上の臭素系難燃剤が用いられる。ここで、これら誘導体は、化合物の一部の分子が置換されたもので、臭素系難燃剤としての機能が損なわれないいずれの誘導体を対象とすることができる。
　臭素系難燃剤は、リン系難燃剤や金属水酸化物に代表される非臭素難燃剤と比較して、長期耐熱性に優れるため、臭素系難燃剤を含有した難燃性樹脂組成物は、長期間にわたり熱源（ＬＥＤなどの照明器具)の周辺において劣化せずに安定して使用することができる。特に、リン系難燃剤は、成形体表面にブリードアウトしやすく、長期経過後に成形体の反射率が低下するおそれがある。さらに、金属水酸化物は、臭素系難燃剤と比較して耐酸性に劣るため、屋外で長期間にわたり、酸性度の高い雨にさらされた場合、急速に劣化が進むおそれがある。
　臭素系難燃剤として、エチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体、デカブロモジフェニルエーテルまたはその誘導体の群から選ばれる少なくとも一種以上は、耐熱性に優れ、成形時の熱分解が少なく、耐候剤との拮抗作用が小さいため成形体の耐候性に優れる点で好ましい。特に、エチレンビスペンタブロモジフェニルは、難燃性樹脂組成物を電気機器である照明装置などの反射体に用いた場合、反射体の長期耐熱性が優れ、経時変化後の耐トラッキング性が高い点で好ましい。
　そして、臭素系難燃剤は、難燃性樹脂組成物全体に対して１質量％以上３０質量％以下で含有される。臭素系難燃剤の含有量が１質量％より少なくなると、難燃性が劣り、照明部材などに用いた場合、耐トラッキング性に劣り発火が生じるおそれがあり、臭素系難燃剤の含有量が３０質量％より多くなると、成形性や成形体の機械的物性の低下が生じるためである。 ((C) Brominated flame retardant)
(C) As the brominated flame retardant, at least one brominated flame retardant selected from the group of ethylene bispentabromodiphenyl or a derivative thereof, ethylene bistetrabromophthalimide or a derivative thereof, decabromodiphenyl ether or a derivative thereof is used. Here, these derivatives can be any derivatives in which some of the molecules of the compound are substituted and do not impair the function as a brominated flame retardant.
Brominated flame retardants are superior in long-term heat resistance compared to non-brominated flame retardants typified by phosphorus-based flame retardants and metal hydroxides, and therefore flame retardant resin compositions containing brominated flame retardants are: It can be used stably for a long time without deterioration in the vicinity of a heat source (lighting fixture such as LED). In particular, the phosphorus-based flame retardant tends to bleed out on the surface of the molded body, and the reflectance of the molded body may decrease after a long period of time. Furthermore, since metal hydroxides are inferior in acid resistance compared to brominated flame retardants, there is a risk of rapid deterioration when exposed to rain with high acidity for a long time outdoors.
As the brominated flame retardant, at least one selected from the group consisting of ethylene bispentabromodiphenyl or a derivative thereof, ethylene bistetrabromophthalimide or a derivative thereof, decabromodiphenyl ether or a derivative thereof is excellent in heat resistance and is thermally decomposed during molding. Is less, and the antagonistic action with the weathering agent is small. In particular, ethylenebispentabromodiphenyl has excellent long-term heat resistance and high tracking resistance after changes over time when the flame retardant resin composition is used in a reflector such as an illuminating device that is an electrical device. Is preferable.
And a brominated flame retardant is contained at 1 mass% or more and 30 mass% or less with respect to the whole flame-retardant resin composition. When the content of brominated flame retardant is less than 1% by mass, the flame retardancy is inferior, and when used for lighting members, the tracking resistance is inferior and ignition may occur, and the content of brominated flame retardant is 30. This is because if the amount is more than mass%, the moldability and the mechanical properties of the molded body are lowered.
　　（添加剤）
　難燃性樹脂組成物は、さらに難燃助剤を内配合で１質量％以上３０質量％以下配合可能である。
　難燃助剤としては、特に限定されないが、例えば、三酸化アンチモン、ホウ酸亜鉛、ポリテトラフルオロエチレン、金属酸化物、二酸化珪素、ハイドロタルサイト、重炭酸マグネシウム、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化バナジウム、酸化モリブデンおよびその表面処理品、メラミン、メラミンシアヌレート、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、モノペンタエリスリトール、トリス（２－ヒドロキシエチル）イソシアヌレート、ポリテトラフルオロエチレンなどを用いることができる。特に、三酸化アンチモン、ホウ酸亜鉛、ポリテトラフルオロエチレン、金属酸化物、二酸化珪素からなる群から選ばれる少なくとも１種以上が、エチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体、デカブロモジフェニルエーテルまたはその誘導体との相乗効果を発現し、樹脂組成物の難燃性を向上する点で好適に用いられる。
　難燃助剤の含有量が、難燃性樹脂組成物全体に対して１質量％より少なくなると難燃性が劣り、照明部材などに用いた場合、耐トラッキング性に劣り発火が生じるおそれがあり、３０質量％より多くなると成形性や成形体の機械的物性の低下が生じるおそれがあるためである。 (Additive)
The flame retardant resin composition may further contain 1% by mass or more and 30% by mass or less of an internal flame retardant aid.
The flame retardant aid is not particularly limited. For example, antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, silicon dioxide, hydrotalcite, magnesium bicarbonate, zinc oxide, aluminum oxide, magnesium oxide , Zirconium oxide, vanadium oxide, molybdenum oxide and its surface-treated product, melamine, melamine cyanurate, pentaerythritol, dipentaerythritol, tripentaerythritol, monopentaerythritol, tris (2-hydroxyethyl) isocyanurate, polytetrafluoroethylene Etc. can be used. In particular, at least one selected from the group consisting of antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, and silicon dioxide is ethylene bispentabromodiphenyl or a derivative thereof, ethylene bistetrabromophthalimide or a derivative thereof It is preferably used in that it exhibits a synergistic effect with decabromodiphenyl ether or a derivative thereof and improves the flame retardancy of the resin composition.
When the content of the flame retardant auxiliary is less than 1% by mass with respect to the entire flame retardant resin composition, the flame retardancy is inferior, and when used for a lighting member or the like, the tracking resistance is inferior and ignition may occur. This is because if it exceeds 30% by mass, the moldability and the mechanical properties of the molded article may be deteriorated.
　また、難燃性樹脂組成物は、さらに紫外線吸収剤と光安定剤との群から選ばれる少なくとも一種以上を、外配合０．０１質量％以上５質量％以下で混合可能である。
　紫外線吸収剤としては、樹脂成分の劣化を促進する紫外線を吸収する成分で、特に限定されないが、例えば、ベンゾフェノン化合物、トリアゾール化合物、ベンゾエート化合物を用いることができる。
　具体的には、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－オクトキシベンゾフェノン、５，５’－メチレンビス（２－ヒドロキシ－４－メトキシベンゾフェノン）などの２－ヒドロキシベンゾフェノン類；２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ第三ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－第三ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－５’－第三オクチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジクミルフェニル）ベンゾトリアゾール、２，２’－メチレンビス（４－第三オクチル－６－（ベンゾトリアゾール）フェノール）、２－（２’－ヒドロキシ－３’－第三ブチル－５’－カルボキシフェニル）ベンゾトリアゾールなどの２－（２’－ヒドロキシフェニル）ベンゾトリアゾール類；フェニルサリシレート、レゾルシノールモノベンゾエート、２，４－ジ第三ブチルフェニル－３，５－ジ第三ブチル－４－ヒドロキシベンゾエート、２，４－ジ第三アミルフェニル－３，５－ジ第三ブチル－４－ヒドロキシベンゾエート、ヘキサデシル－３，５－ジ第三ブチル－４－ヒドロキシベンゾエートなどのベンゾエート類；２－エチル－２’－エトキシオキザニリド、２－エトキシ－４’－ドデシルオキザニリドなどの置換オキザニリド類；エチル－２－シアノ－３，３’－ジフェニルアクリレート、メチル－２－シアノ－３－メチル－３－（ｐ－メトキシフェニル）アクリレートなどのシアノアクリレート類；２－（２－ヒドロキシ－４－オクトキシフェニル）－４，６－ビス（２，４－ジ第三ブチルフェニル）－ｓ－トリアジン、２－（２－ヒドロキシ－４－メトキシフェニル）－４，６－ジフェニル－ｓ－トリアジン、２－（２－ヒドロキシ－４－プロポキシ－５－メチルフェニル）－４，６－ビス（２，４－ジ第三ブチルフェニル）－ｓ－トリアジンなどのトリアリールトリアジン類などが挙げられる。これらは、２種以上混合して使用してもよい。 In addition, the flame retardant resin composition can be further mixed with at least one selected from the group consisting of ultraviolet absorbers and light stabilizers in an external formulation of 0.01% by mass to 5% by mass.
The ultraviolet absorber is a component that absorbs ultraviolet rays that promote deterioration of the resin component, and is not particularly limited. For example, a benzophenone compound, a triazole compound, or a benzoate compound can be used.
Specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone) and the like 2 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary octyl-6 2- (2′-hydroxyphenyl) benzotriazoles such as (benzotriazole) phenol) and 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol mono Benzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, Benzoates such as hexadecyl-3,5-ditertiarybutyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl -2-Cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3 Cyanoacrylates such as (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 (2,4-diter And triaryltriazines such as tributylphenyl) -s-triazine. You may use these in mixture of 2 or more types.
　光安定剤としては、樹脂成分の劣化を促進するラジカルを取り込む成分で、特に限定されないが、例えば、Ｎ－Ｈ型ヒンダートアミン化合物、Ｎ－メチル型ヒンダートアミン化合物、Ｎ－Ｏ－Ｒ型ヒンダートアミン化合物を用いることができる。
　具体的には、２，２，６，６－テトラメチル－４－ピペリジルステアレート、１，２，２，６，６－ペンタメチル－４－ピペリジルステアレート、２，２，６，６－テトラメチル－４－ピペリジルベンゾエート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ビス（Ｎ－メチル－２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ビス（１－オクトキシ－２，２，６，６－テトラメチル－４－ピペリジル）セバケート、テトラキス（２，２，６，６－テトラメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）・ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）・ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－２－ブチル－２－（３，５－ジ第三ブチル－４－ヒドロキシベンジル）マロネート、１－（２－ヒドロキシエチル）－２，２，６，６－テトラメチル－４－ピペリジノール／コハク酸ジエチル重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－モルホリノ－ｓ－トリアジン重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－第三オクチルアミノ－ｓ－トリアジン重縮合物、１，５，８，１２－テトラキス〔２，４－ビス（Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕－１，５，８，１２－テトラアザドデカン、１，５，８，１２－テトラキス〔２，４－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕－１，５，８，１２－テトラアザドデカン、１，６，１１－トリス〔２，４－ビス（Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕アミノウンデカン、１，６，１１－トリス〔２，４－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕アミノウンデカンなどのヒンダードアミン化合物などが挙げられる。これらは、２種以上混合して使用してもよい。 The light stabilizer is a component that takes in radicals that promote deterioration of the resin component, and is not particularly limited. For example, an NH type hindered amine compound, an N-methyl type hindered amine compound, and an NOR type A hindered amine compound can be used.
Specifically, 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-butanetetracarboxyl , Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4- Peridyl) .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-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- And hindered amine compounds such as piperidyl) amino) -s-triazin-6-yl] aminoundecane. You may use these in mixture of 2 or more types.
　なお、紫外線吸収剤および光安定剤とは、特に混合して用いることにより、樹脂成分の劣化をより防止できるが、それぞれ単独で使用してもよい。
　そして、紫外線吸収剤および光安定剤との群から選ばれる少なくとも一種以上の配合量が、外配合０．０１質量％（０．０１質量部）より少なくなると、屋外や光源近傍で、成形体が使用された場合、長期経過後に成形体表面が、光による劣化が生じ、変色および反射率の低下が生じるおそれがあり、外配合５質量％（５質量部）より多くなると成形体表面へ耐候剤がブリードすることにより、表面外観および反射率の低下が生じるおそれがあるため、上記範囲で配合される。 In addition, although especially an ultraviolet absorber and a light stabilizer can prevent deterioration of a resin component more by mixing and using, you may use individually, respectively.
And when the compounding quantity of at least 1 sort (s) chosen from the group of a ultraviolet absorber and a light stabilizer becomes less than 0.01 mass% (0.01 mass part) of external compounding, a molded object will be in the outdoors or near a light source. When used, the surface of the molded body may deteriorate due to light after a long period of time, causing discoloration and a decrease in reflectance. When the amount exceeds 5% by mass (5 parts by mass), the weathering agent is added to the surface of the molded body. Since bleed may cause a decrease in surface appearance and reflectance, it is blended in the above range.
　難燃性樹脂組成物には、さらに、フェノール系酸化防止剤やリン系酸化防止剤あるいはチオ系酸化防止剤などの酸化防止剤、滑剤、軟化剤、結晶核剤、帯電防止剤、充填剤などの添加剤を含有させてもよい。
　そして、難燃性樹脂組成物は、例えば、各原料を溶融混練し、ペレタイザーにてペレットとして調製される。ペレットとされた難燃性樹脂組成物を、所定の形状に成形したり、シート状に成形し、あらかじめ成形された基体の表面に積層させたり、難燃性樹脂組成物を他の樹脂と共押出して難燃性樹脂組成物の層を少なくとも１層以上有した積層構造体を形成し、この積層構造体を成形したりして、反射体が形成される。 In addition to flame retardant resin compositions, antioxidants such as phenolic antioxidants, phosphorus antioxidants or thio antioxidants, lubricants, softeners, crystal nucleating agents, antistatic agents, fillers, etc. These additives may be included.
The flame-retardant resin composition is prepared, for example, by melting and kneading each raw material and using a pelletizer as pellets. The flame-retardant resin composition in the form of pellets is molded into a predetermined shape, formed into a sheet, and laminated on the surface of a preformed substrate, or the flame-retardant resin composition is used together with other resins. Extrusion is performed to form a laminated structure having at least one layer of the flame retardant resin composition, and the laminated structure is molded to form a reflector.
　次に、実施例に基づいて本発明をさらに具体的に説明する。
　なお、本発明は、以下の実施例および比較例により制限されるものではない。 Next, the present invention will be described more specifically based on examples.
The present invention is not limited by the following examples and comparative examples.
　（実施例１～４、比較例１～５）
　［原料］
　以下の実施例１～４および比較例１～５で用いる原料は、以下の通り。
　・ポリプロピレン系樹脂（以下ＰＰ）；Ｅ－１８５Ｇ（商品名、株式会社プライムポリマー製　密度＝０．９１０ｇ／ｃｍ３　２３０℃でのメルトフローレート＝０．３ｇ／１０分）
　・ポリエチレン系樹脂（以下ＰＥ）；５３０５Ｅ（商品名、株式会社プライムポリマー製　密度＝０．９５１ｇ／ｃｍ３　１９０℃でのメルトフローレート＝０．８ｇ／１０分）
　・難燃剤－Ａ；サイテックス８０１０（商品名、アルベマール日本株式会社製）
　・難燃剤－Ｂ；アデカスタブＦＰ２１００Ｊ（商品名、株式会社ＡＤＥＫＡ製）
　・難燃剤－Ｃ；キスマ５Ａ（商品名、協和化学工業株式会社製）
　・難燃助剤；三酸化アンチモンＦＣＰ－ＡＴ３（商品名、株式会社鈴裕化学製）
　・二酸化チタン；ＰＦ－６９０（商品名、石原産業株式会社製）
　・紫外線吸収剤；ケミソーブ１１４（商品名、ケミプロ化成株式会社製
　・光安定剤；チヌビンＸＴ８５０　ＢＡＳＦジャパン製 (Examples 1 to 4, Comparative Examples 1 to 5)
[material]
The raw materials used in the following Examples 1 to 4 and Comparative Examples 1 to 5 are as follows.
Polypropylene resin (hereinafter PP); E-185G (trade name, manufactured by Prime Polymer Co., Ltd. Density = 0.910 g / cm 3 Melt flow rate at 230 ° C. = 0.3 g / 10 min)
Polyethylene resin (hereinafter PE): 5305E (trade name, manufactured by Prime Polymer Co., Ltd. Density = 0.951 g / cm 3 Melt flow rate at 190 ° C. = 0.8 g / 10 min)
・ Flame retardant-A; Cytex 8010 (trade name, manufactured by Albemarle Japan Co., Ltd.)
・ Flame retardant-B; ADK STAB FP2100J (trade name, manufactured by ADEKA Corporation)
・ Flame retardant-C: Kisuma 5A (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.)
・ Flame retardant aid: Antimony trioxide FCP-AT3 (trade name, manufactured by Suzuhiro Chemical Co., Ltd.)
・ Titanium dioxide; PF-690 (trade name, manufactured by Ishihara Sangyo Co., Ltd.)
・ UV absorber; Chemisorb 114 (trade name, manufactured by Chemipro Kasei Co., Ltd.) ・ Light stabilizer: manufactured by Tinuvin XT850 BASF Japan
　　（造粒工程）
　上記原料を以下の表１，２に示す割合で配合し、シリンダー温度を２６０℃に設定したスクリュー口径３０ｍｍの二軸押出機を用い溶融混練し、ダイスから吐出されたストランドを冷却バスにより冷却し、ペレタイザーにて切断して、ペレット化した難燃性樹脂組成物を調製した。 (Granulation process)
The above raw materials are blended in the proportions shown in Tables 1 and 2 below, melt kneaded using a twin screw extruder with a screw diameter of 30 mm set at a cylinder temperature of 260 ° C., and the strand discharged from the die is cooled by a cooling bath. The flame-retardant resin composition was prepared by cutting with a pelletizer and pelletizing.
　［試験片の作製］
　表１，２に示す配合で調製されたペレットを用い、射出成形機にて、シリンダー温度２１０℃、金型温度５０℃の成形条件において、平板（８０×８０ｍｍ、厚み；３．２ｍｍ）と、燃焼試験片（１２７ｍｍ×１２．７ｍｍ、厚み；３．２ｍｍ）とを作製した。
　また、表１，２に示す配合で調製されたペレットを用い、スクリュー口径６５ｍｍシート押出機にて、シリンダー温度２３０℃、賦形ロール温度６０℃の成形条件においてシート（厚み１．０ｍｍ）を作製した。 [Preparation of test piece]
Using pellets prepared with the formulations shown in Tables 1 and 2, in an injection molding machine, under molding conditions of a cylinder temperature of 210 ° C. and a mold temperature of 50 ° C., a flat plate (80 × 80 mm, thickness; 3.2 mm), A combustion test piece (127 mm × 12.7 mm, thickness; 3.2 mm) was prepared.
Also, using pellets prepared with the formulation shown in Tables 1 and 2, a sheet (thickness: 1.0 mm) was produced under molding conditions of a cylinder temperature of 230 ° C. and a forming roll temperature of 60 ° C. with a 65 mm screw extruder. did.
　［評価］
　各配合における試験片を、難燃性、反射率、耐候性、賦形性で評価した。
　　（難燃性）
　難燃性は、ＪＩＳ　Ｋ６９１１　Ａ法に準拠する方法で評価した。
　具体的には、上述の方法で作製した燃焼試験片を試料とし、炎の高さを２５ｍｍに設定し、炎を３０°傾けた状態で試験片に３０秒接炎後、１８０秒以上燃焼した場合は可燃性。１８０秒以内に消火し、かつ燃焼距離が２５ｍｍを超え１００ｍｍ以下の場合は自消性。１８０秒以内に消火し、かつ燃焼距離が２５ｍｍ以下の場合は不燃性と判定した。
　その結果を、表１，２に示す。 [Evaluation]
The test piece in each formulation was evaluated by flame retardancy, reflectance, weather resistance, and formability.
(Flame retardance)
Flame retardancy was evaluated by a method based on JIS K6911 A method.
Specifically, the combustion test piece produced by the above method was used as a sample, the flame height was set to 25 mm, the flame was tilted by 30 °, and the test piece was in contact with the test piece for 30 seconds and then burned for 180 seconds or more If flammable. If the fire extinguishes within 180 seconds and the combustion distance exceeds 25 mm and is 100 mm or less, it is self extinguishing. When the fire was extinguished within 180 seconds and the combustion distance was 25 mm or less, it was determined to be nonflammable.
The results are shown in Tables 1 and 2.
　　（反射率）
　上述の方法で作製した平板を反射率測定用試料とし、反射率は、分光光度計（ＧＲＥＴＡＧＭＡＣＢＥＴＨ社製、商品名ＣＯＬＯＲ－Ｅｙｅ ７０００Ａ）を用い、Ｄ６５光源で１０度視野の条件で測定した。
　その結果を表１，２に示す。 (Reflectance)
The flat plate produced by the above-mentioned method was used as a reflectance measurement sample, and the reflectance was measured using a spectrophotometer (trade name COLOR-Eye 7000A, manufactured by GRETAGMACBETH) under the condition of a 10-degree field of view with a D65 light source.
The results are shown in Tables 1 and 2.
　　（耐候性）
　上述の方法で作製した平板を耐候性測定用試料とし、ＪＩＳ　Ｂ７７５３に準拠した耐候試験機を用いて、バックパネル温度６３℃、降雨１２分／６０分条件にて２０００時間耐候促進劣化処理を行い、この耐候促進劣化処理後の平板について、上記分光光度計を用いて反射率を測定した。
　さらに、耐候促進劣化処理後の平板と、耐候促進劣化処理を実施していない未処理の平板とについて、色差Δ(デルタ)Ｅ*を測定（スガ試験機株式会社製　商品名ＳＭカラーコンピューターＳＭ４５、条件；光源２度視野）した。
　結果を、以下の表１，２に示す。 (Weatherability)
Using the flat plate produced by the above-mentioned method as a sample for weather resistance measurement, using a weather tester compliant with JIS B7753, a weather resistance accelerated deterioration treatment was performed for 2000 hours at a back panel temperature of 63 ° C. and a rainfall of 12 minutes / 60 minutes. The reflectance of the flat plate after the weathering accelerated deterioration treatment was measured using the spectrophotometer.
Further, the color difference Δ (delta) E * was measured for the flat plate after the weathering accelerated deterioration treatment and the untreated flat plate not subjected to the weathering accelerated deterioration treatment (trade name SM color computer SM45, manufactured by Suga Test Instruments Co., Ltd.). Condition; light source 2 degree field of view).
The results are shown in Tables 1 and 2 below.
　　（賦形性）
　上述の方法で作製したシートおよびペレットを用いて、ドローダウン性、溶融張力を測定することで、シートを二次加工する際に、指標となる真空成形等熱成形時の賦形性を評価した。
　ドローダウン性は、上記方法で得られたシートを、３３０ｍｍ×３３０ｍｍに加工し、４５０℃で３０秒間間接加熱した際の垂下量を測定し、ドローダウン性の評価とした。上記方法で得られた垂下量を元に、ドローダウン性を以下の基準で判定した。
　　　　Ａ：垂下量が２０ｍｍ以下の場合
　　　　Ｂ：垂下量が２０ｍｍを超える場合
　また溶融張力（単位；ｍＮ）は、キャピラリーレオメータ（(株)東洋精機製作所製）を用いて、２３０℃に加熱し溶融した試料を、直径１ｍｍのノズルから２３℃の大気中に３０ｍｍ／ｍｉｎの速度となるように押出し、得られたストランドを６ｍ／ｍｉｎの速度で引き取る際の張力を測定した。
　上記評法で得られた溶融張力を、以下の基準で判定した。
　　　Ａ：３０ｍＮ以上の場合
　　　Ｂ：３０ｍＮ未満の場合
　結果を、以下の表１，２に示す。 (Shaping property)
Using the sheet and pellet produced by the above-mentioned method, by measuring the drawdown property and melt tension, the shapeability at the time of thermoforming such as vacuum forming as an index was evaluated when the sheet was subjected to secondary processing. .
The draw-down property was evaluated as the draw-down property by measuring the amount of sag when the sheet obtained by the above method was processed to 330 mm × 330 mm and indirectly heated at 450 ° C. for 30 seconds. Based on the amount of droop obtained by the above method, the drawdown property was determined according to the following criteria.
A: When the drooping amount is 20 mm or less B: When the drooping amount exceeds 20 mm Further, the melt tension (unit: mN) was melted by heating to 230 ° C. using a capillary rheometer (manufactured by Toyo Seiki Seisakusho). The sample was extruded from a nozzle having a diameter of 1 mm into the atmosphere at 23 ° C. so as to have a speed of 30 mm / min, and the tension when the obtained strand was drawn at a speed of 6 m / min was measured.
The melt tension obtained by the above evaluation method was determined according to the following criteria.
A: When 30 mN or more B: When less than 30 mN The results are shown in Tables 1 and 2 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（比較例６，７）
　比較例６，７おいては、以下の原料を用いた以外は、実施例１～４および比較例１～５と同様に行った。結果を、以下の表３に示す。
　［原料］
　以下の比較例６，７で用いる原料は、以下の通り。
　・ポリプロピレン系樹脂（以下ＰＰ）；Ｅ－１８５Ｇ（商品名、株式会社プライムポリマー製　密度＝０．９１０ｇ／ｃｍ３　２３０℃でのメルトフローレート＝０．３ｇ／１０分）
　・ポリエチレン系樹脂（以下ＰＥ）；５３０５Ｅ（商品名、株式会社プライムポリマー製　密度＝０．９５１ｇ／ｃｍ３　１９０℃でのメルトフローレート＝０．８ｇ／１０分）
　・難燃剤－Ｄ；フレームカット１２０Ｇ（商品名、東ソー株式会社製）（テトラブロモビスフェノール－Ａ）
　・難燃剤－Ｅ；ファイヤーガード３６００（商品名、帝人化成株式会社製）（テトラブロモビスフェノール－Ａ ジグリシジルエーテル）
　・難燃助剤；三酸化アンチモンＦＣＰ－ＡＴ３（商品名、株式会社鈴裕化学製）
　・二酸化チタン；ＰＦ－６９１（商品名、石原産業株式会社製）
　・紫外線吸収剤；ケミソーブ１１４（商品名、ケミプロ化成株式会社製
　・光安定剤；チヌビンＸＴ８５０（商品名、ＢＡＳＦジャパン製） (Comparative Examples 6 and 7)
Comparative Examples 6 and 7 were carried out in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 5 except that the following raw materials were used. The results are shown in Table 3 below.
[material]
The raw materials used in the following Comparative Examples 6 and 7 are as follows.
Polypropylene resin (hereinafter PP); E-185G (trade name, manufactured by Prime Polymer Co., Ltd. Density = 0.910 g / cm 3 Melt flow rate at 230 ° C. = 0.3 g / 10 min)
Polyethylene resin (hereinafter PE): 5305E (trade name, manufactured by Prime Polymer Co., Ltd. Density = 0.951 g / cm 3 Melt flow rate at 190 ° C. = 0.8 g / 10 min)
・ Flame Retardant-D: Flame Cut 120G (trade name, manufactured by Tosoh Corporation) (Tetrabromobisphenol-A)
・ Flame retardant-E; Fireguard 3600 (trade name, manufactured by Teijin Chemicals Ltd.) (tetrabromobisphenol-A diglycidyl ether)
・ Flame retardant aid: Antimony trioxide FCP-AT3 (trade name, manufactured by Suzuhiro Chemical Co., Ltd.)
・ Titanium dioxide; PF-691 (trade name, manufactured by Ishihara Sangyo Co., Ltd.)
UV absorber; Chemisorb 114 (trade name, manufactured by Chemipro Kasei Co., Ltd.) Light stabilizer: Tinuvin XT850 (trade name, manufactured by BASF Japan)
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　（実施例５～８、比較例８，９）
　実施例５～８、比較例８，９においては、以下の原料を用いた以外は、実施例１～４および比較例１～５と同様に行った。結果を、以下の表４に示す。
　［原料］
　以下の実施例５～８および比較例８，９で用いる原料は、以下の通り。
　・ポリプロピレン系樹脂（以下ＰＰ）；Ｅ－１８５Ｇ（商品名、株式会社プライムポリマー製　密度＝０．９１０ｇ／ｃｍ３　２３０℃でのメルトフローレート＝０．３ｇ／１０分）
　・ポリエチレン系樹脂（以下ＰＥ）；５３０５Ｅ（商品名、株式会社プライムポリマー製　密度＝０．９５１ｇ／ｃｍ３　１９０℃でのメルトフローレート＝０．８ｇ／１０分）
　・難燃剤－Ａ；サイテックスＢＴ－９３（商品名、アルベマール日本株式会社製）（エチレンビステトラブロモフタルイミド）
　・難燃剤－Ｂ；アデカスタブＦＰ２１００Ｊ（商品名、株式会社ＡＤＥＫＡ製）（リン酸塩化合物）
　・難燃剤－Ｃ；キスマ５Ａ（商品名、協和化学工業株式会社製）（水酸化マグネシウム）
　・難燃剤－Ｄ；ＸＺ－６８００（商品名、寿光市海洋化工有限公司製）（２，２’－ビス［４－（２，３－（ジブロモプロピルオキシ））－３，５－ジブロモフェニル］プロパン］）
　・難燃助剤；三酸化アンチモンＦＣＰ－ＡＴ３（商品名、株式会社鈴裕化学製）
　・二酸化チタン；ＰＦ－６９０（商品名、石原産業株式会社製）
　・紫外線吸収剤；ケミソーブ１１４（商品名、ケミプロ化成株式会社製
　・光安定剤；チヌビンＸＴ８５０（商品名、ＢＡＳＦジャパン製） (Examples 5 to 8, Comparative Examples 8 and 9)
Examples 5 to 8 and Comparative Examples 8 and 9 were carried out in the same manner as Examples 1 to 4 and Comparative Examples 1 to 5 except that the following raw materials were used. The results are shown in Table 4 below.
[material]
The raw materials used in the following Examples 5 to 8 and Comparative Examples 8 and 9 are as follows.
Polypropylene resin (hereinafter PP); E-185G (trade name, manufactured by Prime Polymer Co., Ltd. Density = 0.910 g / cm 3 Melt flow rate at 230 ° C. = 0.3 g / 10 min)
Polyethylene resin (hereinafter PE): 5305E (trade name, manufactured by Prime Polymer Co., Ltd. Density = 0.951 g / cm 3 Melt flow rate at 190 ° C. = 0.8 g / 10 min)
・ Flame retardant-A; Cytex BT-93 (trade name, manufactured by Albemarle Japan Co., Ltd.) (ethylene bistetrabromophthalimide)
・ Flame retardant-B; ADK STAB FP2100J (trade name, manufactured by ADEKA Corporation) (phosphate compound)
・ Flame retardant -C; Kisuma 5A (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) (magnesium hydroxide)
・ Flame retardant-D; XZ-6800 (trade name, manufactured by Shogyo Kaikai Chemical Co., Ltd.) (2,2'-bis [4- (2,3- (dibromopropyloxy))-3,5-dibromophenyl] propane])
・ Flame retardant aid: Antimony trioxide FCP-AT3 (trade name, manufactured by Suzuhiro Chemical Co., Ltd.)
・ Titanium dioxide; PF-690 (trade name, manufactured by Ishihara Sangyo Co., Ltd.)
UV absorber; Chemisorb 114 (trade name, manufactured by Chemipro Kasei Co., Ltd.) Light stabilizer: Tinuvin XT850 (trade name, manufactured by BASF Japan)
Figure JPOXMLDOC01-appb-T000004
※１：測定不可(試験片破壊のため)
※２：耐候性促進処理にてクレーズ等の割れにより破壊。なお、100hrにてΔＥ*＝１３
Figure JPOXMLDOC01-appb-T000004
* 1: Measurement not possible (due to specimen breakage)
* 2: Destroyed due to cracking of craze etc. in the weather resistance promotion treatment. Note that ΔE * = 13 at 100 hr.
　［評価結果］
　上記表１，２，３，４に示す結果から、本発明の実施例は比較例に比べ、燃焼性を抑制した不燃性または自消性を有しながら反射率に優れ、さらに耐候促進処理でも明らかに長期経過後の反射率および色相の低下を抑制し、シートの二次加工性である熱成形性にも優れていることが明らかである。 [Evaluation results]
From the results shown in the above Tables 1, 2, 3, and 4, the examples of the present invention are superior in reflectance while having non-flammability or self-extinguishing properties with suppressed flammability as compared with the comparative examples, and even in the weathering acceleration treatment. Obviously, the reflectance and hue after a long period of time are suppressed, and it is clear that the sheet is excellent in thermoformability, which is the secondary workability of the sheet.
　本発明は、発光ダイオードや有機ＥＬ（Electro Luminescence）を光源とした電飾看板または照明装置、あるいはディスプレイの反射板などの成形体や積層構造体、これらの難燃性樹脂組成物に好適に用いられる。 INDUSTRIAL APPLICABILITY The present invention is suitably used for an electric signboard or lighting device using a light emitting diode or an organic EL (Electro Luminescence) as a light source, a molded body such as a reflection plate of a display, a laminated structure, or a flame retardant resin composition thereof It is done.

Claims (17)

  1. 　（Ａ）ポリプロピレン系樹脂を５５質量％以上含有するポリプロピレン系樹脂組成物５０質量％以上と、
    　（Ｂ）二酸化チタンを５質量％以上２０質量％以下と、
    　（Ｃ）エチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体、デカブロモジフェニルエーテルまたはその誘導体の群から選ばれる少なくとも一種以上の臭素系難燃剤を１質量％以上３０質量％以下と、を混合してなる
    　ことを特徴とする難燃性樹脂組成物。     (A) 50% by mass or more of a polypropylene resin composition containing 55% by mass or more of a polypropylene resin,
    (B) 5% by mass or more and 20% by mass or less of titanium dioxide;
    (C) 1% by mass or more and 30% by mass or less of at least one brominated flame retardant selected from the group of ethylene bispentabromodiphenyl or a derivative thereof, ethylene bistetrabromophthalimide or a derivative thereof, decabromodiphenyl ether or a derivative thereof A flame retardant resin composition characterized by being mixed.
  2. 　（Ａ）ポリプロピレン系樹脂を５５質量％以上含有するポリプロピレン系樹脂組成物５０質量％以上と、
    　（Ｂ）二酸化チタンを５質量％以上２０質量％以下と、
    　（Ｃ）臭素系難燃剤を１質量％以上３０質量％以下と、を混合してなる難燃性樹脂組成物であって、
    　前記臭素系難燃剤がエチレンビスペンタブロモジフェニル、エチレンビステトラブロモフタルイミド、デカブロモジフェニルエーテルの群から選ばれる少なくとも一種以上含有する
    　ことを特徴とする難燃性樹脂組成物。     (A) 50% by mass or more of a polypropylene resin composition containing 55% by mass or more of a polypropylene resin,
    (B) 5% by mass or more and 20% by mass or less of titanium dioxide;
    (C) A flame retardant resin composition obtained by mixing a brominated flame retardant with 1% by mass or more and 30% by mass or less,
    The flame retardant resin composition, wherein the brominated flame retardant contains at least one selected from the group consisting of ethylene bispentabromodiphenyl, ethylene bistetrabromophthalimide, and decabromodiphenyl ether.
  3. 　請求項１に記載の難燃性樹脂組成物において、
    　前記臭素系難燃剤がエチレンビスペンタブロモジフェニルまたはその誘導体、エチレンビステトラブロモフタルイミドまたはその誘導体の群から選ばれる少なくとも一種以上含有する
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to claim 1,
    The flame retardant resin composition, wherein the brominated flame retardant contains at least one selected from the group of ethylene bispentabromodiphenyl or a derivative thereof, ethylene bistetrabromophthalimide or a derivative thereof.
  4. 　請求項１に記載の難燃性樹脂組成物において、
    　前記臭素系難燃剤がエチレンビスペンタブロモジフェニルまたはその誘導体の群から選ばれる少なくとも一種以上含有する
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to claim 1,
    The flame retardant resin composition, wherein the brominated flame retardant contains at least one selected from the group consisting of ethylene bispentabromodiphenyl and derivatives thereof.
  5. 　請求項２に記載の難燃性樹脂組成物において、
    　前記臭素系難燃剤がエチレンビスペンタブロモジフェニルを含有する
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to claim 2,
    The flame retardant resin composition, wherein the brominated flame retardant contains ethylene bispentabromodiphenyl.
  6. 　請求項１から請求項５のいずれか一項に記載の難燃性樹脂組成物において、
    　さらに難燃助剤を内配合で１質量％以上３０質量％以下混合してなる
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to any one of claims 1 to 5,
    Further, a flame retardant resin composition comprising a flame retardant aid mixed in an amount of 1% by mass to 30% by mass.
  7. 　請求項６に記載の難燃性樹脂組成物において、
    　前記難燃助剤は、三酸化アンチモンと、ホウ酸亜鉛と、ポリテトラフルオロエチレンと、金属酸化物と、二酸化珪素との群から選ばれる少なくとも一種以上である
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to claim 6,
    The flame retardant aid is at least one selected from the group consisting of antimony trioxide, zinc borate, polytetrafluoroethylene, metal oxide, and silicon dioxide. Composition.
  8. 　請求項１から請求項７までのいずれか一項に記載の難燃性樹脂組成物において、
    　前記二酸化チタンは、二酸化珪素および酸化アルミニウムの群から選ばれる少なくとも一種以上で表面処理されている
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to any one of claims 1 to 7,
    The titanium dioxide is surface-treated with at least one selected from the group consisting of silicon dioxide and aluminum oxide.
  9. 　請求項１から請求項８までのいずれか一項に記載の難燃性樹脂組成物において、
    　前記ポリプロピレン系樹脂は、プロピレンの単独重合体、プロピレンとプロピレン以外のα－オレフィンとのランダム共重合体、および、プロピレンとプロピレン以外のα－オレフィンとのブロック共重合体の群から選ばれる少なくとも一種以上である
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to any one of claims 1 to 8,
    The polypropylene resin is at least one selected from the group consisting of a homopolymer of propylene, a random copolymer of propylene and an α-olefin other than propylene, and a block copolymer of propylene and an α-olefin other than propylene. It is the above, The flame-retardant resin composition characterized by the above-mentioned.
  10. 　請求項１から請求項９までのいずれか一項に記載の難燃性樹脂組成物において、
    　紫外線吸収剤と光安定剤との群から選ばれる少なくとも一種以上を、外配合で０．０１質量％以上５質量％以下混合してなる
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to any one of claims 1 to 9,
    A flame retardant resin composition comprising at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer mixed by 0.01% by mass or more and 5% by mass or less by external blending.
  11. 　請求項１から請求項１０までのいずれか一項に記載の難燃性樹脂組成物において、
    　前記ポリプロピレン系樹脂組成物は、ポリエチレン系樹脂を含有する
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to any one of claims 1 to 10,
    The said polypropylene resin composition contains a polyethylene-type resin. The flame-retardant resin composition characterized by the above-mentioned.
  12. 　請求項１から請求項１１までのいずれか一項に記載の難燃性樹脂組成物において、
    　前記ポリエチレン系樹脂は、密度０．９１０ｇ／ｃｍ３以上０．９６５ｇ／ｃｍ３以下、１９０℃でのメルトマスフローレート０．０１ｇ／１０分以上５０ｇ／１０分以下であるエチレン単独重合体、エチレンとエチレン以外のα－オレフィンとの共重合体の群から選ばれる少なくとも一種以上である
    　ことを特徴とする難燃性樹脂組成物。     In the flame-retardant resin composition according to any one of claims 1 to 11,
    The polyethylene resin has a density 0.910 g / cm 3 or more 0.965 g / cm 3 or less, ethylene homopolymer or less 50 g / 10 min melt mass flow rate 0.01 g / 10 minutes or more at 190 ° C., and ethylene A flame retardant resin composition comprising at least one selected from the group of copolymers with α-olefins other than ethylene.
  13. 　請求項１から請求項１２までのいずれか一項に記載の難燃性樹脂組成物を成形してなる
    　ことを特徴とする成形体。     A molded body obtained by molding the flame retardant resin composition according to any one of claims 1 to 12.
  14. 　請求項１から請求項１２までのいずれか一項に記載の難燃性樹脂組成物からなる層を少なくとも１層以上有している
    　ことを特徴とする積層構造体。     It has at least 1 layer or more layers which consist of a flame-retardant resin composition as described in any one of Claim 1- Claim 12. The laminated structure characterized by the above-mentioned.
  15. 　請求項１４に記載の積層構造体において、
    　前記難燃性樹脂組成物からなる層は、表面層である
    　ことを特徴とする積層構造体。     The laminated structure according to claim 14, wherein
    The layer composed of the flame retardant resin composition is a surface layer.
  16. 　請求項１から請求項１２までのいずれか一項に記載の難燃性樹脂組成物を成形してなる
    　ことを特徴とする反射板。     A reflector made by molding the flame retardant resin composition according to any one of claims 1 to 12.
  17. 　請求項１６に記載の反射板を備えた
    　ことを特徴とする照明装置。     An illuminating device comprising the reflector according to claim 16.
PCT/JP2013/051414 2012-01-27 2013-01-24 Flame-retardant resin composition, molded body, laminated structure, reflective plate and lighting device WO2013111808A1 (en)

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