WO2007007663A1 - Composition de resine ignifuge - Google Patents

Composition de resine ignifuge Download PDF

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Publication number
WO2007007663A1
WO2007007663A1 PCT/JP2006/313561 JP2006313561W WO2007007663A1 WO 2007007663 A1 WO2007007663 A1 WO 2007007663A1 JP 2006313561 W JP2006313561 W JP 2006313561W WO 2007007663 A1 WO2007007663 A1 WO 2007007663A1
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WO
WIPO (PCT)
Prior art keywords
acid
resin
salt
metal
compound
Prior art date
Application number
PCT/JP2006/313561
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English (en)
Japanese (ja)
Inventor
Hatsuhiko Harashina
Original Assignee
Polyplastics Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co., Ltd. filed Critical Polyplastics Co., Ltd.
Priority to CN2006800249249A priority Critical patent/CN101218305B/zh
Priority to DE112006001824T priority patent/DE112006001824T5/de
Priority to JP2007524623A priority patent/JP5186210B2/ja
Publication of WO2007007663A1 publication Critical patent/WO2007007663A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

  • the present invention relates to a resin composition that is excellent in flame retardancy and moldability, and has improved electrical characteristics, and a molded article formed from the composition.
  • thermoplastic resins polyester-based resins such as polybutylene terephthalate (PBT) and polyamide-based resins have excellent mechanical properties, electrical properties, weather resistance, water resistance, and chemical resistance. Due to its solvent resistance, it is used in various applications such as electric / electronic parts, mechanical mechanism parts, and automobile parts.
  • the thermoplastic resin is required to be flame retardant for safety as well as improved mechanical properties as the application field expands.
  • a method of flame retardant by adding a halogen-based flame retardant, a non-halogen-based flame retardant such as a phosphorus compound, a nitrogen-containing compound, etc.
  • the halogen-based flame retardant is capable of flame-retarding the resin with a small amount having high flame retardancy as compared with the non-halogen-based flame retardant.
  • thermoplastic rosin composition
  • JP-A-10-251528 Patent Document 1
  • a thermoplastic resin 100 parts by weight of a thermoplastic resin, and (b) an ammonium polyphosphate. 0.5 to 50 parts by weight, (c) 5 to 50 parts by weight of a halogen-based polymer flame retardant such as brominated polystyrene flame retardant, (d) 0 to 15 parts by weight of antimony trioxide, (e)
  • a flame retardant thermoplastic resin composition excellent in tracking resistance characterized by comprising 0 to 50 parts by weight of a filler, is disclosed.
  • Sarasako, JP-A-11-343389 includes (A) 100 parts by weight of thermoplastic resin, (B) melamine salt of inorganic acid and Z or condensed phosphoric acid amide 0.5. ⁇ 50 parts by weight, (C) 5-50 parts by weight of a flame retardant such as a brominated polymer flame retardant, etc., (D) 0-15 parts by weight of antimony trimonate and (E) A flame-retardant thermoplastic resin composition excellent in tracking resistance, characterized by comprising 0 to 50 parts by weight of an inorganic filler, is disclosed.
  • the greaves described in these documents Even in adult products, the effect of improving tracking resistance under severe U and conditions is insufficient.
  • Patent Document 3 improves the flame retardancy of thermoplastic resin by using a specific (di) phosphinate and a halogen-based flame retardant together. It shows what you can do.
  • the composition described in this document is insufficient in the effect of improving electrical characteristics such as tracking resistance.
  • Patent Document 4 Japanese Patent Laid-Open No. 10-114854
  • Patent Document 10273589 Japanese Patent Laid-Open No. 10-273589
  • Patent Document 5 includes polyester resin or polyamide resin, halogenated flame retardant, organic filler, Na HP O, K H P O, Na H P O, KNaH P O, Na H P O,
  • a flammable resin molding composition is disclosed.
  • This document states that in order to improve the comparative tracking index (CTI), an olefin polymer such as an ethylene monoalkyl (meth) acrylate copolymer may be further included.
  • CTI comparative tracking index
  • an olefin polymer such as an ethylene monoalkyl (meth) acrylate copolymer may be further included.
  • the CTI improvement effect varies greatly depending on the type and amount of components used. For example, in the compositions of Patent Document 4 and Patent Document 5, the anti-tracking effect is improved.
  • inpolymer and pyro or alkali metal polyphosphate are not sufficient, and it is expressed by the combined use of inorganic substances (inorganic fillers) having a synergistic effect such as alkaline earth metal sulfate and talc.
  • inorganic substances inorganic fillers
  • the compositions of these documents certainly cause a significant decrease in physical properties, which can improve the tracking resistance at a certain level (for example, about 425 to 600 volts).
  • thermally unstable pyro or alkali metal polyphosphate is used, so that the thermal stability of the resin decreases, and the manufacturability and moldability of the resin composition. Is also unsuitable.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-251528 (Claim 1)
  • Patent Document 2 JP-A-11 343389 (Claim 1)
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-339510 (Claim 1)
  • Patent Document 4 JP-A-10-114854 (Claim 1, paragraph number [0013], Example)
  • Patent Document 5 JP-A-10-273589 (Claim 1, Claim 20, Example) Disclosure Problems to be solved by the invention
  • an object of the present invention is to provide a flame retardant resin composition that is excellent in flame retardancy and can improve electrical characteristics, and a molded product thereof.
  • Another object of the present invention is to provide a flame retardant resin composition and a molded body thereof that can reliably improve electrical characteristics such as tracking resistance at a high level.
  • the present inventor has found that a halogen-based flame retardant, a specific organic inorganic salt, an olefin-based resin, a fluorine-based resin, and a Group 4 metal compound.
  • a halogen-based flame retardant a specific organic inorganic salt, an olefin-based resin, a fluorine-based resin, and a Group 4 metal compound.
  • at least one selected electrical property improver we have found that the flame retardancy and electrical properties of the base resin can be reliably improved or improved at a high level without impairing the moldability.
  • the present invention has been completed.
  • the flame retardant resin composition of the present invention comprises a base resin (A), a halogenated flame retardant (B), an organic phosphinate (C 1) and a basic nitrogen-containing compound.
  • a flame retardant composition comprising at least one organic or inorganic acid salt (C) selected from the product oxalate (C2) and an electrical property improver (D) and having improved electrical properties.
  • It is a fat composition, wherein the electrical property improver (D) is composed of at least one selected from olefin-based resin, fluorine-based resin and Group 4 metal compound of the periodic table.
  • the base resin (A) includes a polyester-based resin, a polyamide-based resin, a polycarbonate-based resin, a polyphenylene oxide resin, a polyphenylene sulfide-based resin, a styrene-based resin, and a bull. It may be composed of at least one kind of thermoplastic resin selected from system resin.
  • the base resin (A) is a small amount selected from 1,4-cyclohexanedimethylene terephthalate, C alkylene terephthalate and C alkylene naphthalate.
  • It may be composed of a homo- or copolyester having at least one unit, and is typically composed of polybutylene terephthalate, copolyester mainly composed of butylene terephthalate units, polypropylene terephthalate, propylene terephthalate units.
  • Copolyester, polyethylene terephthalate, and copolyester force mainly composed of ethylene terephthalate units may be selected and may be composed of at least one selected.
  • the halogen flame retardant (B) is a bromine-containing acrylic resin (for example, brominated polyben Zyl (meth) acrylate resin), bromine-containing styrene resin (eg brominated styrene resin, brominated styrene monomer homopolymer or copolymer, etc.) ), Bromine-containing polycarbonate resin (brominated bisphenol-type polycarbonate resin, etc.), bromine-containing epoxy compounds (brominated bisphenol-type epoxy resin, brominated bisphenol-type phenoloxy resin, etc.), brominated polyaryl Etheric compounds, brominated aromatic imido compounds [eg, alkylene bis brominated phthalimide (eg, ethylene bis brominated phthalimide), etc.], brominated biaryl compounds and brominated tri (aryloxy) At least one bromine atom-containing flame retardant having a selected triazine compound strength may also be used.
  • bromine-containing acrylic resin for example
  • the organic phosphinic acid salt (C1) is, for example, an aliphatic phosphinic acid salt that may have a substituent, and Z or a alicyclic phosphinic acid that may have a substituent. It can be salt.
  • the organic phosphinate (C1) has a substituent! However, it may have a dialkylphosphinic acid, a substituent! /, Or may have a dicycloalkylphosphinic acid, an alkylenephosphinic acid which may have a substituent, or a substituent. Alkali-phosphinic acid, with substituents!
  • a salt with at least one selected from The oxo acid salt (C2) has a condensed phosphoric acid, sulfuric acid, and pyrosulfuric acid strength, and has at least one selected oxo acid, ammonia, urine compound, guanidine compound, and aminotriazine compound. It may be a salt with at least one selected basic nitrogen-containing compound! /.
  • the organic phosphinic acid salt (C1) includes a dialkylphosphinic acid optionally having a substituent, a dicycloalkylphosphinic acid optionally having a substituent, and a substituent. It may have an alkylene phosphinic acid, it has a substituent!
  • the oxo acid salt (C2) which may be a salt with at least one selected melon force, is a salt of polyphosphoric acid and aminotriazine compound, sulfuric acid and aminotriazine compound. Or at least one selected from a salt of pyrosulfuric acid and an aminotriazine compound, and a condensed phosphoric acid amide.
  • the organic / inorganic acid salt (C) may be composed of an organic phosphinic acid salt (C1) and an oxo acid salt (C2).
  • the electrical property improver (D) may be composed of at least olefin-based resin and Z or a periodic table Group 4 metal compound. In addition, the electrical property improver (D)
  • Olefin homo- or copolymer, and acid-titanium power may be at least one selected.
  • the proportion of the halogen-based flame retardant (B) may be about 2 to 20 parts by weight with respect to 100 parts by weight of the base resin (A).
  • the proportion of inorganic acid salt (C) may be about 3 to 30 parts by weight with respect to 100 parts by weight of the base resin (A).
  • the ratio of the organic inorganic salt (C) is about 20 to 500 parts by weight with respect to 100 parts by weight of the halogen flame retardant (B), and the electrical property improver (D ) May be about 10 to 150 parts by weight.
  • the resin composition further comprises a salt of an aminotriazine compound (for example, melamine cyanurate, etc.), a (hydrous) metal silicate (eg, talc, kaolin, etc.), a (hydrous) metal borate, Salt (for example, (hydrated) zinc borate, (hydrated) calcium borate, etc.), (hydrated) metal stannate (for example, (hydrated) zinc stannate), metal oxide (for example, zinc oxide) ), Metal sulfides (for example, zinc sulfate zinc), and alkaline earth metal compounds (for example, calcium carbonate, calcium hydrogen phosphate, etc.) May be included.
  • an aminotriazine compound for example, melamine cyanurate, etc.
  • a (hydrous) metal silicate eg, talc, kaolin, etc.
  • a (hydrous) metal borate, Salt for example, (hydrated) zinc borate, (hydrated) calcium borate, etc.
  • (hydrated) metal stannate
  • the resin composition may contain at least one flame retardant aid (F) selected from an aromatic compound, a phosphorus-containing compound, and an antimony-containing compound.
  • the aromatic compound (or flame retardant aid (F)) is a phenolic resin, a polyphenylene oxide resin, an aromatic epoxy resin, a phenoxy resin, a polyphenylene sulfide resin, a polycarbonate resin.
  • the phosphorus-containing compound (or flame retardant aid (F)) is (condensed) phosphate ester, (condensed) phosphate ester amide, (crosslinked) aryloxyphosphazene, (sub) phosphate metal salt, It may be at least one selected from metal hypophosphite, organic (phosphorous) phosphonate, organic (phosphorous) phosphonic acid metal salt, and organic (phosphorous) phosphonic acid aminotriazine salt.
  • the phosphorus-containing compound (or flame retardant aid (F)) is at least selected from alkyl (sulfur) phosphonic acid metal salts, (sulfurous) phosphate salts and hypophosphite metal salts. Both may be of a kind.
  • the resin composition may contain at least one additive selected from a filler, a heat stabilizer, a processing stabilizer, and a reactive stabilizer.
  • the resin composition of the present invention is excellent in flame retardancy and electrical properties.
  • [A] (i) When measured at a test piece thickness of 0.8 mm, the composition complies with UL94 combustion test. Flame retardancy is V—1 or higher (especially V—0 or higher), and (ii) Comparative tracking index according to IEC (International Electrotechnical Commission, same below) 112 is 350 V or higher (especially 400 V or higher) It may be.
  • IEC International Electrotechnical Commission, same below
  • the resin composition of the present invention has a [ ⁇ ] (0 test piece thickness of 1.6 mm, flame retardancy in accordance with UL94 flammability test is V-2 or more (preferably V-1 or more).
  • the comparative tracking index according to IEC 112 may be 500 V or more (preferably 650 V or more).
  • the present invention also includes a molded body formed of the above-mentioned rosin composition.
  • a molded body may be an electrical / electronic component, an office automation device component, a home appliance component, an automobile component, or a mechanical mechanism component.
  • the flame-retardant resin composition of the present invention comprises a base resin, a halogen-based flame retardant, a specific organic inorganic salt, and an electrical property improver having characteristics for improving electrical properties. Combined with it, it has excellent flame retardancy and electrical characteristics. In the present invention, the electrical characteristics such as tracking resistance can be reliably improved at a high level by the combination.
  • the flame retardant resin composition of the present invention is composed of at least a base resin, a halogen-based flame retardant, a specific organic / inorganic acid salt, and a specific electrical property improver.
  • a resin composition also has improved electrical properties (such as tracking resistance represented by a comparative tracking index) as well as flame retardancy.
  • the base resin (A) is not particularly limited, and various types of resin such as thermoplastic resin [for example, polyester resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, Polyphenylene sulfide resin, polyacetal resin, ketone resin, polysulfone resin (for example, polysulfone), polyether ketone resin (polyether ketone, etc.), polyetherimide, polyurethane resin, polyimide, Polyoxy benzylene, acrylic resin, styrene resin, bur resin, thermoplastic elastomer, etc.], thermosetting resin (phenol resin, amino resin, thermosetting polyester resin, epoxy resin) Fat, silicone-based resin, bull ester-based resin, polyurethane-based resin, etc.).
  • thermoplastic resin for example, polyester resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, Polyphenylene sulfide resin, polyacetal resin, ketone resin, polysulfone resin (for example, polysulfone), polyether
  • the polyester-based resin is a homopolyester or copolyester obtained by polycondensation of a dicarboxylic acid component and a diol component, polycondensation of oxycarboxylic acid or rataton, or polycondensation of these components.
  • Preferred polyester-based resins generally include saturated polyester-based resins, particularly aromatic saturated polyester-based resins.
  • dicarboxylic acid component examples include aliphatic dicarboxylic acids (C dicarboxylic acids such as succinic acid, dartaric acid, adipic acid, hexadecanedicarboxylic acid, dimer acid, and the like.
  • C dicarboxylic acids such as succinic acid, dartaric acid, adipic acid, hexadecanedicarboxylic acid, dimer acid, and the like.
  • dicarboxylic acids such as dicarboxylic acids
  • alicyclic dicarboxylic acids hexahydrophthalic acid, hexa C dicarboxylic acids such as hydroterephthalic acid and hymic acid
  • aromatic dicarboxylic acids such as aromatic dicarboxylic acids
  • Terfenic acid norevonic acid, etc. bispheninoresigenic power norlevonic acid (4,4'-bipheninoresicanolenoic acid, diphenol ether-4,4'-dicarboxylic acid, diphenylalkanedicarboxylic acid (4,4 ⁇ -diphene) -Lumethanedicarboxylic acid, etc.), 4, 4'-diphenylketone dicarboxylic acid, etc.]], derivatives thereof (eg, derivatives capable of forming an ester such as lower alkyl esters, acid anhydrides, etc.).
  • the dicarboxylic acid components may be used alone or in combination of two or more.
  • polycarboxylic acids such as trimellitic acid and pyromellitic acid may be used in combination!
  • the dicarboxylic acid component includes aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid.
  • the diol component includes, for example, an aliphatic diol [eg, alkylene glycol (eg, C alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4 butane diol, hexane diol, preferably C A
  • alkylene glycol eg, C alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4 butane diol, hexane diol, preferably C
  • alkylene glycol eg, C alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4 butane diol, hexane diol, preferably C
  • alkylene glycol eg, C alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4 butane diol, hexane diol, preferably C A
  • Glycols such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, polytetramethylene glycol, etc.
  • alicyclic diols eg 1,4-cyclohexanediol, cycloalkane dialkanol ( 1, 4 C cycloalkane di C alkanol such as cyclohexane dimethanol
  • Aromatic diols such as 2,2bis (4hydroxyphenol) propane, 2,2bis (4— (2hydroxyethoxy) phenol) propane or brominated derivatives thereof, and xylylene alcohol May be used together.
  • the diol components may be used alone or in combination of two or more.
  • polyols such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol may be used in combination.
  • Preferred diol components include C alkylene glycol (ethylene glycol, trimer
  • Linear alkyls such as tylene glycol, propylene glycol, and 1,4 butanediol Render alcohol
  • polyalkylene glycol having an oxyalkylene unit with a repeat number of about 2 to 4 [including poly (oxy-c alkylene) unit such as diethylene glycol]
  • oxycarboxylic acid examples include oxybenzoic acid, oxynaphthoic acid, 4 carboxy-4'-hydroxybiphenyl, hydroxyphenol acetic acid, glycolic acid, D-, L or DZL lactic acid, oxycaproic acid. And oxycarboxylic acids such as these or derivatives thereof.
  • the ratataton includes C ratatones such as propiolatataton, butyrolatathon, valerolatataton, and force prolatataton (eg, ⁇ -force prolatataton).
  • Preferred polyester-based resins include cycloalkanedialkylene arylate units (such as 1,4-cyclohexanedimethylene terephthalate units) and alkylene arylate units (such as alkylene terephthalate and ⁇ or alkylene naphthalate units such as C Al
  • Having at least one unit [for example as a main component (for example, 50 to: LOO wt%, preferably 75 to about LOO wt%)] homopolyester or copolyester [for example poly 1,4-cyclohex Sandimethylene terephthalate, polyalkylene terephthalate (eg, poly C alkylene terephthalate such as polyethylene terephthalate (PET), polypropylene terephthalate ( ⁇ ), polybutylene terephthalate (PBT)), polyalkyl
  • Homopolyesters such as lennaphthalates (eg poly c alkylene naphthalates such as polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate)
  • lennaphthalates eg poly c alkylene naphthalates such as polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate
  • Particularly preferred polyester-based resin is a polybutylene terephthalate-based resin containing a butylene terephthalate unit as a main component [for example, polybutylene terephthalate, a copolyester having a butylene terephthalate unit as a main component (polybutylene terephthalate copolyester: , Isophthalic acid-modified polybutylene terephthalate, etc.)], polypropylene terephthalate resin containing propylene terephthalate unit as the main component [for example, polypropylene terephthalate, polypropylene Copolyesters based on propylene terephthalate units (polypropylene terephthalate
  • the copolymerizable monomer may be a C alkylene radical.
  • Cole such as linear alkylene glycol such as ethylene glycol
  • polyalkylene glycol oxyethylene units such as diethylene glycol and polytetramethylene glycol having an oxyalkylene unit with 2 to 4 repetitions.
  • aliphatic dicarboxylic acids such as dartaric acid, adipic acid, sebacic acid
  • Bisphenols such as alicyclic diols (1,4-cyclohexanedimethanol, etc.), aromatic diols [eg, 2,2-bis (4- (2-hydroxyethoxy) phenol) propane (DC alkylene) Case with oxide, hydroquinone, resorcin, 3, 3, one or 4, 3, one
  • aromatic dicarboxylic acid [(non) symmetric aromatic dicarboxylic acid (phthalic acid, isophthalic acid, monosodium 5-sulfoisophthalic acid Salt), diphenyl dicarboxylic acid (4, 4, diphenyl dicarboxylic acid, etc.), naphthalene dicarboxylic acid (2, 6 naphthalene dicarboxylic acid, etc.)], oxybenzoic acid (3- or 4-hydroxybenzoic acid, etc.) , Oxynaphthoic acid (6-hydroxy-2 naphthoic acid, 6-hydroxy 1-naphthoic acid, etc.), 4 carboxy-hydroxybiphenyl, etc.].
  • the polyester-based resin may be crosslinked as well as linear as long as the melt moldability is not impaired.
  • the polyester-based resin may be a liquid crystal polyester.
  • polyester-based resins include amino group-containing monomers (for example, 3- or 4-aminophenol, 3- or 4-aminobenzoic acid, tetramethylenediamine, hexamethylenediamine, noname). Also included are (liquid crystal) polyester amides modified with tylenediamine, m-xylylenediamine, and the like.
  • the polyester-based resin can be produced by a conventional method such as transesterification or direct esterification.
  • the intrinsic viscosity of the polyester resin may be, for example, about 0.4 to 2.0, preferably about 0.5 to 1.8, and more preferably about 0.6 to 1.5.
  • Polyamides include polyamides derived from diamines and dicarboxylic acids; aminocarboxylic acids, polyamides obtained by combining diamines and / or dicarboxylic acids as required; lactams, and optionally diamines and Z or dicarboxylic acids And polyamides induced by the combined use.
  • Polyamide includes copolyamide. Diamine, dicarboxylic acid, aminocarboxylic acid, and ratatam can be used alone or in combination of two or more.
  • diamine examples include C, such as tetramethylene diamine and hexamethylene diamine.
  • cycloaliphatic diamines such as alicyclic diamines (having substituents such as alkyl groups, and bis (amino C cycloalkyl) C alkanes). If necessary
  • aromatic diamines such as phenylenediamine and metaxylylenediamine may be used in combination.
  • dicarboxylic acids include C aliphatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, and dodecanedioic acid (C alkane dicarboxylic acid, etc.);
  • Acid (dimer acid); cyclohexane-1,4-dicarboxylic acid cyclohexane-1,3-dicarboxylic acid and other alicyclic dicarboxylic acids; phthalic acid, phthalic anhydride, isophthalic acid terephthalic acid, naphthalene Examples thereof include aromatic dicarboxylic acids such as carboxylic acids.
  • the aminocarboxylic acid include C-aminocarboxylic acids such as aminoaminobutanoic acid, aminononanoic acid, and aminoundecanoic acid. As ratata, for example, force prolatata,
  • C ratatam such as dodecaractam.
  • Polyamide-based resin includes aliphatic polyamides such as polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11 and polyamide 12; bis (aminocyclohexyl) C alkanes, etc. Fats such as alicyclic diamine and C-alkanedicarboxylic acid
  • Alicyclic polyamides obtained from aliphatic dicarboxylic acids aromatic dicarboxylic acids (eg, terephthalic acid and Z or isophthalic acid) and aliphatic diamines (eg, hexamethylenediamine, nonamethylenediamine)
  • aromatic dicarboxylic acids eg, terephthalic acid and Z or isophthalic acid
  • aliphatic diamines eg, hexamethylenediamine, nonamethylenediamine
  • Polyamides obtained from and aromatic and aliphatic dicarboxylic acids examples thereof include polyamides obtained from acids (for example, terephthalic acid and adipic acid) and aliphatic diamines (for example, hexamethylene diamine).
  • Polyamide-based resin can be used alone or in combination of two or more.
  • non-aromatic or aliphatic polyamides polyamide 46, polyamide, 6, positive amide, 66, positive amide, 610, positive amide, 612, positive amide, 11, positive amide, 12, etc.
  • Semi-aromatic polyamide Polyamide MXD6, Polyamide 9T, etc.
  • Semi-aromatic copolymer polyamide Polyamide, 6T / 6, Polyamide, 6 ⁇ / 66, Polyamide, 6 ⁇ / 11, Polyamide, 6 ⁇ / 12, Polyamide ⁇ 6l / 6, Polyamide, 61/66, Polyamide, 6 ⁇ / 6 ⁇ ⁇ ⁇ ⁇ , Polyamide, 6T / 6l / 6, Polyamide, 6 ⁇ / 6 ⁇ / 66, Polyamide 6 ⁇ 5 ⁇ , etc.
  • Polycarbonate-based resins include polymers obtained by reacting dihydroxy compounds (such as alicyclic diols and bisphenol compounds) with carbonate esters such as phosgene or diphenol carbonate.
  • Bisphenol compounds include bis (4-hydroxyphenol) methane, bis (hydroxyaryl) C alkanes such as 2,2bis (4hydroxyphenol) propane, 1, 1-bis (4 hydroxy) Bis) cyclohexane and other bis
  • Preferred polycarbonate-based resin includes bisphenol-type polycarbonate.
  • the polyphenylene oxide-based resin includes homopolymers and copolymers.
  • Homopolymers include poly (2,6 dimethyl-1,4 phenylene) oxide, poly (2,5 dimethyl-1,4 phenylene) oxide, poly (2,5 dimethyl 1,4 phenylene) Poly (such as oxide or tri-C alkyl-phenol)
  • copolymer of polyphenylene-oxide a monomer unit of the homopolymer is used.
  • Copolymers having two or more types eg, random copolymers having 2,6 dimethyl-1,4 phenoxide units and 2,3,6 trimethyl 1,4 phenoxide units
  • benzeneformaldehyde resin Such as phenol resin
  • alkylbenzeneformaldehyde resin alkylphenol-modified benzeneformaldehyde resin block obtained by reacting alkylphenol such as talesol, and poly-phenoloxide block as the main structure
  • the modified modified graft copolymer include grafting.
  • Polyphenylene sulfide resin is a homopolymer and copolymer having a phenylsulfide skeleton (Ar— S) [wherein Ar represents a phenol group] Is included.
  • phenylene group one Ar—
  • examples of the phenylene group include p-, m-, or o-phenylene groups, and substituted phenylene groups (for example, C alkyl groups).
  • Polyphenol-sulfide-based fats are
  • phenol-sulfide units composed of a phenylene group it may be a homopolymer using the same repeating unit or a copolymer containing different repeating units.
  • the homopolymer is preferably a substantially linear polymer having a p-phenylene sulfide group as a repeating unit.
  • Copolymers can be used in combination of two or more different types of the above-mentioned ferrosulfide groups.
  • Polyphenylene sulfide resin may be a polymer obtained by oxidative crosslinking or thermal crosslinking of a low molecular weight linear polymer. Alternatively, it may be a polymer having a linear structure. Polypheresis The rufud resin includes a branched or cross-linked polyphenylene sulfide resin polymerized by combining monomers having three or more functional groups, and a resin composition obtained by blending this resin with the linear polymer.
  • polyphenylene sulfide-based resin polyphenylene sulfide, polybiphenylene sulfide (PBPS), polyphenylene sulfide ketone (PPSK), polybiphenyl sulfide sulfone (PBSS) and the like can be used.
  • PBPS polybiphenylene sulfide
  • PPSK polyphenylene sulfide ketone
  • PBSS polybiphenyl sulfide sulfone
  • Styrenic resin includes styrene monomers (styrene, butyltoluene, etc.) or copolymers; styrene monomers and vinyl monomers [(meth) acrylic monomers (for example, (Meth) acrylonitrile, (meth) acrylic acid ester, (meth) acrylic acid, etc.), ⁇ , ⁇ monoolefinic unsaturated carboxylic acid or acid anhydride or ester such as maleic anhydride, etc.]; Examples thereof include styrene-based graft copolymers and styrene-based block copolymers.
  • styrene resin polystyrene (GPPS), styrene-methyl methacrylate copolymer, styrene (meth) acrylic acid copolymer, styrene acrylonitrile copolymer (AS resin) , Rubber components (polybutadiene, acrylic rubber, styrene-butadiene copolymer rubber, EPDM, EVA, etc.) are polymerized with styrene monomers and, if necessary, copolymerizable monomers (acrylo-tolyl, methyl methacrylate, etc.) Graft copolymers [impact-resistant polystyrene (HIPS), ABS resin, MBS resin, etc.], copolymers composed of polystyrene blocks and gen or olefin blocks [for example, styrene butadiene styrene ( SGPPS), styrene-methyl methacrylate copolymer, st
  • BS block copolymer
  • styrene isoprene block copolymer styrene isoprene styrene (SIS) block copolymer
  • SE BS hydrogenated styrene butadiene styrene
  • SEPS hydrogenated styrene isoprene styrene
  • a bull-type monomer for example, a bull ester such as acetic acid bull; a chlorine-containing bull monomer (for example, salt-type bull)); a vinyl ketone; a vinyl ether; (Buramines such as carbazole, etc.) Or a copolymer with other copolymerizable monomers is included.
  • a bull-type monomer for example, a bull ester such as acetic acid bull; a chlorine-containing bull monomer (for example, salt-type bull)); a vinyl ketone; a vinyl ether; (Buramines such as carbazole, etc.) Or a copolymer with other copolymerizable monomers is included.
  • the vinyl-based rosin for example, polybulacetal such as polybulal alcohol, polybul formal, polybulbutyral, and ethylene acetate bur copolymer
  • rosins or polymer compounds may be used alone or in combination of two or more.
  • the base resin may be a liquid crystalline polyester! /
  • a thermoplastic resin such as a polyester-based resin, a styrene-based resin, a polyamide-based resin, or a polyphenylene oxide-based resin (especially At least one kind of thermoplastic resin selected from polyamide-based resin and polyester-based resin, more preferably polyester-based resin (PBT-based resin, PPT-based resin, PET-based resin, etc.) Etc.
  • the number average molecular weight of the base resin is not particularly limited and is appropriately selected according to the type and use of the resin, for example, 5 10 3 to 200 10 4 , preferably 1 10 4 to 150 10 4. More preferably, a range force of about 1 ⁇ 10 4 to: LOO ⁇ 10 4 can be selected.
  • the base resin is a polyester-based resin
  • the number average molecular weight is, for example, 5 X 10 3 to: LOO X 10 4 , preferably 1 10 4 to 70 10 4 , more preferably 1.2 X 10 It may be about 4 to 30 ⁇ 10 4 .
  • the organic and halogenated flame retardants (B) can be organic halides.
  • Organic halides usually contain at least one selected from chlorine, bromine and iodine nuclear power.
  • halogen-based flame retardant examples include bromination of halogen-containing acrylic resin [halogenated polybenzyl (meth) acrylate resin such as poly (pentabromobenzyl (meth) acrylate)].
  • Halogenated benzyl (meth) acrylate such as polybenzyl (meth) acrylate, poly (pentachlorobenzyl (meth) acrylate), or copolymers, etc.] solids, logene-containing styrenic resin [for example, styrene Halogenated styrene resin (brominated polystyrene, chlorinated polystyrene, etc.) obtained by halogenation treatment (for example, chlorine, bromine, bromine chloride treatment, etc.) ), Halogenated styrene monomer alone or copolymer], halogen-containing polycarbonate Fat (halogenated polycarbonate such as brominated polycarbonate and chlorinated polycarbonate),
  • Halogenated polyarylether compounds for example, bis (halogenary) reel ethers such as octa-decabutor diphenyl ether, octa-decachlorodiphenyl ether, etc. Logene ether) etc .; halogen-containing polyphenylene oxide resins such as brominated polyphenylene ether], halogenated aromatic imido compounds [eg alkylene bis brominated phthalimide (eg ethylene C such as bisbrominated phthalimide Bromine such as alkylenebisbrominated phthalimide)
  • Aromatic imide compounds such as bisimide compounds
  • halogenated biaryl compounds eg, bis (halogenated C aryl) such as brominated diphenyls
  • Halogenated bisphenols such as A, or derivatives thereof (such as brominated polyesters obtained by polymerizing ethylene oxide adducts of halogenated bisphenols), halogenated alicyclic hydrocarbons (cross-linked cyclic saturated or Unsaturated halogenated alicyclic hydrocarbons such as halogenated polycycloalkanes such as dodecachloropentacyclotadeca 7, 15-gen), halogenated tri (aryloxy) triazine compounds [for example, brominated triphenoxy Brominated tri (allyloxy) triazine compounds such as citriazine.
  • Halogen flame retardants can be used alone or in combination of two or more.
  • halogenated flame retardants compounds containing chlorine atoms and Z or bromine atoms are preferred, especially brominated organic bromides (bromine-containing acrylic resins, bromine-containing styrene resins, bromine-containing polycarbonate-based resins).
  • Fat for example, brominated bisphenol type polycarbonate resin such as brominated bisphenol A type polycarbonate resin
  • bromine-containing epoxy compound for example, brominated bisphenol type epoxy resin (brominated bisphenol type A epoxy resin)
  • brominated epoxy resins such as brominated bisphenol type phenoxy resins (such as brominated bisphenol A type phenoxy resins), brominated polyaryl ether compounds (Such as bis (brominated aryl) etheric compounds such as Otta Bromodiphenyl ether), odor Elemental aromatic imido compounds, Brominated atom-containing flame retardants such as brominated bisaryl compounds, brominated tri (aryloxy) triazine compounds, etc.] are preferred.
  • bromine atom-containing flame retardants in particular, fluorinated polybenzyl (meth) acrylate resin, brominated styrene resin [for example, brominated products of styrene resin such as brominated polystyrene (or styrene) Brominated products of rosin), homo- or copolymers of brominated styrene monomers (for example, polybrominated styrene, etc.), brominated bisphenol-type polycarbonate resin, brominated bisphenol Type epoxy resins, brominated bisphenol type phenoxy resins and alkylene bis brominated phthalimides (eg, C
  • Subbrominated phthalimide and the like) and at least one kind of selected force are preferable.
  • the proportion of the halogen flame retardant is, for example, 1 to 30 parts by weight, preferably 2 to 25 parts by weight (eg 2 to 20 parts by weight), more preferably 100 parts by weight of the base resin. About 3 to 20 parts by weight (for example, 5 to 18 parts by weight).
  • Organic / inorganic acid salt (C) is at least selected from organic phosphinic acid salt (C1) and basic nitrogen-containing compound oxo acid salt (C2) (salt of oxo acid and basic nitrogen-containing compound). It consists of one kind.
  • organic phosphinic acid salt (C1) examples include organic group-substituted phosphinic acid and polyvalent phosphinic acid (polyhydric phosphinic acid (polyvalent phosphinic acid) in which phosphinic acid is substituted with an organic group (V having a substituent, or hydrocarbon group))
  • Organic phosphinic acid salts such as polyphosphinic acid in which multiple phosphinic acids are linked by a valent organic group (metal, boron, ammonium and basic nitrogen-containing compounds) at least one selected And salts with other salt-forming components (such as metal salts, boron salts (borori compounds, etc.), ammonium salts, salts with amino group-containing nitrogen compounds, etc.) and the like.
  • organic phosphinates can improve the electrical properties of the resin even when a halogen-based flame retardant is used. Therefore, organic phosphinates appear to function as electrical property improvers.
  • the organic phosphinic acid salt the organic phosphinic acid is substituted with a substituent (for example, a hydroxyl group, an unsaturated group [for example, a carboxyl group, an acyl group, an alkoxycarbonyl group (such as a methoxycarbonyl group), etc.) Bond-containing groups], hydrocarbon groups ( For example, an alkyl group such as a methyl group), an alkoxy group (such as a methoxy group), and the like.
  • Organic phosphinic acid may have these substituents alone or in combination of two or more. /.
  • organic phosphinic acid salt (C1) as a typical organic phosphinic acid, for example, it may have a substituent, and may be a mono- or dialkylphosphinic acid [dialkylphosphinic acid (such as di-C alkylphosphinic acid), For example, dimethylphosphinic acid, methylethyl
  • / May be mono or dicycloalkylphosphinic acid [eg, monocycloalkylphosphinic acid (eg, cycloalkylalkylphosphinic acid such as cyclohexylmethylphosphinic acid) ), Dicycloalkylphosphinic acid (for example, dicyclohexylphosphinic acid, etc.) mono- or dicycloalkylphosphinic acid (mono- or di-C cycloalkylphosphinic acid, etc.)
  • monocycloalkylphosphinic acid eg, cycloalkylalkylphosphinic acid such as cyclohexylmethylphosphinic acid
  • Dicycloalkylphosphinic acid for example, dicyclohexylphosphinic acid, etc.
  • mono- or dicycloalkylphosphinic acid mono- or dicycloalkylphosphinic acid (mono- or di-C cyclo
  • aryl phosphinic acid 6-10 6-10 aryl phosphinic acid; mono- or diaryl phosphines such as alkyl aryl phosphinic acids (such as methyl phenol phosphinic acid etc. alkyl-C aryl-phosphinic acid etc.)
  • Alkene-phosphinic acid which may have a substituent (for example, 1-hydroxy 2,3 dihydro-1H-phosphole 1-oxide, 1-hydroxy 2,5 dihydr 1-phosphorus 1-oxide, 1 —Hydroxy-1,3-methyl 2,5 dihydro-1,1H —Cyclo Calkene-phosphinic acid such as phosphole 1-oxide), substituents
  • cycloalkylenephosphinic acid for example, 1,3 cyclobutylene phosphinic acid, 1,3 cyclopentylenephosphinic acid, 1,4 cyclooctylenephosphinic acid, 1,5 cyclooctylene
  • C cycloalkylene phosphines such as phosphinic acid
  • a bicycloalkene-phosphinic acid that may have a substituent
  • a polyvalent phosphinic acid in which multiple phosphinic acids (or organic phosphinic acids) are linked by a polyvalent organic group for example, substituted Anolecan bisphosphinic acid which may have a group [C alkanebis (phosphinic acid) such as ethane-1,2-bis (phosphinic acid)], etc. ! /
  • Nolecanbis anolequinolephosphinic acid
  • Calkanebis C alkylphosphinic acid
  • ethane-1,2-bis metalhinolephosphinic acid
  • Metals that form organic phosphinates include Group 1 metals (alkali metals) (lithium, potassium, sodium, etc.) and Group 2 metals (alkaline earth metals) (magnesium, calcium, noble metals) of the periodic table. Lithium, etc.), periodic table group 4 metals (titanium, zirconium, etc.), transition metals (manganese and other periodic table group 7 metals; iron and other periodic table group 8 metals; cobalt and other periodic table group 9 metals; Periodic Table Group 10 metals such as nickel; Periodic Table Group 11 metals such as copper), Periodic Table Group 12 metals such as zinc, Periodic Table Group 13 metals such as aluminum, Periodic Table 14 such as tin Group 15 metals such as group metals and antimony are included.
  • the metal salt is a hydrate salt such as a hydrate magnesium salt, a hydrate calcium salt, or a hydrate aluminum salt. It may be a hydrous zinc salt.
  • the metal salt also includes a salt in which the metal is partially oxidized (for example, a titanium salt, a zirconium salt, etc.).
  • a basic nitrogen-containing compound that forms a salt for example, a nitrogen-containing compound having an amino group [aminotriazine compound (melamine, guanamine, benzoguanamine and Z or a condensate thereof (melam, melem)
  • the organic phosphinic acid salt includes a double salt of an organic phosphinic acid and a plurality of salt-forming components, for example, a melamine 'melam' melem double salt, a melamine 'melam' melem 'melon double salt and the like.
  • Group 1 metal, Group 2 metal, Group 4 metal, Group 7 metal, Group 8 metal, Group 10 metal, Group 10 metal, Group 10 Group 11 metals, Group 12 metals, Group 13 metals, Group 14 metals, Group 15 metals and aminotriazine compounds are preferred.
  • a part or all of the acid groups of the organic phosphinic acid having an acid group (such as a carboxy group) as a substituent in the organic phosphinic acid salt is a salt (eg, the salt exemplified above, The same metal as the acid or a salt such as a nitrogen-containing compound) may be formed (for example, force ruxylate! /, May! /).
  • the organic phosphinic acid salt may have a substituent! /?
  • An aliphatic phosphinic acid salt and Z or an alicyclic phosphinic acid salt optionally having a substituent for example, Have a substituent! /, May have a dialkylphosphinic acid, have a substituent! /, May have a dicycloalkylphosphinic acid, an optionally substituted alkylenephosphinic acid, substituted Have a group!
  • Aluminum salts Methyl ethyl phosphinic acid Ti salt, Jetyl phosphinic acid Ti salt, Ethyl butyl phosphinic acid Ti salt, Dibutyl phosphinic acid Ti salt, and Ti salt corresponding to these salts, etc.
  • Aminotriazine compound salts dimethyl phosphinic acid melamine salt, methyl ethyl phosphinic acid melamine salt, jetyl phosphinic acid melamine salt, ethyl butyl phosphinic acid melamine salt, dibutyl phosphinic acid melamine salt, these melamine salts
  • Aminotriazine compounds such as the corresponding melamine 'melam' melem double salt And the like)]
  • an alkylene phosphinic acid salt which may have a substituent [for example, 1-hydroxyphosphorane 1-oxide alkaline earth metal salt (
  • Organic phosphinates have substituents! /, Dialkylphosphinic acids, optionally substituted dicycloalkylphosphinic acids, and substituents. May be selected from alkylene phosphinic acid, having a substituent! /, Alkalkylene phosphinic acid, and having a substituent, alkane bis (alkyl phosphinic acid). Selected from organic phosphinic acids, Group 2 metals (such as calcium), Group 13 metals (such as aluminum), and aminotriazine compounds (such as melamine, melam, melem, and melon) And at least one salt formed. Organic phosphinates are used alone or in combination You may combine.
  • organic phosphinic acid salt examples include, for example, JP-A-55-5979, JP-A-8-73720, JP-A-9-278784, and JP-A-11-236392.
  • Examples of the oxo acid (oxo acid other than the organic phosphinic acid) constituting the oxo salt (C2) include nitric acid, chloric acid (perchloric acid, chloric acid, chlorous acid, hypochlorous acid, etc.), phosphorus Acid [Non-condensed phosphoric acid such as orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid; pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polymetaphosphoric acid, phosphoric anhydride (pentanoic acid ⁇ niline), etc.
  • Condensed phosphoric acid (polyphosphoric acid etc.)], organic phosphoric acid (phosphoric acid (phosphoric acid other than hypophosphorous acid) and partial esters of alcohols such as alcoholic alcohol and alkylene glycol (for example, dimethyl phosphate) Such as mono- or dialkyl phosphate), sulfuric acid (non-condensed sulfuric acid such as peroxomonosulfuric acid, sulfuric acid, sulfurous acid; condensed sulfuric acid such as peroxodisulfuric acid, pyrosulfuric acid, etc.), boric acid (such as orthoboric acid, metaboric acid, etc.) Non-condensed boric acid; Oxalic acid, boric anhydride, condensed boric acid, etc.), chromic acid, antimonic acid, molybdic acid, tungstic acid, etc.
  • oxo acids can be used alone or in combination of two or more.
  • condensed phosphoric acid pyrophosphoric acid, polyphosphoric acid, polymetaphosphoric acid, etc.
  • sulfuric acid condensed sulfuric acid, etc.
  • condensed sulfuric acid pyrosulfuric acid, etc.
  • the basic nitrogen-containing compound (nitrogen-containing compound) constituting the oxoacid salt (C2) includes, for example, a hydrogen atom (amino group (-NH 2) or imino group (-NH-) bonded to a nitrogen atom.
  • Nitrogen-containing compounds chain or cyclic compounds having hydrogen atoms, ie active hydrogen atoms, such as ammonia, urea compounds (urea, etc.), guagin compounds (dicyandiamide, guanidine, gua-) Lurea, etc.), aminotriazine compounds [melamine, guanamine, Nzoguanamine and z or condensates thereof (melamine condensates such as melam, melem, melon etc.) and the like. These nitrogen-containing compounds can be used alone or in combination of two or more. Of the nitrogen-containing compounds, ammonia, urea, guanidine, dicyandiamide, melamine, and melamine condensates (melam, melem, melon, etc.) are preferable.
  • the oxo acid salt (C2) may be a polycondensate or the like as long as it is a reaction (and calcination) product of oxo acid and a basic nitrogen-containing compound.
  • polycondensates with the above triazine compounds such as melamine, the above guanidine compounds, etc.
  • Such a polycondensate can be obtained, for example, by calcining and condensing the oxo acid and the cyanamide derivative, if necessary, in the presence of a binder (urea and Z or urea oxalate). In many cases, it is a polymer compound having an amide bond.
  • a polycondensate usually, as the oxo acid, in addition to the exemplified phosphoric acid and organic phosphoric acid, the nitrogen-containing compound phosphate (ammonium polyphosphate, phosphoric acid) Urea etc.) (especially organic phosphoric acid and Z or condensed phosphoric acid) condensed phosphoric acid amide (or polyphosphoric acid amide) can be used.
  • phosphate amide urea and Z or urea phosphate are often used as the binder.
  • the polycondensates can be used alone or in combination of two or more.
  • JP-A-7-138463 can be referred to.
  • Such polyphosphoric acid amide can be produced by the method described in JP-B-51-39271 and JP-B-53-2170.
  • Polyphosphoric acid amides are commercially available, for example, as “Sumisafe PM” [Sumitomo Chemical Co., Ltd.], “Tyen S” [Taihei Chemical Industrial Co., Ltd.], etc.
  • Preferable oxoacid salts include, for example, salts of polyphosphoric acid and aminotriazine compound [for example, polyphosphoric acid such as melamine polyphosphate, melam polyphosphate, melem polyphosphate, and Z or melamine Salt with condensate (especially melamine or melamine condensate)], salt with sulfuric acid and aminotriazine mixture [eg sulfuric acid (di) melamine, sulfuric acid (di) melam, sulfuric acid (di) melem, melamine sulfate melam) Salts of sulfuric acid such as melem double salt and melamine and / or melamine condensate], salts of pyrosulfuric acid and aminotriazine compound [for example, pyrosulfuric acid (di) melamine, pyrosulfuric acid (di ) Melam, pyrosulfuric acid (di) melem, salt of pyrosulfurfuric acid
  • Such an oxoacid salt can improve the electrical properties of the resin even when a halogen-based flame retardant is used. Therefore, the oxoacid salt seems to function as an electrical property improver.
  • organic / inorganic acid salt (C) may be used alone or in combination of two or more.
  • organic 'organic acid salts (C) may be composed of organic phosphinic acid salts (C1) and oxo acid salts (C2) to further improve electrical properties! / ⁇ .
  • the former ⁇ latter (weight ratio) 99Zl to lZ99, preferably 95 ⁇ 5 to 5 ⁇ 95, more preferably about 90ZlO to 10Z90 .
  • the ratio of the organic / inorganic acid salt (C) is, for example, 1 to 60 parts by weight (for example, 2 to 50 parts by weight), preferably 3 to 40 parts by weight with respect to 100 parts by weight of the base resin. (For example, 4 to 35 parts by weight), more preferably about 3 to 30 parts by weight (for example, 8 to 25 parts by weight).
  • the proportion of the organic-inorganic acid salt (C) is, for example, 5 to 500 parts by weight, preferably 10 to 350 parts by weight, more preferably 20 to 200 parts by weight with respect to 100 parts by weight of the halogenated flame retardant ( ⁇ ). It may be 300 parts by weight (for example, 30 to 280 parts by weight), particularly about 40 to 270 parts by weight, and usually about 20 to 500 parts by weight.
  • the electrical property improver (D) is a component for improving the electrical properties of the base resin at a high level in combination with a halogen-based flame retardant (and organic 'inorganic acid salt). And at least one selected from fluorine-based resin and Group 4 metal compounds.
  • the resin-like electrical property improver (olefin-based resin, fluorine-based resin) is a resin different from the base resin (resin).
  • olefin-based resin examples include olefin monomers [ethylene-propylene, 1-butene, 3-methyl-1-pentene, 4-methyl-1-butene, 1-hexene, 1-octene, etc. — C olefin); cyclic olefin ⁇ e.g.
  • Cycloalkenes such as lobene, cyclopentene, cyclohexene (C cycloalkene
  • cycloalkynes such as cyclopentine and cyclohexyne; bridged cyclic olefins
  • Typical olefin-based resins include, for example, ⁇ -olefin-based resins [for example, a-C olefins such as polyethylene, polypropylene, and propylene-ethylene copolymers.
  • ⁇ -olefin-based resins for example, a-C olefins such as polyethylene, polypropylene, and propylene-ethylene copolymers.
  • ⁇ -C olefin and copolymerizable monomers such as acid glycidyl ester copolymers
  • a modified olefinic resin for example, an olefinic resin (single or copolymer of olefin)
  • an acid component for example, a, j8-unsaturated carboxylic acid ((meth) acrylic acid)
  • acid-modified olefinic resins modified with Z or acid anhydrides thereof, etc. cyclic olefinic resins (eg For example, a homopolymer of cyclic olefin, a-C olefin-cyclic olefin copolymer
  • Olefin-based resin can be used alone or in combination of two or more.
  • ⁇ -C olefins are homopolymers or copolymers (polyethylene).
  • Tylene polypropylene, ethylene ⁇ -propylene copolymer, etc., especially polypropylene, ethylene-propylene copolymer), a C olefin (meth) acrylic acid copolymer, a
  • acid-modified olefin-based resin for example, ⁇ -C olefin homopolymer or copolymer is modified with an acid component.
  • olefin-based resins particularly acid-modified polypropylene such as maleic anhydride-modified polypropylene
  • the number average molecular weight of the olefin-based rosin is not particularly limited, but is, for example, about 300-20 X 10 5 , preferably about 500 to 10 X 10 4 .
  • Fluorine-based resins include fluorine-containing monomers alone or as copolymers, such as fluorine-containing monomers (tetrafluoroethylene, black trifluoroethylene, beryllium).
  • fluorine-containing monomers tetrafluoroethylene, black trifluoroethylene, beryllium.
  • olefin monomers and copolymers with (acrylic monomers such as (meth) acrylate).
  • fluorinated resins include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene monohexafluoro.
  • copolymers such as propylene copolymer, tetrafluoroethylene perfluoroalkyl butyl ether copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene-chlorotrifluoroethylene copolymer. it can.
  • the average particle size of the fluorine-containing coffin that may be used in the form of particles is, for example, about 10 to 5000 ⁇ m, preferably about 100 to 1000 ⁇ m, and more preferably 100 to 700. It may be about ⁇ m.
  • the Group 4 metal compound of the periodic table includes, for example, metal compounds such as titanium, zirconium and hafnium, and is usually titanium or zirconium (particularly titanium) compound in many cases.
  • Typical Group 4 metal compounds of the periodic table include titanium compounds [for example, titanates or hydroxides (for example, titanium oxides such as titanium dioxide), halogenated titanium (fluorine). Etc.), oxalates of titanium (eg titanium sulfate), hydrates thereof (eg, acid or titanium mono- or dihydrate)], zirconium compounds corresponding to these titanium compounds (acid Zirconium etc.).
  • Preferred Group 4 metal compounds of the periodic table include titanium oxide. These periodic table Group 4 metal compounds may be used alone or in combination of two or more.
  • the Group 4 metal compound of the periodic table may be used in the form of particles (or powder), and the average particle size of the Group 4 metal compound in the periodic table is, for example, 0.01 to 20 / ⁇ ⁇ , preferably 0.02 to 10 ⁇ m, more preferably about 0.05 to 5 m.
  • the electrical property improver (D) may be used alone or in combination of two or more.
  • the electrical property improver (D) may be composed of at least olefin-based resin and Z or a periodic table Group 4 metal compound (particularly olefin-based resin).
  • the organic / inorganic acid salt (C) is an organic phosphinic acid salt
  • the electrical property improver (D) is often composed of at least olefin-based resin and Z or a periodic table Group 4 metal compound.
  • the ratio of the electrical property improver (D) is, for example, 0.5 to 30 parts by weight (for example, 1 to 25 parts by weight), preferably 2 to 20 parts by weight with respect to 100 parts by weight of the base resin. (For example, 3 to 18 parts by weight), more preferably about 3 to 15 parts by weight.
  • the proportion of the electrical property improver (D) is, for example, 3 to 300 parts by weight, preferably 5 to 200 parts by weight, and more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the halogen flame retardant. (For example, 15 to 130 parts by weight) Usually, it may be about 30 to 180 parts by weight (for example, 40 to 160 parts by weight, preferably 50 ⁇ 140 parts by weight).
  • the resin composition of the present invention may further contain an electrical property improving aid.
  • an electrical property improving aid any of the above components (B) to (D), which is a compound and acts as an aid for improving electrical properties, for example, a nitrogen-containing salt.
  • preferable electrical property enhancing aids include organic acid salts of aminotriazine compounds (especially cyanuric acid salts), silicate metal salts, metal borate salts, alkaline earth metal compounds, and the like. . These electrical property improving aids can be used alone or in combination of two or more.
  • the proportion of the electrical property improving aid (E) is, for example, 0 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts per 100 parts by weight of the base resin. It may be about parts by weight (for example, 1.5 to: LO parts by weight).
  • the rosin composition of the present invention may further contain a flame retardant aid (F).
  • Flame retardant aids (F) include aromatic compounds (phenolic resin, arlin-based resin, poly-phenoxide-based resin, aromatic epoxy resin (bisphenol-type epoxy resin, novolak-type resin). Epoxy Resin), phenoxy resin, polyphenylene sulfide resin, polycarbonate resin, polyarylate resin, aromatic polyamide resin, aromatic polyester resin (for example, aromatic which may be liquid crystalline) Polyester-based resin), aromatic polyesteramide-based resin (for example, liquid crystalline '! Aromatic polyesteramide-based resin)
  • Phosphorus-containing compounds phosphorus-containing compounds that do not belong to the category of the above-mentioned organic inorganic salt (C) such as organic phosphinic acid), antimony-containing compounds, molybdenum-containing compounds (molybdenum oxide) Etc.), tungsten-containing compounds (such as acid-tungsten), bismuth-containing compounds (such as bismuth oxide), tin-containing compounds (such as tin oxide), iron-containing compounds (such as iron oxide), copper-containing compounds (oxidized) Copper, etc.), silicon-containing compounds [(poly) organosiloxane (silicone resin such as polydimethylsiloxane and polymethylphenol siloxane, silicone oil, polysilsesquioxane, etc.), layered silicate (smectite type such as montmorillonite) Layered silicate, Li-type fluorine theolite, Na-type fluorine theolite, Li-type tetracathenium fluor
  • Phosphorus-containing compounds include (condensed) phosphate esters [eg, resorcinol bis (diphenylenophosphate), nodoquinone bis (diphenol-nophosphate), biphenolinobis (diphenol-nophosphate), bisphenolore A (diphenol-nophosphate) , Resorcinol bis (di-1,6 xylyl phosphate), hydroquinone bis (di 1,2 xylyl phosphate), biphenol bis (di 1,6 xylyl phosphate), bisphenol bis A bis (di —2, 6-xylinolephosphate), pentaerythritol diphenol-nophosphate, pentaerythritol di 2,6 xylyl phosphate, 2, 6, 7 trioxa 1-phosphabicyclo [2.2.2] octane-4 methanol 1oxide, And U.S.
  • phospho-tolyl compounds for example, aryloxyphosphazene (phenoxyphosphazene, triloxyphosphazene, xylylo). Cyclic and / or chain phosphazene compounds such as xyphosphazenes, phenoxytriloxy phosphazenes, phenoxysilyl phosphazenes, etc., and their crosslinked phosphazene compounds (for example, phenoxy crosslinked with bisphenol residues).
  • organic (sub) phosphonic acid compounds for example, organic phosphonic acid Esters, organic (sub) phosphonic acid metal salts (Li, Na, K, Mg, Ca, Al, Sb, Sn, Metal salts such as Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn), basic nitrogen compound salts of organic (sub) phosphonic acid (melamine salt, guanamine salt, benzoguanamine salt and Z or theirs) Condensate salts (such as melamine condensates such as melam, melem, melon, etc.), and inorganic phosphorus compounds [eg, red phosphorus, (phosphite) metal phosphates (phosphorous calcium, calcium hypophosphite, phosphorous Aluminum oxide, phosphoric acid, aluminum phosphite double salt, boron phosphat
  • organic (sub) phosphonic acid compound examples include, for example, methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, isobutylphosphonic acid, octylphosphonic acid, hydroxyalkyl Phosphonic acid (hydroxymethyl phosphonic acid, hydroxyethyl phosphonic acid, hydroxypropyl phosphonic acid, etc.), anorecoxy anoleno phosphonic acid (methoxy methino phosphonic acid, ethoxy ethino phosphonic acid, etc.), canoleboxy Norequinolephosphonic acid (such as canoleboxoxymethinorephosphonic acid, 2-force noreboxetylphosphonic acid), methylphosphonous acid, ethylphosphonous acid, n-propyl phosphonous acid, isopropylphosphonous acid, n-butyl Phosphorous acid, is
  • alkylene diphosphonic acid etc. 2--6 alkylene diphosphonic acid etc.); 1-hydroxyethylidene 1, 1, diphosphonic acid etc. It may be substituted with alkylidene diphosphonic acid (C alkylidene diphosphonic acid).
  • Etc . have substituents (such as hydroxyl groups) such as nitrilotris (methylphosphonic acid)! / ⁇ , nitrilotris (alkylphosphonic acid) [nitrilotris (C alkylphosphonic acid)
  • -Polymeric phosphonic acids such as polyphosphonic acid and polyallylphosphonic acid; esters of these organic (phosphorous) phosphonic acids [methylphosphonic acid monomethyl ester, 2-carboxyethyl phosphonate, triethyl carboxymethylphosphonate, carboxyethylphospho It may have a substituent such as triethyl acid, and may be a mono- or polyalkyl ester of alkyl (sub) phosphonic acid (C alkyl (sub) phosphonic acid mono- or di-C alkyl ester).
  • Organic (sub) phosphonic acid metal salt Melamine salt of phosphonic acid, melamine salt of ethyl phosphonic acid, melamine salt of n-propyl phosphonic acid, melamine salt of isopropyl phosphonic acid, melamine salt of n-butyl phosphonic acid, isobutyl Melamine salt of phosphonic acid, Melamine salt of octyl phosphonic acid, Melam salt, Melem salt, Melon salt, Melamine 'Melam' Melem double salt, Melamine 'Melam' Melem 'Melon double salt corresponding to these melamine salts , 1-hydroxyethylidene-1, 1-diphosphonic acid mono to tetramelamine salts, nitrilotris (methylphosphonic acid) mono to hexane melamine salts and other aminotriazine compounds (such as melamine or condensates thereof) Organic (phosphorous) aminotriazine salts
  • organic (sub) phosphonic acid compounds include, for example, JP-A-48-57988, JP-A-55-5979, JP-A-56-84750, JP-A-63. — 22866, JP-A-1-226891, JP-A-2-180875, JP-A-4-234893, JP-A-7-224078, JP-A-7-247112, JP-A-8- No.
  • organic (sub) phosphate compounds or salts thereof may be used alone or in combination of two or more. Can be used.
  • the flame retardant aid (F) includes (condensed) phosphoric acid ester, (condensed) phosphoric acid ester amide, (cross-linked) aryloxyphosphazene, (sub) phosphorous acid metal salt, hypophosphorous acid. It includes at least one selected from acid metal salts, organic (phosphorous) phosphonic acid esters, organic (phosphorous) phosphonic acid metal salts, and organic (phosphorous) phosphonic acid aminotriazine salts. ) Includes at least one selected from an alkyl (phosphite) metal salt, a (phosphite) metal salt, and a hypophosphite metal salt.
  • Antimony-containing compounds include, for example, acid-antimony [antiacid trimonate (Sb)
  • antimonate [metal antimonate (for example, alkali metal such as sodium antimonate, alkaline earth metal such as magnesium antimonate), ammonium antimonate, etc.) .
  • metal antimonate for example, alkali metal such as sodium antimonate, alkaline earth metal such as magnesium antimonate, ammonium antimonate, etc.
  • antimony-containing compounds can be used alone or in combination of two or more.
  • acid diantimones and alkali metal salts of antimonic acid are preferred.
  • the antimony-containing compound may be surface-treated with a surface treatment agent such as an epoxy compound, a silane compound, an isocyanate compound, and Z or titanate compound, if necessary.
  • a surface treatment agent such as an epoxy compound, a silane compound, an isocyanate compound, and Z or titanate compound, if necessary.
  • the average particle size of the antimony-containing compound may be, for example, about 0.02 to 5 ⁇ m, preferably about 0.1 to 3111.
  • flame retardant aids it is particularly preferable to use at least one selected from aromatic compounds, phosphorus-containing compounds and antimony-containing compounds.
  • an oxo acid salt (C2) of a basic nitrogen-containing compound is used as the organic inorganic salt (C)
  • the flame retardancy can be further improved by using an antimony-containing compound.
  • the resin composition of the present invention is reliably flame retardant at a high level even if it does not contain such a flame retardant aid by combining the components (B) to (D). And excellent electrical properties
  • the ratio of the flame retardant aid (F) is, for example, 0 to 30 parts by weight (for example, 0.05 to 20 parts by weight), preferably 0 with respect to 100 parts by weight of the base resin (A). 1-20 parts by weight (eg 0.3-10 Parts by weight), more preferably about 0.5 to 5 parts by weight.
  • the flame-retardant resin composition of the present invention further comprises other additives such as other flame retardants (nitrogen-based, phosphorus-based flame retardants, etc.), fillers, stabilizers (ultraviolet absorbers, weather resistance (light) stability). Agents, heat stabilizers, processing stabilizers, phosphorus stabilizers, reactive stabilizers, etc.), antistatic agents, lubricants, mold release agents, crystallization nucleating agents, plasticizers, colorants (dyes, pigments, etc.), lubrication An agent, an anti-dripping agent, etc. may be contained. These other additives can be used alone or in combination of two or more.
  • the resin composition may contain, in particular, a filler, a heat stabilizer, a processing stabilizer, and the like.
  • Examples of the filler include conventional fibrous, plate-like, and granular fillers.
  • Examples of the fibrous filler include inorganic fibers (glass fiber, carbon fiber, boron fiber, potassium titanate fiber (whisker), etc.), organic fiber (amide fiber, etc.) and the like.
  • Examples of the plate filler include glass flake, my strength, graphite, and various metal foils.
  • particulate fillers examples include metal oxides (such as zinc oxide and alumina), sulfates (such as calcium sulfate and magnesium sulfate), carbonates (such as calcium carbonate), and glasses (milled fiber, glass beads, glass balloons, etc.) ), Sulfides (disulfurized molybdenum, disulfurized tungsten, etc.), carbides (fluorinated graphite, silicon carbide, etc.), activated carbon, boron nitride and the like.
  • Preferred fillers include inorganic fibers (especially glass fibers). The fillers can be used alone or in combination of two or more.
  • the amount of filler used is, for example, 0 to: LOO parts by weight, preferably 1 to 80 parts by weight (for example, 5 to 75 parts by weight), more preferably 100 parts by weight of the base resin. May be about 10 to 70 parts by weight (for example, 20 to 65 parts by weight).
  • Heat resistant stabilizers include hindered phenolic compounds (hindered phenolic acid inhibitors) such as 2,6 di-tert-butyl-cresole, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2 , 2'-thiobis (4-methyl-6-t-buty Rufenol), 4, 4'-thiobis (6-t-butyl-m cresol), triethylene glycol-bis- (3- (3-tert-butyl-5-methyl-4-hydroxyphenol) propionate), pentaerythritol -Branched C alkylphenols such as tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)], phosphorus compounds
  • hindered phenolic compounds hindered phenolic acid inhibitors
  • hindered phenolic acid inhibitors such as 2,6 di-tert-butyl-cresole, 2,2'-methylenebis (4-methyl-6-tert-butylphenol),
  • amine-based acid inhibitors amamine-based acid inhibitors [for example, naphthylamine, phenol-naphthylamine, 1,4 phenol-diamine, bis (2, 2, 6, 6 —Hetarded amines such as tetramethyl-4-piperidyl) senocate and bis (1, 2, 2, 6, 6 pentamethyl-4-piperidyl) sebacate], hydroquinone compounds (hydroquinone acid oxidants) [eg , 2,5 di-t-butylhydroquinone, etc.], quinoline compounds (quinoline-based acid / antioxidant) [eg, 6 ethoxy-1,2,2,4 trimethyl
  • At least a hindered phenol compound may be used as a heat stabilizer.
  • the heat stabilizer may be a hindered phenol compound that may be composed of a hindered phenol compound alone and another heat stabilizer (for example, a phosphorus compound, an alkali or alkali earth metal compound, and a hydride). And at least one selected from the site).
  • a hindered phenol compound that may be composed of a hindered phenol compound alone and another heat stabilizer (for example, a phosphorus compound, an alkali or alkali earth metal compound, and a hydride). And at least one selected from the site).
  • the ratio of the heat stabilizer is, for example, 0 to 15 parts by weight (for example, 0.001 to: L0 part by weight), preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the base resin. More preferably (especially 0 .5 to 2 parts by weight).
  • Processing stabilizers include, for example, long chain fatty acids (e.g., force puric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, stearic acid, araquinic acid, behenic acid, montanoic acid, oleic acid, linoleic acid, C-saturated or unsaturated fatty acids such as linolenic acid, arachidonic acid, erucic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid), long chain fatty acid amino acids
  • long chain fatty acids e.g., force puric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, stearic acid, araquinic acid, behenic acid, montanoic acid, oleic acid, linoleic acid, C-saturated or unsaturated fatty acids such as linolenic acid
  • Long chain fatty acid esters eg, ethylene glycol distearate, glycerol monostearate, trimethylolpropane monostearate, pentaerythritol stearate ester
  • Sorbitan monostearic acid ester monostearic acid ester of polyalkylene glycol (polyethylene glycol, etc.), corresponding palmitic acid ester, lauric acid ester, behenic acid ester, montanic acid ester, oleic acid ester, etc.
  • Long chain fatty acid esters Long chain fatty acid esters
  • polyalkylene glycols polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene copolymers, etc.
  • silicone compounds silicone compounds
  • waxes eg natural paraffin, synthetic Paraffin, microwax, polyolefin wax (polyethylene wax, polypropylene wax, etc.) and the like. Processing stabilizers can be used alone or in combination of two or more.
  • the ratio of the processing stabilizer is, for example, 0 to 20 parts by weight, preferably 0.1 to: LO parts by weight, more preferably about 0.5 to 5 parts by weight, with respect to 100 parts by weight of the base resin. It may be.
  • (Reactive stabilizer) is, for example, 0 to 20 parts by weight, preferably 0.1 to: LO parts by weight, more preferably about 0.5 to 5 parts by weight, with respect to 100 parts by weight of the base resin. It may be.
  • reactive stabilizers examples include epoxy-based reactive stabilizers [glycidyl ether compounds (bisphenol-A diglycidyl ether, phenol-glycidyl ether, etc.), glycidyl ester compounds (benzoic acid glycidyl ester, versatic acid glycidyl ester).
  • oxetane-based reactive stabilizers [1, 4 bis ⁇ [3 ethyl-3-oxeta-lmethoxy] methyl ⁇ benzene, di [1-ethyl (3-oxetanyl) Methyl] ethers, etc.]
  • oxazoline-based reactive stabilizers [1,3 phenylene bis (2-oxazoline), 1,4 phenylene bis (2-oxazoline), etc.]
  • carpositimide-based reactive stabilizers polyaryl carbopositimide , Polyalkylimide, polycarboimide, etc.].
  • These reactive stabilizers may be used alone or in combination of two or more.
  • the proportion of the reactive stabilizer is, for example, 0 to 20 parts by weight, preferably 0.05 to 8 parts by weight, and more preferably about 0.1 to 5 parts by weight with respect to 100 parts by weight of the base resin. You can select from a range of
  • the flame-retardant resin composition of the present invention comprises a base resin (A), a halogen-based flame retardant (B), an organic 'inorganic acid, which may be a powder mixture or a molten mixture. It can be prepared by mixing the salt (C), the electrical property improver (D), and if necessary, other components (electrical property enhancer, flame retardant aid, additive, etc.) by a conventional method.
  • the present invention also includes a molded body formed from the flame retardant resin composition (for example, a resin composition (molded body) formed by solidifying the molten mixture).
  • the flame-retardant resin composition and the molded body are, for example, (1) a method of mixing each component, kneading and extruding with a uniaxial or biaxial extruder to prepare pellets, 2) —Method of preparing pellets (masterbatch) with different compositions, mixing (diluting) the pellets in a predetermined amount and using them for molding, and (3) A method of directly charging and molding one or more components can be employed.
  • all or a part of the components other than the base resin may be mixed in advance and mixed with the base resin.
  • the components other than the base resin may be mixed directly with the base resin without mixing them in advance. Good.
  • other than the base resin The order of addition of the components is not particularly limited, and after adding some components that may be added all at once to the base fat, the remaining ingredients (if necessary It may be added in several batches).
  • the molded body can be produced by melt-kneading the flame-retardant resin composition by a conventional method, and molding by a conventional method such as extrusion molding, injection molding or compression molding.
  • the flame-retardant resin composition (and molded product) of the present invention has high flame retardancy and electrical properties, despite the fact that it contains a halogen-based flame retardant, without impairing moldability. It is possible to reliably achieve both levels.
  • the resin composition (and molded product) of the present invention has a flame retardancy of SV-2 or more, preferably V-1 in accordance with UL94 flammability test when measured with a test piece thickness of 1.6 mm. Above, more preferably V-0 or more.
  • the comparative tracking index (CTI) based on IEC112 (UL746A) is 400 V or more (for example, about 400 to 1000 V), preferably 450 V or more (for example, About 450 to 900 V), more preferably 500 V or more (for example, about 500 to 850 V).
  • the resin composition of the present invention combines a halogen-based flame retardant, a specific organic inorganic salt, and a specific electrical property improver, so that the electrical properties can be reliably improved at a remarkably high level.
  • the comparative tracking index (CTI) can be 600 V or higher (for example, about 600 to 850 V), preferably 650 V or higher (for example, about 650 to 750 V).
  • the resin composition (and molded product) of the present invention has a flame retardancy of V-1 or more, preferably according to UL94 flammability test, when measured with a test piece thickness of 0.8 mm.
  • V—more than 0, powerful comparative tracking index (CTI) according to IEC112 (UL746A) is 350V or more (eg about 350 to 1000V), preferably 400V or more (eg about 400 to 900V), and more Preferably, it may be 450 V or more (for example, about 450 to 850 V).
  • the flame-retardant resin composition (and molded product) of the present invention is excellent in flame retardancy and electrical properties, and is used in various applications such as electrical and electronic parts, office automation (OA) equipment parts, It can be suitably used for home appliance parts, automobile parts, machine mechanism parts, and the like.
  • OA office automation
  • the flammability was evaluated at a test piece thickness of 1.6 mm or 0.8 mm.
  • CTI comparative tracking index
  • Inorganic acid salt (C), electrical property improver (D), electrical property enhancer (E), flame retardant aid (F), filler (G), heat stabilizer (H), processing stabilizer (I), reactive stabilizer ⁇ is as follows
  • ( ⁇ -5) Brominated bisphenol ⁇ type epoxy resin [SRT5000, Sakamoto Pharmaceutical Co., Ltd.]
  • B-6 Brominated bisphenol A type polycarbonate resin [Fiaguard FG-7500, manufactured by Teijin Chemicals Ltd.].
  • Acidic pyrophosphate metal salt (C3: used in comparative examples)
  • D1-3 Maleic anhydride modified polyolefin [Tafmer MP, manufactured by Mitsui Chemicals, Inc.]
  • D1-4 Polypropylene [Noblen J, manufactured by Sumitomo Chemical Co., Ltd.]
  • Aromatic compounds (F1) Aromatic compounds (F1)
  • G-2 Glass fiber (chopped strand having a diameter of 10 ⁇ m and a length of 3 mm).
  • Hyde mouth talcite (H2-4): Hyde mouth talcite [DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.].
  • Q- 2) Polycardiimide [Carpolite HMV—8CA, manufactured by Nisshinbo Industries, Inc.].
  • Filling base resin (A) with halogenated flame retardant (B), organic 'inorganic acid salt (C), electrical property improver (D), electrical property improver (E), flame retardant aid (F), filling Agent (G), heat-resistant stabilizer (H), and processing stabilizer (I) were mixed in the proportions (parts by weight) shown in Table 6, and kneaded and extruded with an extruder to prepare a pellet-shaped resin composition. Using the obtained pellets, test molded articles were produced by injection molding, and flammability (0.8 mm) and tracking resistance (comparative tracking index) were evaluated. The results are shown in Table 6.

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Abstract

L'invention concerne une composition de résine ignifuge présentant d'excellentes propriétés ignifuges et des caractéristiques électriques grandement améliorées. L'invention concerne en particulier une composition de résine comprenant (A) une résine de base (plus spécifiquement une résine polyester, une résine polyamide ou analogue), (B) un ignifugeant halogène (plus spécifiquement un ignifugeant contenant du brome tel qu'une résine polybenzyl(méth)acrylate bromée ou une résine styrène bromée), (C) un sel d'acide organique/inorganique, plus spécifiquement un phosphinate organique (tel qu'un sel métallique ou un sel d'un composé aminotriazine) ou un sel d'un oxoacide (tel qu'un polyphosphate ou un (pyro)sulfate) d’un composé basique contenant de l'azote (tel qu'un composé aminotriazine), et (D) un améliorant de caractéristiques électriques, plus spécifiquement une résine oléfine (telle qu'un copolymère α-C2-3oléfine-(méth)acrylate), une résine fluorée, ou un composé d'un métal du groupe IV (tel que l'oxyde de titane).
PCT/JP2006/313561 2005-07-08 2006-07-07 Composition de resine ignifuge WO2007007663A1 (fr)

Priority Applications (3)

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CN2006800249249A CN101218305B (zh) 2005-07-08 2006-07-07 阻燃性树脂组合物
DE112006001824T DE112006001824T5 (de) 2005-07-08 2006-07-07 Flammenhemmende Harzzusammensetzung
JP2007524623A JP5186210B2 (ja) 2005-07-08 2006-07-07 難燃性樹脂組成物

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WO2014034474A1 (fr) * 2012-08-29 2014-03-06 東洋紡株式会社 Composition de résine pour le scellement de composants électriques et électroniques, procédé de fabrication d'un agent de scellement de composants électriques et électroniques, et agent de scellement de composants électriques et électroniques
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JP7454343B2 (ja) 2019-07-31 2024-03-22 ポリプラスチックス株式会社 難燃性ポリブチレンテレフタレート樹脂組成物
CN112480657A (zh) * 2019-09-11 2021-03-12 广东广山新材料股份有限公司 一种聚酰胺树脂组合物及其制备方法和应用
WO2021153414A1 (fr) * 2020-01-31 2021-08-05 東レ株式会社 Composition de résine de polyester thermoplastique et article moulé
JPWO2021153414A1 (fr) * 2020-01-31 2021-08-05
WO2023027069A1 (fr) * 2021-08-24 2023-03-02 ポリプラスチックス株式会社 Composition de résine de polytéréphtalate de butylène et article moulé
KR102660598B1 (ko) * 2023-09-18 2024-04-26 에이치디씨현대이피 주식회사 자외선 안정성이 높은 열가소성 수지 조성물

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JPWO2007007663A1 (ja) 2009-01-29

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