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WO2018163341A1 - Retardateur de flamme élastomère et composition de résine thermoplastique comprenant un retardateur de flamme - Google Patents

Retardateur de flamme élastomère et composition de résine thermoplastique comprenant un retardateur de flamme Download PDF

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Publication number
WO2018163341A1
WO2018163341A1 PCT/JP2017/009394 JP2017009394W WO2018163341A1 WO 2018163341 A1 WO2018163341 A1 WO 2018163341A1 JP 2017009394 W JP2017009394 W JP 2017009394W WO 2018163341 A1 WO2018163341 A1 WO 2018163341A1
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Prior art keywords
flame retardant
compound
elastomer
thermoplastic resin
resin
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PCT/JP2017/009394
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English (en)
Japanese (ja)
Inventor
西田耕治
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ポリマーアソシエイツ合同会社
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Priority to PCT/JP2017/009394 priority Critical patent/WO2018163341A1/fr
Priority to JP2017540661A priority patent/JP6279167B1/ja
Publication of WO2018163341A1 publication Critical patent/WO2018163341A1/fr

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    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials

Definitions

  • the present invention relates to an elastomer flame retardant capable of simultaneously solving the impact improvement and flame retardancy of a thermoplastic resin, and a thermoplastic resin composition containing the flame retardant.
  • the conventional technical system improves the impact strength.
  • materials and products have been developed to improve the impact strength by blending elastomers and blend flame retardants to ensure the flame retardancy of the composition.
  • most elastomers are styrene-butadiene-styrene copolymers and their hydrogenated products, ethylene- ⁇ olefin elastomer acid anhydride modification, olefin terpolymer elastomer acid anhydride modification, ethylene- ⁇ olefin copolymer epoxy.
  • Group-introduced modified materials, core-shell elastomers, etc., and impact strength is improved by blending with thermoplastic resins.
  • the molecular structure has a low oxygen index. Therefore, in order to ensure the flame retardancy of the entire composition, it is necessary to increase the amount of the flame retardant. In the first place, since the effect of improving flame retardancy is extremely small, the amount of the elastomer is limited. There is. Furthermore, many of the phosphorus-based flame retardants are known to greatly reduce the thermal deformation of thermoplastic resins, and it is difficult to break the trade-off between the three factors of thermal deformation temperature, impact strength, and flame retardancy. there were.
  • CFRP impregnated with a thermosetting resin for example, an attempt has been made to relieve stress by dispersing and improving an elastomer or super engineering plastic in an epoxy resin in order to prevent cracking due to a thermal cycle or adjust a damping rate.
  • CFRP CFRP impregnated with a thermosetting resin
  • Prior art relating to elastomer flame retardants and prior art relating to multilayering of thermoplastic resins are as follows.
  • Patent Document 1 the present inventor has found a material to ensure flame retardancy.
  • a technology for applying a flame retardant to a composite resin containing an elastomer has been widely applied, but there is no prior art in which the elastomer itself acts as a flame retardant.
  • two-layer extrusion molding there are known techniques such as core-sheath fiber and two-layer pipe extrusion. These applications include the production of double-layered pellets, which have been filed for a die structure, specifying the material as a difference from the known technology.
  • Patent Document 2 Two-layer olefin resin pellets and manufacturing method thereof
  • Patent Document 3 Two-layer pellets and resin molded products
  • Patent Document 5 Two-layer olefin resin pellets and manufacturing method thereof
  • Patent Document 6 Two-layer structure olefin for insect repellent resin composition
  • Patent Document 7 a resin pellet
  • Patent Document 8 a manufacturing method and an apparatus of a multilayer pellet
  • Patent Document 9 a manufacturing method and an apparatus of a multilayer pellet
  • Patent Document 9 a core material and a sheath material are supplied to a die apparatus in which a plurality of extrusion-molded portions are arranged along the circumference, and the sheath material is concentrically formed on the outer periphery of the core material from each extrusion-molded portion. It is coated and multi-layered.
  • Japanese Patent No. 5913756 Japanese Unexamined Patent Publication No. 2015-105369 JP 2009-242591 (Patent No. 5373306) JP 2008-255277 A JP 2006-272629 A (Patent No. 4642520) JP 2006-272628 A (Patent No. 4571351) JP 2005-139329 A (Patent No. 4649104) JP2003-048991A JP 2001-198918 (Patent No. 4542252)
  • the present invention provides an elastomer flame retardant having flame retardancy and capable of further improving impact, and a thermoplastic resin composition containing the flame retardant.
  • the compound (B) is rich in the ratio of compound (A) / compound (B).
  • the ratio of the compound (B) in the compound (A) and the compound (B) is 60 to 80%, and even if it is 40%, the impact improvement effect is confirmed in the glass fiber composite material system as a result of the elastomeric property.
  • the elastomeric property exceeds 60%, the adhesiveness of the strand obtained by cooling the melt strand after melt-kneading with a water bath is high.
  • blend anti-blocking agents such as silicone
  • blend anti-blocking agents such as silicone
  • a cooling water tank or to mix calcium carbonate, aerosil, calcium carbonate, etc. on the pellet surface.
  • silicone residues there is a defect in the flame retardant application material for electronic components, and a large amount of aerosil mixing limits the working environment, and mixing of calcium carbonate and talc inorganic fillers is also separated by vibration during transportation. Therefore, non-adhesiveness is required to withstand use in a wide range of temperature environments, and the present invention has been achieved.
  • Multi-layer sheet forming and multi-layer film forming apparatuses operate in their respective industries, and are great for creating new business for each industry. Naturally, extruding products with excellent flame retardancy and impact strength can be obtained by in-line multilayering of thermoplastic resin with excellent mechanical and heat resistance on the skin layer without fusing and sealing. .
  • the final compound (B) concentration is determined by the layer composition ratio and the component concentration of each compound (B). If the dispersion of the material of the skin layer is good in the thermoplastic resin finally blended, the skin layer can be applied as a single thermoplastic resin.
  • the elastomer flame retardant according to one embodiment of the present invention, A flame retardant composition in which at least one of the formula A-1 and the formula A-2 (compound (A)) and a phosphate ester flame retardant (compound (B)) are melt-mixed,
  • the fuel composition is a molded body cut from a pellet or sheet containing at least a core layer (C) and a skin layer (D), and the core layer (C) comprises the compound (A) and the compound (B ) Is a weight ratio (A) / (B) of 15/75 to 40/60, and the skin layer (D) is a thermoplastic resin or a weight ratio of the compound (A) to the compound (B).
  • (A) / (B) is 95/5 to 50/50, and the molded body is mixed with a thermoplastic resin.
  • the weight ratio (C) / (D) between the core layer (C) and the skin layer (D) may be 90/10 to 50/50.
  • the thermoplastic resin of the skin layer (D) is polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polylactic acid, polyethylene naphthalate, polyarylate, styrene resin, polyphenylene ether, polyolefin, polyamide resin. , A thermoplastic epoxy resin, and a polymer alloy containing at least one selected from these.
  • thermoplastic resin composition according to one embodiment of the present invention may contain the above-described elastomer flame retardant.
  • the present invention can provide an elastomer flame retardant having flame retardancy and capable of further improving impact, and a thermoplastic resin composition containing the flame retardant.
  • thermoplastic resin composition containing the flame retardant are not limited to the following embodiments or examples.
  • various modifications can be made without departing from the scope of the present invention.
  • FIG. 1 shows a schematic diagram of a molded body constituting an elastomer flame retardant according to one embodiment of the present invention.
  • FIG. 2 shows a schematic view of another molded body constituting the elastomer flame retardant according to one embodiment of the present invention.
  • FIG. 3 shows a forming process of a molded body constituting the elastomer flame retardant according to one embodiment of the present invention.
  • the flame retardant composition constituting the elastomer flame retardant of the present invention has a compound (C) in which a compound (A) and a compound (B) are melt-mixed.
  • This flame retardant composition is a molded body cut from a pellet or sheet containing at least a core layer (C) and a skin layer (D). And this molded object is mixed with a thermoplastic resin, and the elastomer flame retardant of this invention is formed. Details of the compounds (A), (B), and (C) will be described later.
  • a molded body 10 constituting the elastomer flame retardant of the present invention includes a core layer 11 and a skin layer 12 covering the entire core layer 11.
  • the molded object 10 may contain the core layer 11, the skin layer 12, and the intermediate
  • the intermediate layer 20 may be a multilayer, and may be constituted by, for example, a core layer 21 and a skin layer 22 (see FIG. 2B).
  • the core layers (C) 11 and 21 desirably contain more compound (B) than compound (A).
  • the weight ratio (A) / compound (A) / compound (B) (B) is preferably 15/75 to 40/60.
  • the compound (A) is the same as the compound (B) or contained more than the compound (B).
  • the compound (A) and the compound (B) The weight ratio (A) / (B) is preferably 95/5 to 50/50.
  • the skin layers (D) 12 and 22 may be thermoplastic resins.
  • the weight ratio (C) / (D) of the core layers (C) 11 and 21 and the skin layers (D) 12 and 22 is preferably 90/10 to 50/50.
  • the weight ratio (C) / (D) is more preferably 60/40 or 70/30.
  • the core layer 11 is the same as the core layer 21, or more preferably, the compound B is higher than the core layer 21. Concentration is preferred.
  • the skin layer 12 is the same as the skin layer 22 or, more preferably, it is desirable that the concentration of the compound A is higher than that of the skin layer 22.
  • the flame retardant composition constituting the elastomer flame retardant of the present invention is, for example, a molded product cut from pellets or sheets.
  • the sheet 1 including the core layer 11 and the skin layer 12 shown in FIG. 3A is cut, and the molded body 10 is cut as shown in FIG. 3B, or as shown in FIG.
  • the molded body 10 is divided.
  • thermoplastic resin composition of the present invention may include the above-described elastomer flame retardant of the present invention.
  • Compound (A) consists of at least one of formula A-1 and formula A-2. That is, the compound (A) is any one of a compound comprising Formula A-1, a compound comprising Formula A-2, and a compound comprising Formula A-1 and Formula A-2.
  • the compound (A) is shown in Table 1 below.
  • Compound (B) is a phosphate ester compound.
  • the phosphate ester is not particularly limited, but it is preferable to use a monophosphate ester, a condensed phosphate ester, or the like.
  • the monophosphate is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid Sulfate, diphenyl-2-acryloy
  • the condensed phosphate ester is not particularly limited, and examples thereof include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (trade name PX- manufactured by Daihachi Chemical Industry Co., Ltd.). 200), hydroquinone poly (2,6-xylyl) phosphate and condensed phosphates such as condensates thereof.
  • Resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade names CR-741, FP-600, FP-700), aromatic condensed phosphate ester (trade name CR747), resorcinol polyphenyl phosphate (Trade name ADK STAB PFR manufactured by ADEKA) and the like.
  • composition of Compound (C) It is obvious that the normal temperature solid compound (B) is solid even if mixed with the compound (A) in any composition. In order to solidify the liquid compound (B), it depends on the composition with the compound (A) and the viscosity of the compound (A). If the compound (B) is less than 5%, it does not depend on the molecular weight and is solidified by mixing with many compounds (A), but it has both advantages in combination with the compound (A). Not a combination. On the other hand, even if the composition in which the liquid compound (B) exceeds 80%, even if it is solidified, it has surface stickiness in the environment of high temperature and long time storage and in the manufacturing work site. Aggregates.
  • ⁇ is a viscosity (cps) measured by a Brookfield B-type viscometer (270 ° C.) of a formula A-1, formula A-2, or a mixture of formulas A-1 and A-2. It is.
  • a liquid condensed phosphate ester is melt-kneaded with a solid polycarbonate resin and can be included up to about 20% by weight. However, when it exceeds 20% by weight, bleeding is observed on the product surface. Is done. From this, it was impossible to predict that the compound (B) was mixed with the compound (A) to a considerably high concentration and solidified. Thereby, it is very industrially significant that the liquid compound (B) is solidified.
  • thermoplastic resin that is the subject of the present invention is suitable as an engineering resin, for example, the following resins. However, it is not limited to the resin illustrated below.
  • the polycarbonate resin is an aromatic polycarbonate, an aliphatic polycarbonate, or an aromatic-aliphatic polycarbonate.
  • the aromatic polycarbonate is obtained by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with phosgene or a diester of carbonic acid, and includes those obtained by converting the aromatic hydroxy compound into a plant-derived isosorbide. It is also possible to use a polymer or oligomer containing both terminal phenolic OH groups each having a siloxane structure for the purpose of introducing a branching agent and assisting flame retardancy.
  • polyester resins include polyethylene phthalate, polybutylene terephthalate, polylactic acid, polyethylene naphthalate, LCP, terephthalic acid and / or isophthalic acid, ethylene glycol and / or cyclohexanedimethanol (CHDM) and And / or 2,2,4,4-tetramethyl-1,3cyclobutanediol (TMCD) copolymer (eg, PETG, PCTG, PCTA, TRITAN, etc. sold by Eastman Chemical).
  • CHDM cyclohexanedimethanol
  • TMCD 2,2,4,4-tetramethyl-1,3cyclobutanediol
  • polyamide-based resin includes polyamide 6, polyamide 6-6, copolymerized polyamide 6 / 6-6, polyamide 11, polyamide 12, polyamide 4, polyamide 4-6, polyamide 6-10, and Amorphous polyamide.
  • D Polyacrylate resin, polyacrylonitrile resin
  • e Polystyrene resin
  • polystyrene resin is high impact polystyrene, syndiotactic polystyrene, and polyacrylonitrile butadiene copolymer.
  • urethane system is a thermoplastic polyurethane or a thermoplastic polyurethane elastomer.
  • J Polysulfone
  • k Polyetheretherketone
  • l Thermoplastic epoxy resin
  • thermoplastic resin a single system composed of any one of the above (a) to (k), a blend of two or more components, and a polymer alloy of two or more components are applied.
  • the polymer alloy include polycarbonate / polyacrylonitrile butadiene styrene copolymer alloy, polycarbonate / polyethylene terephthalate, polycarbonate / polybutylene terephthalate, polyphenylene ether / high impact polystyrene, polyphenylene ether / polyamide, polyphenylene ether / polypropylene and the like.
  • the present invention can be used as long as the polyolefin does not exceed 50% by weight compared to engineering plastics.
  • polystyrene resin examples include polyethylene, polypropylene, poly-4-methylpentene-1, ethylene-alpha olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene ionomer resin, ethylene- Propylene copolymer elastomer, ethylene-butene copolymer elastomer, ethylene-hexene copolymer elastomer, ethylene-octene copolymer elastomer, ethylene-propylene-ethylidene norbornene copolymer, etc.
  • ABA type elastomers are also targeted.
  • ethylene-propylene-butadiene copolymer ethylene-propylene-isoprene copolymer
  • styrene-butadiene-styrene block copolymer styrene-isoprene-styrene block copolymer
  • styrene-butadiene-styrene block copolymer examples thereof include a hydrogenated product of a combination and a hydrogenated product of a styrene-isoprene-styrene block copolymer.
  • methacrylic acid ester-butadiene-styrene core / shell graft copolymer methacrylic acid ester-acrylonitrile-styrene core / shell graft copolymer
  • acrylic acid ester-silicone-styrene core / shell graft copolymer examples thereof include polymer acrylate-based core / shell graft copolymers.
  • the olefin resin can be used alone if the ratio of the D layer is 20% or less.
  • thermoplastic resin composition of the present invention various known components such as inorganic fillers and other components may be used at the time of mixing or kneading the raw materials or at the time of molding, as long as the properties are not significantly impaired.
  • Organic filler, plasticizer, heat stabilizer, ultraviolet absorber, antioxidant, light stabilizer, antistatic agent, conductive carbon, lubricant, nucleating agent, foaming agent, cross-linking agent, radical generator, release agent , Surfactants, antibacterial / antifungal agents, dyes, pigments and the like may be blended.
  • a flame retardant auxiliary layered inorganic compounds such as montmorillonite and clay, carbon nanotubes and the like are preferable.
  • composition ⁇ Production of composition>
  • various kneaders such as uniaxial and multi-axial kneaders, Banbury mixers are used in the production of ordinary thermoplastic resin compositions.
  • a method of melting and kneading the above components with a roll, a Brabender plastogram, etc., and then cooling and solidifying is applied, but it is not limited.
  • the kneader is more advantageous in a continuous kneader such as a twin screw extruder.
  • the length and shape of various elements such as screws, kneading discs, rotors, and cylinders, and the position and number of raw material supply ports can be freely changed.
  • the grade of flame retardant A and the type of flame retardant B (phosphate ester) they can be used in appropriate combinations.
  • the raw material supply ports are set at two locations: the first cylinder top (No. 1 supply port) and the middle cylinder upper part (No. 2 supply port) between the first cylinder and die head. After placing the kneading disc between the No. 1 supply port and No.
  • thermoplastic resin and a flame retardant A are supplied from 1 supply port, and a compound B (phosphate ester flame retardant) is supplied from No. 2 and No. 3 supply ports.
  • compound (B) is a liquid flame retardant, a liquid supply device is required.
  • the device can mix Compound B at a melting point of Compound A or higher.
  • a tank with a heating jacket and a stirring device is generally possible. This can be industrially incorporated into the liquid flame retardant production process, and can be easily taken out and cooled to obtain a solid flame retardant composition (compound C) at room temperature.
  • a compounding apparatus can be used by utilizing the high molecular weight of Compound A. In this case as well, a biaxial kneading extruder is useful. That is, after compound A is supplied from the No. 1 supply port and melt plasticized, liquid compound B is supplied from the No.
  • the strand is extruded from the die, water-cooled, air-cooled, and then desired by a strand cutter Pellets cut to the size of can be obtained.
  • the obtained flame retardant pellets are further mixed with a thermoplastic resin, it is preferable to obtain the composition with a similar melt-kneading extruder.
  • the composition may be directly blended with the raw material during molding.
  • the method for molding the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resins, that is, injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, Select from various molding methods such as plug-assisted pneumatic molding, film molding, sheet molding, rotational molding, laminate molding, foam molding, etc., depending on the formulation of the thermoplastic resin composition and the use of the packaging container. be able to.
  • the elastomer flame retardant of the present invention is formed by mixing a molded body composed of a flame retardant composition with a thermoplastic resin, but is not limited thereto.
  • a thermoplastic resin but is not limited thereto.
  • FIG. 4 shows an experimental apparatus used in the example of the present invention.
  • FIG. 5 shows the contents of the materials used in the experiments relating to the examples and comparative examples of the present invention.
  • the first step is the formation of the skin layer.
  • 80 parts of FRX-Polymer's Nofia-100L from the first feed part of the Nippon Steel Works twin screw kneader TEX30 ⁇ and 20 parts of ADEKA flame retardant FP600 from the second feed Is done.
  • the screw rotation is 230rpm
  • the cylinder temperature is set to 230 ° C under the first feed and 190 ° C under the second feed, compounded under the set extrusion conditions of 5kg / hr., Cooled in the water tank, and cut with a pelletizer.
  • a pellet is created.
  • this pellet is once heated and pressed. Thereby, a sheet is created.
  • the heating conditions are a temperature of 210 ° C. and a pressure of 3 MPa.
  • the sheet size is 200 mm wide, 200 mm long, and 0.25 mm thick.
  • the second step is multi-layering of the core layer compound and the sheet obtained in the first step.
  • the compound composition of the core layer is the ratio of the material system used in the first process, with 30 parts of Nofia-100L and 70 parts of FP600, the temperature under the first feed is 220 ° C, the temperature under the second feed Extruding under the same conditions as the others, except that the temperature was 190 ° C.
  • the die is loaded with a hanger coat die having a width of 150 mm and a die gap of 2 mm at the tip of the kneader.
  • the film used in the first step is laid on a metal press sheet, and a 2 mm thick sheet of T-die melt corresponding to the core layer to be discharged is laminated in accordance with the outflow.
  • a three-layer sheet of skin layer / core layer / skin layer is cooled while being weakly pressed with a pressure of 1 MPa by a cooling press. Then, after cooling, cut the sheet to about 5-7mm with scissors. There is no surging at the time of extruding the skin layer or the core layer, and it is a stable compound.
  • the three-layer sheet had no adhesion, and no trouble due to adhesion was observed even when it was cut with scissors.
  • Example-2 In the flame retardant compounding in the first step (skin layer) molding of Example-1, 60 parts of Nofia-100L and 40 parts of FP600 are used. Thereby, substantially the same good results were obtained.
  • Example-3 In Example 1, 90 parts of Nofia-100L in the first step (skin layer), 10 parts of FP600, and FR-2 grade in the second step (core layer) are A-2 type copolymer with PC. The same experiment as in Example 1 is performed except that Nofia-CO60 is used. As a result, it was found that the Charpy impact strength was as high as 18 J / m 2 and the flame retardancy was maintained at V0.
  • Example-4 In Example-1, the flame retardant Nofia-100L in the first step (skin layer) molding was switched to Nofia-9000, the second step was changed to Nofia-CO60 applied in Example-3, and other conditions were as in Example A polycarbonate composition was obtained in the same manner as -1. Even in this case, the molten composition obtained in the first step was easily solidified, a film could be formed, and there was no tackiness. Further, by adopting A-2 type which is a copolymer with PC in the core layer, the elastomericity is higher, and as a result, the impact of the glass fiber reinforced polycarbonate is high and the flame retardancy can be secured.
  • A-2 type which is a copolymer with PC in the core layer
  • Example-5 A film of polycarbonate (Mitsubishi Engineering Plastics Sales Iupilon S2000) containing no flame retardant is prepared in the skin layer, and the composition of Example-1 is multilayered in the core layer. However, the ratio of the core layer is 0.8. As a result, the multilayered flame retardant was not sticky, the impact of the final glass fiber reinforced polycarbonate was high, and the flame retardancy was ensured.
  • polycarbonate Mitsubishi Engineering Plastics Sales Iupilon S2000
  • Example-6 The material used in the first step is a polybutylene phthalate (substantially PBT) (Novaduran 5010) manufactured by Mitsubishi Engineering Plastics Co., Ltd., and the Nofia in the second step is 30 parts of A-2 type Nofia-CO60. And 70 parts of FP600, and the ratio of the skin layer to the core layer is 0.9.
  • the multilayered flame retardant was not sticky, and there was no problem in compounding with the PBT resin in the next step.
  • the number of flame retardant parts in the three layers was increased to 18 parts.
  • the impact strength in the PBT system was as high as 12 J / m 2 , and the flame retardancy was V0. It can be seen that this example has high practical value when compared with Comparative Example-4.
  • Example-1 In the first step, pellets of the flame retardant Nofia-100L used in Example-1 are once prepared in a biaxial kneader as in the example. Thereafter, a composition comprising 16 parts of this sample, 37 parts of polycarbonate resin and 45 parts of glass fiber was compounded with a biaxial kneader, and the quality after preparation of test pieces similar to the examples was evaluated.
  • the V-notched Charpy impact strength was 5.5 J / m 2 , and the flame retardancy was at a V2 level with drip.
  • This comparative example also reproduces that the flame retardancy is improved by forming the flame retardant alloy of the component (B) in Patent No. 5913756.
  • the impact strength with v-notch is cited as a comparison target.
  • Example 3 16 parts of the flame retardant composition containing only the skin layer not including the core layer, 39 parts of polycarbonate resin, and 45 parts of glass fiber are compounded by a biaxial kneader.
  • the flame retardancy is V0
  • the reproducibility of Patent No. 5913756 is obtained
  • the Charpy impact strength is 8.8 J / m 2 which is relatively high, but the impact value of Example-2 is much higher It turned out to be expensive.
  • Example-4 PBT5010 used in Example-6 is compounded with 18 wt% of phosphorus-based flame retardant FP600 and 45 wt% of glass fiber. It was found that the flame retardant FP600 was floating on the surface of the water tank when the extruded strand was passed through the water tank, and the obtained pellets were slightly sticky. This composition had a v-notched Charpy impact strength of 8 J / m 2 . In the flame retardant evaluation, there was a drip and it was V2.
  • Example-5 In Example-1, the core layer ratio is 0.95. In this case, it was found that the adhesiveness was strong at the time of sheet cutting, and it was not suitable for compounding with a thermoplastic resin.
  • Example-6 In Example-1, the core layer ratio is 0.25. In this case, there was no problem in compounding with the thermoplastic resin at the time of cutting the sheet, but the impact strength was found to be lower than that in Example-1. Compared to conventional flame retardant systems, this level is also highly evaluated, but in the present invention, it was judged that the core layer ratio in the claims is suitable.
  • Representative flame retardants include halogen flame retardants, red phosphorus, phosphine flame retardants, condensed phosphate esters and intumescent flame retardants.
  • halogen flame retardants red phosphorus, phosphine flame retardants, condensed phosphate esters and intumescent flame retardants.
  • an elastomer is blended to recover the impact strength.
  • fluorine-based and silicone-based elastomers general-purpose elastomers, on the contrary, reduce the flame retardant effect.
  • silicone-based and fluorine-based elastomers may be inferior in compatibility with the resin, and the impact strength is not improved so much.
  • the present invention provides a thermoplastic resin comprising a non-adhesive (A) / (B) composition or a thermoplastic resin as a skin layer, and a particularly highly elastomeric (A) / (B) composition as a core layer. It was proved that both the impact strength and the flame retardancy were satisfied by blending into the above.
  • the greatest feature of the present invention is an elastomer flame retardant.
  • various elastomers have been used as impact strength.
  • flame retardancy may not be provided in the first place, and it is necessary to add a flame retardant from the outside. In such a case, flame retardancy is insufficient, and it has been dealt with by increasing the thickness of the product to cover it.
  • the range of application is limited in the recent reduction in weight and thickness. ing.
  • Patent Document 1 clearly shows that excellent flame retardancy is imparted in combination with glass fiber or the like. Conventionally, since glass fiber acts as a combustion gas passage during combustion, it has been difficult to make the glass fiber composite material flame-retardant.
  • the present invention improves the impact strength of the glass fiber composite material system and makes it difficult.
  • the industrial significance of imparting flammability is very large.
  • the elastomer flame retardant of the present invention can act as an impact modifier and a flame retardant.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

L'invention concerne un retardateur de flamme élastomère qui est ignifuge et qui est capable d'améliorer davantage la résistance au choc. Le retardateur de flamme élastomère est une composition ignifuge d'un mélange fondu d'au moins un (composé (A)) de formule A-1 et de formule A-2 représentée par la formule A-1 ou la formule A-2 et un retardateur de flamme à base d'ester de phosphate (composé (B)). La composition du retardateur de flamme est un corps moulé découpé à partir d'une pastille ou d'une feuille comprenant au moins une couche centrale (C) et une couche superficielle (D). La couche centrale (C) a un rapport de poids (A)/(B) du composé (A) au composé (B) de 15/75 à 40/60, et la couche superficielle (D) est une résine thermoplastique ou a un rapport pondéral (A)/(B) du composé (A) au composé (B) de 95/5 à 50/50. Le corps moulé est mélangé dans la résine thermoplastique.
PCT/JP2017/009394 2017-03-09 2017-03-09 Retardateur de flamme élastomère et composition de résine thermoplastique comprenant un retardateur de flamme WO2018163341A1 (fr)

Priority Applications (2)

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PCT/JP2017/009394 WO2018163341A1 (fr) 2017-03-09 2017-03-09 Retardateur de flamme élastomère et composition de résine thermoplastique comprenant un retardateur de flamme
JP2017540661A JP6279167B1 (ja) 2017-03-09 2017-03-09 エラストマー難燃剤及び当該難燃剤を含む熱可塑性樹脂組成物

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PCT/JP2017/009394 WO2018163341A1 (fr) 2017-03-09 2017-03-09 Retardateur de flamme élastomère et composition de résine thermoplastique comprenant un retardateur de flamme

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WO2018163341A1 true WO2018163341A1 (fr) 2018-09-13

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11255955A (ja) * 1998-03-10 1999-09-21 Hitachi Ltd カプセル型難燃剤およびそれを配合した半導体封止用樹脂組成物
JP2006506486A (ja) * 2002-11-13 2006-02-23 ジェイジェイアイ エルエルシー 膨張性専門化学物質を含有する、熱可塑性又は熱硬化性耐火組成物
JP2014047342A (ja) * 2012-09-04 2014-03-17 Fushimi Pharm Co Ltd マイクロカプセル化難燃剤およびそれを含む難燃性樹脂組成物
JP2015044931A (ja) * 2013-08-28 2015-03-12 三菱エンジニアリングプラスチックス株式会社 ポリエステル樹脂組成物成形体
WO2017017780A1 (fr) * 2015-07-28 2017-02-02 ポリマーアソシエイツ合同会社 Retardateur de flamme et composition de résine thermoplastique ignifugeante

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11255955A (ja) * 1998-03-10 1999-09-21 Hitachi Ltd カプセル型難燃剤およびそれを配合した半導体封止用樹脂組成物
JP2006506486A (ja) * 2002-11-13 2006-02-23 ジェイジェイアイ エルエルシー 膨張性専門化学物質を含有する、熱可塑性又は熱硬化性耐火組成物
JP2014047342A (ja) * 2012-09-04 2014-03-17 Fushimi Pharm Co Ltd マイクロカプセル化難燃剤およびそれを含む難燃性樹脂組成物
JP2015044931A (ja) * 2013-08-28 2015-03-12 三菱エンジニアリングプラスチックス株式会社 ポリエステル樹脂組成物成形体
WO2017017780A1 (fr) * 2015-07-28 2017-02-02 ポリマーアソシエイツ合同会社 Retardateur de flamme et composition de résine thermoplastique ignifugeante

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