WO2007007663A1 - Flame retardant resin composition - Google Patents

Flame retardant resin composition 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
Other languages
French (fr)
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/en
Priority to DE112006001824T priority patent/DE112006001824T5/en
Priority to JP2007524623A priority patent/JP5186210B2/en
Publication of WO2007007663A1 publication Critical patent/WO2007007663A1/en

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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

Disclosed is a flame retardant resin composition which is excellent in flame retardance and greatly improved in electrical characteristics. Specifically disclosed is a resin composition composed of (A) a base resin (specifically, a polyester resin, a polyamide resin or the like), (B) a halogen flame retardant (specifically, a bromine-containing flame retardant such as a brominated polybenzyl(meth)acrylate resin or a brominated styrene resin), (C) an organic/inorganic acid salt, specifically an organic phosphinate (such as a metal salt or an aminotriazine compound salt) or an oxo acid salt (such as a polyphosphate or (pyro)sulfate) of a basic nitrogen-containing compound (such as an aminotriazine compound), and (D) an electrical characteristics improver, specifically an olefin resin (such as α-C2-3olefin-(meth)acrylate copolymer), a fluorine resin or a group IV metal compound (such as titanium oxide).

Description

明 細 書  Specification
難燃性樹脂組成物  Flame retardant resin composition
技術分野  Technical field
[0001] 本発明は、難燃性および成形性に優れるとともに、電気特性が改良された榭脂組 成物及びこの組成物で形成された成形体に関する。  TECHNICAL FIELD [0001] 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.
背景技術  Background art
[0002] 熱可塑性榭脂のうち、ポリブチレンテレフタレート（PBT)などのポリエステル系榭脂 やポリアミド系榭脂などは、優れた機械的特性、電気的特性、耐候性、耐水性、耐薬 品性ゃ耐溶剤性を有するため、電気 ·電子部品、機械機構部品、自動車部品など種 々の用途に利用されている。一方、前記熱可塑性榭脂には、利用分野が拡大するに つれ、機械的特性の向上とともに、安全上、難燃性であることが要求される。一般的 には、熱可塑性榭脂に、ハロゲン系難燃剤や、リン系化合物、窒素含有化合物など の非ハロゲン系難燃剤を添加することにより、難燃ィ匕する方法が知られている。ハロ ゲン系難燃剤は、非ハロゲン系難燃剤に比べ、難燃性が高ぐ少量で樹脂を難燃ィ匕 することが可能である。  [0002] Among 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. On the other hand, the thermoplastic resin is required to be flame retardant for safety as well as improved mechanical properties as the application field expands. In general, there is known 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. to a thermoplastic resin. 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.
[0003] そして、このような熱可塑性榭脂 (組成物）には、難燃性に加えて、用途に応じて、 高い電気的特性が要求される。このような榭脂の電気的特性を改善するため、特開 平 10— 251528号公報 (特許文献 1)には、（a)熱可塑性榭脂 100重量部に対し、 ( b)ポリリン酸アンモ-ゥム 0. 5〜50重量部、（c)臭素系ポリスチレン難燃剤などのハ ロゲン系高分子難燃剤 5〜50重量部、（d)三酸化アンチモン 0〜 15重量部、（e)無 機充填剤 0〜50重量部とからなることを特徴とする耐トラッキング特性に優れた難燃 性熱可塑性榭脂組成物が開示されている。さら〖こ、特開平 11— 343389号公報 (特 許文献 2)には、（A)熱可塑性榭脂 100重量部と、（B)無機酸のメラミン塩および Z または縮合リン酸アミド 0. 5〜50重量部と、（C)臭素系高分子難燃剤などのハロゲン 系難燃剤などの難燃剤 5〜50重量部と、（D)三酸ィ匕アンチモン 0〜 15重量部と、 (E )無機充填剤 0〜50重量部とからなることを特徴とする耐トラッキング特性に優れた難 燃性熱可塑性榭脂組成物が開示されている。しかし、これらの文献に記載の榭脂組 成物でも、厳 U、条件下での耐トラッキング性の改善効果は不十分である。 [0003] In addition to flame retardancy, such thermoplastic rosin (composition) is required to have high electrical characteristics depending on the application. In order to improve the electrical properties of such a resin, JP-A-10-251528 (Patent Document 1) describes (a) 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 (Patent Document 2) 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. However, the greaves described in these documents Even in adult products, the effect of improving tracking resistance under severe U and conditions is insufficient.
[0004] 一方、特開 2004— 339510号公報（特許文献 3)には、特定の（ジ)ホスフィン酸塩 とハロゲン系難燃剤とを併用することにより、熱可塑性榭脂の難燃性を向上できること が示されている。しかし、この文献に記載の組成物では、耐トラッキング性などの電気 特性の改善効果は不充分である。 [0004] On the other hand, Japanese Patent Application Laid-Open No. 2004-339510 (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. However, the composition described in this document is insufficient in the effect of improving electrical characteristics such as tracking resistance.
[0005] また、特開平 10— 114854号公報（特許文献 4)及び特開平 10— 273589号公報 [0005] Also, Japanese Patent Laid-Open No. 10-114854 (Patent Document 4) and Japanese Patent Laid-Open No. 10-273589
(特許文献 5)には、ポリエステル榭脂又はポリアミド榭脂と、ハロゲン化難燃剤と、無 機充填剤と、 Na HP O、 K H P O、 Na H P O 、 KNaH P O、 Na H P O、  (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,
3 2 7 2 2 2 7 3 2 3 10 2 2 7 2 2 2 7 3 2 7 2 2 2 7 3 2 3 10 2 2 7 2 2 2 7
Na P O などの（酸性)ピロ又はポリリン酸金属塩とを含み、電気特性の向上した難Containing (acidic) pyro or polyphosphate metal salts such as Na 2 P 2
8 6 19 8 6 19
燃性榭脂成形組成物が開示されている。この文献には、比較トラッキング指数 (CTI) を向上するため、さらにエチレン一アルキル (メタ）アタリレートコポリマーなどのォレフ インポリマーを含んでいてもよいことが記載されている。しかし、これらの文献の組成 物でも、十分に耐トラッキング性を改善できない。また、これらの文献では、 CTIの改 善効果は用いる成分の種類及び量などに応じて大きく変化しており、例えば、特許 文献 4および特許文献 5の組成物では、耐トラッキング改善効果はォレフインポリマー とピロ又はポリリン酸アルカリ金属塩の併用では不充分であり、さらに硫酸アルカリ土 類金属塩やタルクなどの相乗効果を有する無機物質 (無機充填剤)の多量併用配合 によって発現している。このため、これらの文献の組成物では、確かにある程度のレ ベル (例えば、 425〜600ボルト程度）で耐トラッキング性を改善できる力 著しい物 性低下を生じる。し力も、これらの文献に記載の方法でも、熱的に不安定なピロ又は ポリリン酸アルカリ金属塩を使用するので、榭脂の熱安定性が低下し、榭脂組成物の 製造性、成形性も不向きである。  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. However, even the compositions of these documents cannot sufficiently improve the tracking resistance. Also, in these documents, 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. The combined use of inpolymer and pyro or alkali metal polyphosphate is 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. For this reason, 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). However, even in the methods described in these documents, 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.
特許文献 1 :特開平 10— 251528号公報 (請求項 1)  Patent Document 1: Japanese Patent Laid-Open No. 10-251528 (Claim 1)
特許文献 2：特開平 11 343389号公報 (請求項 1)  Patent Document 2: JP-A-11 343389 (Claim 1)
特許文献 3 :特開 2004— 339510号公報 (請求項 1)  Patent Document 3: Japanese Patent Application Laid-Open No. 2004-339510 (Claim 1)
特許文献 4:特開平 10— 114854号公報 (請求項 1、段落番号 [0013]、実施例） 特許文献 5 :特開平 10— 273589号公報 (請求項 1、請求項 20、実施例） 発明の開示 発明が解決しょうとする課題 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
[0006] 従って、本発明の目的は、難燃性に優れるとともに電気特性を向上できる難燃性榭 脂組成物及びその成形体を提供することにある。  [0006] Therefore, 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.
[0007] 本発明の他の目的は、耐トラッキング性などの電気特性を高!ヽレベルで確実に向 上できる難燃性榭脂組成物及びその成形体を提供することにある。 [0007] 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.
課題を解決するための手段  Means for solving the problem
[0008] 本発明者は、前記課題を達成するため鋭意検討した結果、ハロゲン系難燃剤と、 特定の有機'無機酸塩と、ォレフィン系榭脂、フッ素系榭脂および第 4族金属化合物 カゝら選択された少なくとも 1種の電気特性向上剤とを組み合わせると、成形性を損な うことなぐベース榭脂の難燃性及び電気特性を高 ヽレベルで確実に改善又は向上 できることを見いだし、本発明を完成した。  [0008] As a result of intensive studies to achieve the above-mentioned problems, 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. In combination with 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.
[0009] すなわち、本発明の難燃性榭脂組成物は、ベース榭脂 (A)と、ハロゲン系難燃剤 ( B)と、有機ホスフィン酸塩 (C 1)および塩基性窒素含有ィ匕合物のォキソ酸塩 (C2)か ら選択された少なくとも 1種の有機，無機酸塩 (C)と、電気特性向上剤 (D)とで構成さ れ、かつ電気特性の向上した難燃性榭脂組成物であって、前記電気特性向上剤 (D )が、ォレフィン系榭脂、フッ素系榭脂および周期表第 4族金属化合物から選択され た少なくとも 1種で構成されて!、る。  That is, 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.
[0010] 前記ベース榭脂 (A)は、ポリエステル系榭脂、ポリアミド系榭脂、ポリカーボネート 系榭脂、ポリフエ二レン才キシド系榭脂、ポリフエ二レンスルフイド系榭脂、スチレン系 榭脂、及びビュル系榭脂から選択された少なくとも 1種の熱可塑性榭脂で構成されて いてもよい。特に、ベース榭脂（A)は、 1, 4—シクロへキサンジメチレンテレフタレート 、 C アルキレンテレフタレート及び C アルキレンナフタレートから選択された少な [0010] 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. In particular, the base resin (A) is a small amount selected from 1,4-cyclohexanedimethylene terephthalate, C alkylene terephthalate and C alkylene naphthalate.
2-4 2-4 2-4 2-4
くとも 1種の単位を有するホモ又はコポリエステルで構成されていてもよぐ代表的に は、ポリブチレンテレフタレート、ブチレンテレフタレート単位を主成分とするコポリエ ステル、ポリプロピレンテレフタレート、プロピレンテレフタレート単位を主成分とするコ ポリエステル、ポリエチレンテレフタレート、およびエチレンテレフタレート単位を主成 分とするコポリエステル力 選択された少なくとも 1種で構成されていてもよい。  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.
[0011] 前記ハロゲン系難燃剤 (B)は、臭素含有アクリル系榭脂 (例えば、臭素化ポリベン ジル (メタ)アタリレート系榭脂）、臭素含有スチレン系榭脂 (例えば、スチレン系榭脂 の臭素化物、臭素化スチレン系単量体の単独又は共重合体などの臭素化スチレン 系榭脂など）、臭素含有ポリカーボネート系榭脂 (臭素化ビスフエノール型ポリカーボ ネート榭脂など）、臭素含有エポキシ化合物 (臭素化ビスフ ノール型エポキシ榭脂、 臭素化ビスフエノール型フヱノキシ榭脂など）、臭素化ポリアリールエーテルィ匕合物、 臭素化芳香族イミドィ匕合物 [例えば、アルキレンビス臭素化フタルイミド (例えば、ェチ レンビス臭素化フタルイミドなど)など]、臭素化ビスァリールイ匕合物及び臭素化トリ（ァ リールォキシ)トリアジンィ匕合物力も選択された少なくとも一種の臭素原子含有難燃 剤であってもよい。 [0011] 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.
[0012] 前記有機ホスフィン酸塩 (C1)は、例えば、置換基を有していてもよい脂肪族ホスフ イン酸塩、及び Z又は置換基を有して 、てもよ 、脂環族ホスフィン酸塩であってもよ い。  [0012] 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.
[0013] 前記難燃性榭脂組成物において、前記有機ホスフィン酸塩 (C1)が、置換基を有し て！、てもよ 、ジアルキルホスフィン酸、置換基を有して!/、てもよ ヽジシクロアルキルホ スフイン酸、置換基を有していてもよいアルキレンホスフィン酸、置換基を有していて もよ ヽァルケ-レンホスフィン酸、置換基を有して!/、てもよ ヽ（ビ）シクロアルキレンホス フィン酸、及び置換基を有して 、てもよ 、アルカンビス（アルキルホスフィン酸）力 選 択された有機ホスフィン酸と、周期表第 1族金属、周期表第 2族金属、周期表第 4族 金属、周期表第 7族金属、周期表第 8族金属、周期表第 10族金属、周期表第 11族 金属、周期表第 12族金属、周期表第 13族金属、周期表第 14族金属、周期表第 15 族金属、及びアミノトリアジンィ匕合物（例えば、メラミン、メラム、メレム、およびメロン)か ら選択された少なくとも一種との塩であってもよぐ前記ォキソ酸塩 (C2)は、縮合リン 酸、硫酸およびピロ硫酸力 選択された少なくとも 1種のォキソ酸と、アンモニア、尿 素化合物、グァニジンィ匕合物及びアミノトリアジンィ匕合物力も選択された少なくとも一 種の塩基性窒素含有ィ匕合物との塩であってもよ!/、。  [0013] In the flame-retardant resin composition, 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! /, Or (bi) cycloalkylenephosphinic acid, and with substituents, alkanebis (alkylphosphinic acid) Selected organic phosphinic acid, periodic table group 1 metal, periodic table group 2 metal, periodic table group 4 metal, periodic table group 7 metal, periodic table group 8 metal, periodic table group 10 metal, Periodic Table Group 11 metals, Periodic Table Group 12 metals, Periodic Table Group 13 metals, Periodic Table Group 14 metals, Periodic Table Group 15 metals, and aminotriazine compounds (eg, melamine, melam, melem) 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! /.
[0014] 代表的には、前記有機ホスフィン酸塩 (C1)は、置換基を有していてもよいジアルキ ルホスフィン酸、置換基を有していてもよいジシクロアルキルホスフィン酸、置換基を 有して 、てもよ 、アルキレンホスフィン酸、置換基を有して!/、てもよ 、ァルケ-レンホ スフイン酸、及び置換基を有して ヽてもよ ヽアルカンビス（アルキルホスフィン酸）から 選択された有機ホスフィン酸と、周期表第 2族金属、周期表第 13族金属、メラミン、メ ラム、メレム、およびメロン力も選択された少なくとも一種との塩であってもよぐ前記ォ キソ酸塩 (C2)は、ポリリン酸とアミノトリアジンィ匕合物との塩、硫酸とアミノトリアジンィ匕 合物との塩、ピロ硫酸とアミノトリアジン化合物との塩、及び縮合リン酸アミドから選択 された少なくとも 1種であってもよい。 [0014] Typically, 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! An organic phosphinic acid selected from sulphinic acid and a substituent, alkanebis (alkylphosphinic acid), a metal of group 2 of the periodic table, a metal of group 13 of the periodic table, melamine, melam, melem 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.
[0015] 前記有機 ·無機酸塩 (C)は、有機ホスフィン酸塩 (C1)およびォキソ酸塩 (C2)で構 成されていてもよい。 [0015] The organic / inorganic acid salt (C) may be composed of an organic phosphinic acid salt (C1) and an oxo acid salt (C2).
[0016] 前記電気特性向上剤 (D)は、ォレフィン系榭脂及び Z又は周期表第 4族金属化合 物で少なくとも構成されて 、てもよ 、。また、電気特性向上剤 (D)は、 α— C ォレ  [0016] 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)
2-3 フィンの単独又は共重合体、 α - C ォレフィン （メタ）アクリル酸共重合体、 —  2-3 Fin homo- or copolymer, α-C olefin (meth) acrylic acid copolymer, —
2-3  2-3
C ォレフィン （メタ）アクリル酸エステル共重合体 (例えば、 α—C ォレフィン C-olefin (meth) acrylic acid ester copolymer (eg α-C olefin)
2-3 2-32-3 2-3
(メタ）アクリル酸 C アルキルエステル共重合体、 α - C ォレフィン （メタ）アタリ (Meth) acrylic acid C alkyl ester copolymer, α-C olefin (meth) atari
1-4 2-3  1-4 2-3
ル酸グリシジルエステル共重合体など）、酸変性ォレフィン系樹脂、フツイ匕ひ C  Glycidyl phosphate ester copolymer, etc.), acid-modified olefin resin, Futsuhihihi C
2-3 ォレフィンの単独又は共重合体、および酸ィ匕チタン力 選択された少なくとも 1種であ つてもよい。  2-3 Olefin homo- or copolymer, and acid-titanium power may be at least one selected.
[0017] 前記榭脂組成物にお!、て、ハロゲン系難燃剤 (B)の割合はベース榭脂 (A) 100重 量部に対して 2〜20重量部程度であってもよく、有機 ·無機酸塩 (C)の割合はベース 榭脂 (A) 100重量部に対して 3〜30重量部程度であってもよい。また、前記榭脂組 成物において、ハロゲン系難燃剤 (B) 100重量部に対して、有機'無機酸塩 (C)の 割合が 20〜500重量部程度であり、電気特性向上剤 (D)の割合が 10〜150重量 部程度であってもよい。  [0017] 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). Further, in the resin composition, 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.
[0018] 前記榭脂組成物は、さらに、アミノトリアジン化合物の塩 (例えば、メラミンシァヌレー トなど）、（含水)ケィ酸金属塩 (例えば、タルク、カオリンなど）、（含水)ホウ酸金属塩（ 例えば、（含水）ホウ酸亜鉛、（含水）ホウ酸カルシウムなど）、（含水)スズ酸金属塩（ 例えば、（含水)スズ酸亜鉛など）、金属酸化物（例えば、酸ィ匕亜鉛など）、金属硫ィ匕 物（例えば、硫ィ匕亜鉛など）、及びアルカリ土類金属化合物（例えば、炭酸カルシウム 、リン酸水素カルシウムなど)力も選択された少なくとも一種の電気特性向上助剤 (E) を含んでいてもよい。 [0018] 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.
[0019] また、前記榭脂組成物は、芳香族化合物、リン含有化合物及びアンチモン含有ィ匕 合物から選択された少なくとも一種の難燃助剤 (F)を含んで、、てもよ ヽ。前記芳香族 化合物 (又は難燃助剤 (F) )は、フエノール系榭脂、ポリフエ-レンォキシド系榭脂、 芳香族エポキシ榭脂、フエノキシ榭脂、ポリフエ-レンスルフイド系榭脂、ポリカーボネ 一ト系榭脂、ポリアリレート系榭脂、芳香族ポリアミド系榭脂、芳香族ポリエステル系榭 脂 (液晶性であってもよ!、系芳香族ポリエステル榭脂)及び芳香族ポリエステルアミド 系榭脂 (液晶性であってもよ!、芳香族ポリエステルアミド系榭脂)から選択された少な くとも 1種であってもよい。また、前記リン含有化合物 (又は難燃助剤 (F) )は、（縮合） リン酸エステル、（縮合)リン酸エステルアミド、（架橋)ァリールォキシホスファゼン、 ( 亜)リン酸金属塩、次亜リン酸金属塩、有機（亜)ホスホン酸エステル、有機（亜)ホス ホン酸金属塩、及び有機（亜)ホスホン酸アミノトリアジン塩カゝら選択された少なくとも 一種であってもよい。特に、前記リン含有ィ匕合物 (又は難燃助剤 (F) )は、アルキル（ 亜)ホスホン酸金属塩、（亜）リン酸金属塩及び次亜リン酸金属塩から選択された少な くとも一種であってもよい。  [0019] Further, 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. Oil, polyarylate resin, aromatic polyamide resin, aromatic polyester resin (may be liquid crystalline !, aromatic polyester resin) and aromatic polyesteramide resin (liquid crystalline There may be at least one selected from aromatic polyester amides). 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. In particular, 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.
[0020] さらに、前記榭脂組成物は、充填剤、耐熱安定剤、加工安定剤及び反応性安定剤 から選択された少なくとも一種の添加剤を含んで 、てもよ 、。  [0020] Further, the resin composition may contain at least one additive selected from a filler, a heat stabilizer, a processing stabilizer, and a reactive stabilizer.
[0021] 本発明の榭脂組成物は、難燃性及び電気特性に優れており、例えば、 [A] (i)試 験片の厚み 0. 8mmで測定したとき、 UL94燃焼試験に準拠した難燃性が V—1以 上 (特に、 V—0以上)であり、かつ (ii) IEC (国際電気標準会議、以下同じ） 112に準 拠した比較トラッキング指数が 350V以上 (特に 400V以上)であってもよい。また、本 発明の榭脂組成物は、 [Β](0試験片の厚み 1. 6mmで測定したとき、 UL94燃焼性 試験に準拠した難燃性が V— 2以上 (好ましくは V— 1以上、特に V— 0以上)であり、 かつ (ii)IEC 112に準拠した比較トラッキング指数が 500V以上 (好ましくは 650V以 上）であってもよい。  [0021] The resin composition of the present invention is excellent in flame retardancy and electrical properties. For example, [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. In addition, the resin composition of the present invention has a [Β] (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 And (ii) the comparative tracking index according to IEC 112 may be 500 V or more (preferably 650 V or more).
[0022] 本発明には、前記榭脂組成物で形成された成形体も含まれる。このような成形体は 、電気'電子部品、オフィスオートメーション機器部品、家電機器部品、自動車部品、 又は機械機構部品であってもよ 、。 発明の効果 [0022] The present invention also includes a molded body formed of the above-mentioned rosin composition. Such 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 invention's effect
[0023] 本発明の難燃性榭脂組成物は、ベース榭脂と、ハロゲン系難燃剤と、特定の有機' 無機酸塩と、電気特性を向上するための特性の電気特性向上剤とを組み合わせる ので、難燃性に優れるとともに電気特性を向上できる。また、本発明では、前記組み 合わせにより、耐トラッキング性などの電気特性を高!ヽレベルで確実に改善できる。 発明の詳細な説明  [0023] 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. Detailed Description of the Invention
[0024] 本発明の難燃性榭脂組成物は、ベース榭脂と、ハロゲン系難燃剤と、特定の有機' 無機酸塩と、特定の電気特性向上剤とで少なくとも構成されている。このような榭脂 組成物では、難燃性だけでなぐ電気特性 (比較トラッキング指数などで表される耐ト ラッキング性など)も改善されて 、る。  [0024] 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. Such a resin composition also has improved electrical properties (such as tracking resistance represented by a comparative tracking index) as well as flame retardancy.
[0025] [ベース榭脂 (A) ]  [0025] [Base oil (A)]
ベース榭脂 (A)としては、特に制限されず、種々の榭脂、例えば、熱可塑性榭脂 [ 例えば、ポリエステル系榭脂、ポリアミド系榭脂、ポリカーボネート系榭脂、ポリフエ二 レンォキシド系榭脂、ポリフエ二レンスルフイド系榭脂、ポリアセタール榭脂、ケトン榭 脂、ポリスルホン系榭脂（例えば、ポリスルホンなど）、ポリエーテルケトン系榭脂（ポリ エーテルケトンなど）、ポリエーテルイミド、ポリウレタン系榭脂、ポリイミド、ポリオキシ ベンジレン、アクリル系榭脂、スチレン系榭脂、ビュル系榭脂、熱可塑性エラストマ一 など]、熱硬化性榭脂 (フ ノール榭脂、アミノ榭脂、熱硬化性ポリエステル系榭脂、 エポキシ榭脂、シリコーン系榭脂、ビュルエステル系榭脂、ポリウレタン系榭脂など） などが挙げられる。以下、代表的なベース榭脂について詳述する。  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.). Hereinafter, typical base resin is described in detail.
[0026] (ポリエステル系榭脂）  [0026] (Polyester resin)
ポリエステル系榭脂は、ジカルボン酸成分とジオール成分との重縮合、ォキシカル ボン酸又はラタトンの重縮合、またはこれらの成分の重縮合などにより得られるホモポ リエステル又はコポリエステルである。好ましいポリエステル系榭脂には、通常、飽和 ポリエステル系榭脂、特に芳香族飽和ポリエステル系榭脂が含まれる。  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.
[0027] ジカルボン酸成分としては、例えば、脂肪族ジカルボン酸 (コハク酸、ダルタル酸、 アジピン酸、へキサデカンジカルボン酸、ダイマー酸などの C ジカルボン酸、好ま  [0027] Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids (C dicarboxylic acids such as succinic acid, dartaric acid, adipic acid, hexadecanedicarboxylic acid, dimer acid, and the like.
4-40  4-40
しくはじ ジカルボン酸など）、脂環式ジカルボン酸 (へキサヒドロフタル酸、へキサ ヒドロテレフタル酸、ハイミック酸などの c ジカルボン酸など）、芳香族ジカルボン Such as dicarboxylic acids), alicyclic dicarboxylic acids (hexahydrophthalic acid, hexa C) dicarboxylic acids such as hydroterephthalic acid and hymic acid), aromatic dicarboxylic acids
8-12  8-12
酸 [C アレーンジカルボン酸（フタル酸、イソフタル酸、テレフタル酸、 2, 6 ナフ Acid [C arene dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, 2, 6 naphthyl
8-16 8-16
タレンジ力ノレボン酸など）、ビスフエニノレジ力ノレボン酸（4, 4' ービフエニノレジカノレボ ン酸、ジフエ-ルエーテル—4, 4' ージカルボン酸、ジフエ-ルアルカンジカルボン 酸（4, 4^ —ジフエ-ルメタンジカルボン酸など）、 4, 4' —ジフエ二ルケトンジカル ボン酸など）]、これらの誘導体 (低級アルキルエステル、酸無水物などのエステル形 成可能な誘導体など)などが挙げられる。ジカルボン酸成分は、単独で又は二種以 上組み合わせてもよい。さらに、必要に応じて、トリメリット酸、ピロメリット酸などの多価 カルボン酸を併用してもよ!、。  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. Furthermore, if necessary, polycarboxylic acids such as trimellitic acid and pyromellitic acid may be used in combination!
[0028] 好まし!/、ジカルボン酸成分には、テレフタル酸、ナフタレンジカルボン酸などの芳香 族ジカルボン酸が含まれる。  [0028] Preferably, the dicarboxylic acid component includes aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid.
[0029] ジオール成分には、例えば、脂肪族ジオール [例えば、アルキレングリコール (例え ば、エチレングリコール、トリメチレングリコール、プロピレングリコール、 1, 4 ブタン ジオール、へキサンジオールなどの C アルキレングリコール、好ましくは C ァ  [0029] 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
2—12 2—10 ルキレングリコール）、ポリアルキレングリコール（複数のォキシ C アルキレン単位を  2-12 2-10 alkylene glycol), polyalkylene glycol (multiple oxy C alkylene units
2-4  2-4
有するグリコール、例えば、ジエチレングリコール、ジプロピレングリコール、ジテトラメ チレングリコール、トリエチレングリコール、ポリテトラメチレングリコールなど）など]、脂 環族ジオール [例えば、 1, 4ーシクロへキサンジオール、シクロアルカンジアルカノー ル（1, 4 シクロへキサンジメタノールなどの C シクロアルカンジ C アル力ノール  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
5-6 1-2  5-6 1-2
など）、水素化ビスフエノール Aなど]などが挙げられる。また、ハイドロキノン、レゾル シノール、ビフエノール、ビスフエノール類又はその C アルキレンォキシド付加体 [  Etc.), hydrogenated bisphenol A, etc.]. Hydroquinone, resorcinol, biphenol, bisphenols or their C alkylene oxide adducts [
2-3  2-3
2, 2 ビス（4 ヒドロキシフエ-ル）プロパン、 2, 2 ビス一（4— (2 ヒドロキシエト キシ)フエ-ル)プロパン又はこれらの臭素化誘導体など]、キシリレンダリコールなど の芳香族ジオールを併用してもよ ヽ。ジオール成分は単独で又は二種以上組み合 わせて使用してもよい。さらに、必要に応じて、グリセリン、トリメチロールプロパン、トリ メチロールェタン、ペンタエリスリトールなどのポリオールを併用してもよい。  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. Furthermore, if necessary, polyols such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol may be used in combination.
[0030] 好ましいジオール成分には、 C アルキレングリコール（エチレングリコール、トリメ [0030] Preferred diol components include C alkylene glycol (ethylene glycol, trimer
2-6  2-6
チレングリコール、プロピレングリコール、 1, 4 ブタンジオールなどの直鎖状アルキ レンダリコール）、繰返し数が 2〜4程度のォキシアルキレン単位を有するポリアルキ レングリコール [ジエチレングリコールなどのポリ（ォキシ— c アルキレン）単位を含 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]
2-4  2-4
むグリコール]、 1, 4ーシクロへキサンジメタノールなどが含まれる。  Glycol], 1,4-cyclohexanedimethanol and the like.
[0031] ォキシカルボン酸には、例えば、ォキシ安息香酸、ォキシナフトェ酸、 4 カルボキ シ— 4' —ヒドロキシビフエ-ル、ヒドロキシフエ-ル酢酸、グリコール酸、 D— , L 又 は DZL 乳酸、ォキシカプロン酸などのォキシカルボン酸又はこれらの誘導体が含 まれる。 [0031] Examples of the oxycarboxylic acid 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.
[0032] ラタトンには、プロピオラタトン、ブチロラタトン、バレロラタトン、力プロラタトン (例えば 、 ε—力プロラタトンなど）などの C ラタトンなどが含まれる。 [0032] The ratataton includes C ratatones such as propiolatataton, butyrolatathon, valerolatataton, and force prolatataton (eg, ε -force prolatataton).
3-12  3-12
[0033] 好ましいポリエステル系榭脂には、シクロアルカンジアルキレンァリレート単位（1, 4 —シクロへキサンジメチレンテレフタレート単位など）及びアルキレンァリレート単位（ アルキレンテレフタレート及び Ζ又はアルキレンナフタレート単位、例えば、 C アル  [0033] Preferred polyester-based resins include cycloalkanedialkylene arylate units (such as 1,4-cyclohexanedimethylene terephthalate units) and alkylene arylate units (such as alkylene terephthalate and Ζ or alkylene naphthalate units such as C Al
2-4 キレンテレフタレート単位、 c アルキレンナフタレート単位など）から選択された少  2-4 xylene terephthalate unit, c alkylene naphthalate unit, etc.)
2-4  2-4
なくとも一種の単位を有する [例えば、主成分 (例えば、 50〜： LOO重量％、好ましくは 75〜： LOO重量％程度）として有する]ホモポリエステル又はコポリエステル [例えば、 ポリ 1, 4ーシクロへキサンジメチレンテレフタレート、ポリアルキレンテレフタレート（例 えば、ポリエチレンテレフタレート（PET)、ポリプロピレンテレフタレート（ΡΡΤ)、ポリ ブチレンテレフタレート（PBT)などのポリ C アルキレンテレフタレート）、ポリアルキ  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 (ΡΡΤ), polybutylene terephthalate (PBT)), polyalkyl
2-4  2-4
レンナフタレート（例えば、ポリエチレンナフタレート、ポリプロピレンナフタレート、ポリ ブチレンナフタレートなどのポリ c アルキレンナフタレート）などのホモポリエステル  Homopolyesters such as lennaphthalates (eg poly c alkylene naphthalates such as polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate)
2-4  2-4
；シクロアルカンジアルキレンテレフタレート、アルキレンテレフタレート及びアルキレ ンナフタレートから選択された少なくとも一種の単位を主成分 (例えば、 50重量％以 上）として含有するコポリエステル]が含まれる。特に好ましいポリエステル系榭脂には 、ブチレンテレフタレート単位を主成分として含有するポリブチレンテレフタレート系 榭脂 [例えば、ポリブチレンテレフタレート、ブチレンテレフタレート単位を主成分とす るコポリエステル（ポリブチレンテレフタレートコポリエステル：例えば、イソフタル酸変 性ポリブチレンテレフタレートなど） ]、プロピレンテレフタレート単位を主成分として含 有するポリプロピレンテレフタレート系榭脂 [例えば、ポリプロピレンテレフタレート、プ ロピレンテレフタレート単位を主成分とするコポリエステル（ポリプロピレンテレフタレー トコポリエステル) ]、及びエチレンテレフタレート単位を主成分として含有するポリエ チレンテレフタレート系榭脂 [例えば、ポリエチレンテレフタレート、エチレンテレフタレ ート単位を主成分とするコポリエステル（ポリエチレンテレフタレートコポリエステル：例 えば、 1, 4ーシクロへキサンジメタノール変性ポリエチレンテレフタレート、 4ーヒドロキ シ安息香酸変性ポリエチレンテレフタレートなど） ]が含まれる。ポリエステル系榭脂は 単独で又は二種以上組み合わせて使用できる。 A copolyester containing at least one unit selected from cycloalkanedialkylene terephthalate, alkylene terephthalate and alkylene naphthalate as a main component (for example, 50% by weight or more)]. 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 copolyesters)] and polyethylene terephthalate resins containing ethylene terephthalate units as main components [eg, polyethylene terephthalate, ethylene terephthalate units as main components (Polyethylene terephthalate copolyester: for example, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, 4-hydroxybenzoic acid-modified polyethylene terephthalate, etc.)]. Polyester-based resin can be used alone or in combination of two or more.
また、コポリエステルにお 、て、共重合可能な単量体としては、 C アルキレンダリ  In the copolyester, the copolymerizable monomer may be a C alkylene radical.
2-6  2-6
コール（エチレングリコールなどの直鎖状アルキレングリコールなど）、繰返し数が 2〜 4程度のォキシアルキレン単位を有するポリアルキレングリコール（ジエチレングリコー ル、ポリテトラメチレングリコールなどのポリ（ォキシ C アルキレン）単位を含むグリコ Cole (such as linear alkylene glycol such as ethylene glycol) and polyalkylene glycol (oxyethylene units such as diethylene glycol and polytetramethylene glycol) having an oxyalkylene unit with 2 to 4 repetitions. Including glyco
2-4  2-4
ールなど）、 C 脂肪族ジカルボン酸（ダルタル酸、アジピン酸、セバシン酸など）、 C) aliphatic dicarboxylic acids (such as dartaric acid, adipic acid, sebacic acid),
4-12  4-12
脂環族ジオール（1, 4ーシクロへキサンジメタノールなど）、芳香族ジオール [例えば 、 2, 2—ビス（4— (2—ヒドロキシエトキシ）フエ-ル）プロパンなどのビスフエノール類 (DC アルキレンォキシド付カ卩体、ハイドロキノン、レゾルシン、 3, 3，一又は 4, 3， 一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
2-3 2-3
又は 4, 4'ージヒドロキシジフエニル、 1 , 4一又は 2, 6 ジヒドロキシナフタレンなど] 、芳香族ジカルボン酸 [ (非)対称芳香族ジカルボン酸 (フタル酸、イソフタル酸、 5— スルホイソフタル酸モノナトリウム塩など）、ジフエ-ルジカルボン酸（4, 4，ージフエ- ルジカルボン酸など）、ナフタレンジカルボン酸（2, 6 ナフタレンジカルボン酸など） など]、ォキシ安息香酸（3—又は 4ーヒドロキシ安息香酸など）、ォキシナフトェ酸 (6 ーヒドロキシー2 ナフトェ酸、 6 ヒドロキシ 1 ナフトェ酸など）、 4 カルボキシ —ヒドロキシビフエ-ルなど]などが挙げられる。なお、ポリエステル系榭脂は、 溶融成形性などを損なわない限り、直鎖状のみならず分岐鎖状であってもよぐ架橋 されていてもよい。ポリエステル系榭脂は、液晶ポリエステルであってもよい。さらに、 ポリエステル系榭脂には、アミノ基含有単量体 (例えば、 3—又は 4ーァミノフエノール 、 3—又は 4—ァミノ安息香酸、テトラメチレンジァミン、へキサメチレンジァミン、ノナメ チレンジァミン、 m—キシリレンジァミンなど)で変性された (液晶）ポリエステルアミド 系榭脂も含まれる。 [0035] ポリエステル系榭脂は、慣用の方法、例えば、エステル交換、直接エステル化法な どにより製造できる。ポリエステル系榭脂の固有粘度は、例えば、 0. 4〜2. 0、好まし くは 0. 5〜1. 8、さらに好ましくは 0. 6〜1. 5程度であってもよい。 Or 4,4'-dihydroxydiphenyl, 1,4 mono- or 2,6 dihydroxynaphthalene], 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. In addition, 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. [0035] 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.
[0036] (ポリアミド系榭脂）  [0036] (Polyamide resin)
ポリアミドには、ジァミンとジカルボン酸とから誘導されるポリアミド;アミノカルボン酸 、必要に応じてジァミン及び/又はジカルボン酸を併用して得られるポリアミド;ラクタ ム、必要に応じてジァミン及び Z又はジカルボン酸との併用により誘導されたポリアミ ドが含まれる。ポリアミドには、コポリアミドも含まれる。ジァミン、ジカルボン酸、ァミノ カルボン酸、ラタタムは、それぞれ単独で又は 2種以上組み合わせて使用できる。  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.
[0037] ジァミンとしては、例えば、テトラメチレンジァミン、へキサメチレンジァミンなどの C [0037] Examples of diamine include C, such as tetramethylene diamine and hexamethylene diamine.
3- 脂肪族ジァミン、ビス（4—アミノシクロへキシル)メタン、ビス（4—アミノー 3—メチル 3- Aliphatic diamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methyl)
10 Ten
シクロへキシル)メタンなどの脂環族ジァミン (アルキル基などの置換基を有して 、て もよ 、ビス（ァミノ C シクロアルキル） C アルカンなど）が挙げられる。必要であれ  And cycloaliphatic) diamines such as alicyclic diamines (having substituents such as alkyl groups, and bis (amino C cycloalkyl) C alkanes). If necessary
5-8 1-4  5-8 1-4
ば、フエ二レンジァミン、メタキシリレンジァミンなどの芳香族ジァミンを併用してもよい For example, aromatic diamines such as phenylenediamine and metaxylylenediamine may be used in combination.
。ジカルボン酸としては、例えば、アジピン酸、スベリン酸、セバシン酸、ドデカン二酸 などの C 脂肪族ジカルボン酸 (C アルカンジカルボン酸など）；二量体ィヒ脂肪. Examples of dicarboxylic acids include C aliphatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, and dodecanedioic acid (C alkane dicarboxylic acid, etc.);
4-20 6-16 4-20 6-16
酸（ダイマー酸）；シクロへキサン— 1, 4ージカルボン酸ゃシクロへキサン— 1, 3—ジ カルボン酸などの脂環式ジカルボン酸；フタル酸、無水フタル酸、イソフタル酸ゃテレ フタル酸、ナフタレンカルボン酸などの芳香族ジカルボン酸などが挙げられる。ァミノ カルボン酸としては、例えば、ァミノヘプタン酸、アミノノナン酸、アミノウンデカン酸な どの C アミノカルボン酸が例示される。ラタタムとしては、例えば、力プロラタタム、 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. Examples of the aminocarboxylic acid include C-aminocarboxylic acids such as aminoaminobutanoic acid, aminononanoic acid, and aminoundecanoic acid. As ratata, for example, force prolatata,
4-20 4-20
ドデカラクタムなどの C ラタタムが挙げられる。  C ratatam such as dodecaractam.
4-20  4-20
[0038] ポリアミド系榭脂としては、ポリアミド 46、ポリアミド 6、ポリアミド 66、ポリアミド 610、ポ リアミド 612、ポリアミド 11、ポリアミド 12などの脂肪族ポリアミド;ビス (アミノシクロへキ シル） C アルカン類などの脂環族ジァミンと C アルカンジカルボン酸などの脂 [0038] 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
1-3 8-14 1-3 8-14
肪族ジカルボン酸とから得られる脂環族ポリアミド；芳香族ジカルボン酸 (例えば、テ レフタル酸及び Z又はイソフタル酸）と脂肪族ジァミン (例えば、へキサメチレンジアミ ン、ノナメチレンジァミンなど）とから得られるポリアミド;芳香族及び脂肪族ジカルボン 酸 (例えば、テレフタル酸とアジピン酸）と脂肪族ジァミン (例えば、へキサメチレンジ ァミン）とから得られるポリアミドなどが挙げられる。ポリアミド系榭脂は、単独で又は 2 種以上組み合わせて使用できる。 Alicyclic polyamides obtained from aliphatic dicarboxylic acids; aromatic dicarboxylic acids (eg, terephthalic acid and Z or isophthalic acid) and 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.
[0039] これらのポリアミド系榭脂のうち、非芳香族又は脂肪族ポリアミド (ポリアミド 46、ポリ アミド、 6、ポジアミド、 66、ポジアミド、 610、ポジアミド、 612、ポジアミド、 11、ポジアミド、 12など） 、半芳香族ポリアミド (ポリアミド MXD6、ポリアミド 9Tなど）、半芳香族共重合ポリアミ ド、（ポリアミド、 6T/6、ポリアミド、 6Τ/66、ポリアミド、 6Τ/11、ポリアミド、 6Τ/12、ポリア ^ 6l/6,ポリアミド、 61/66、ポリアミド、 6Τ/6Ι、ポリアミド、 6T/6l/6、ポリアミド、 6Τ /6Ι/66,ポリアミド 6ΤΖΜ5Τなど）などが好まし!/、。  [0039] Of these polyamide-based resins, 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, 6Τ / 66, Polyamide, 6Τ / 11, Polyamide, 6Τ / 12, Polyamide ^ 6l / 6, Polyamide, 61/66, Polyamide, 6Τ / 6 ポ リ ア ミ ド, Polyamide, 6T / 6l / 6, Polyamide, 6Τ / 6Ι / 66, Polyamide 6ΤΖΜ5Τ, etc.) are preferred!
[0040] (ポリカーボネート系榭脂）  [0040] (Polycarbonate resin)
ポリカーボネート系榭脂には、ジヒドロキシィ匕合物 (脂環式ジオールやビスフエノー ル化合物など）と、ホスゲン又はジフエ-ルカーボネートなどの炭酸エステルとの反応 により得られる重合体が含まれる。ビスフエノールイ匕合物としては、ビス (4ーヒドロキシ フエ-ル）メタン、 2, 2 ビス（4 ヒドロキシフエ-ル）プロパンなどのビス（ヒドロキシァ リール） C アルカン； 1, 1—ビス（4 ヒドロキシフエ-ル）シクロへキサンなどのビス  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
1-10  1-10
(ヒドロキシァリール） C シクロアルカン； 4, 4' ージヒドロキシジフエニルエーテル；  (Hydroxyaryl) C cycloalkane; 4,4'-dihydroxydiphenyl ether;
4- 10  4- 10
4, 4' —ジヒドロキシジフエニルスルホン； 4, 4' —ジヒドロキシジフエニルスルフイド； 4, 4' ージヒドロキシジフエ-ルケトンなどが挙げられる。  4,4'-dihydroxydiphenyl sulfone; 4,4'-dihydroxydiphenylsulfide; 4,4'-dihydroxydiphenyl ketone.
[0041] 好ましいポリカーボネート系榭脂には、ビスフエノール Α型ポリカーボネートが含ま れる。 [0041] Preferred polycarbonate-based resin includes bisphenol-type polycarbonate.
[0042] (ポリフエ-レンォキシド系榭脂）  [0042] (Polyphenol-Renoxide resin)
ポリフエ-レンォキシド系榭脂（ポリフエ-レンエーテル系榭脂）には、単独重合体 及び共重合体が含まれる。単独重合体としては、ポリ（2, 6 ジメチルー 1, 4 フエ 二レン）ォキシド、ポリ（2, 5 ジメチルー 1, 4 フエ-レン）ォキシド、ポリ（2, 5 ジ ェチル 1, 4 フエ-レン）ォキシド等のポリ（モ入ジ又はトリ C アルキル—フエ- The polyphenylene oxide-based resin (polyphenylene ether-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)
1-6 1-6
レン）ォキシド、ポリ（モノ又はジ C ァリール フエ-レン）ォキシド、ポリ（モノ C  Len) oxide, poly (mono- or di-C allyl phenol-oxide), poly (mono-C)
6— 20 1—6 アルキル モノ c ァリール一フエ-レン）ォキシドなどが挙げられる。  6-20 1-6 alkyl mono-c-aryl-phenol-oxide) and the like.
6-20  6-20
[0043] ポリフエ-レンォキシドの共重合体としては、前記単独重合体のモノマーユニットを 2種以上有する共重合体 (例えば、 2, 6 ジメチルー 1, 4 フエ-レンォキシド単位 と、 2, 3, 6 トリメチル 1, 4 フエ-レンォキシド単位とを有するランダム共重合体 など）、ベンゼンホルムアルデヒド榭脂（フエノール榭脂など）やアルキルベンゼンホル ムアルデヒド榭脂に、タレゾールなどのアルキルフヱノールを反応させて得られるアル キルフエノール変性ベンゼンホルムアルデヒド榭脂ブロックと、主体構造としてのポリ フエ-レンォキシドブロックとで構成された変性ポリフエ-レンォキシド共重合体、ポリ フエ-レンォキシド又はその共重合体にスチレン系重合体及び Z又は不飽和カルボ ン酸又は無水物（ (メタ)アクリル酸、無水マレイン酸など）がグラフトして 、る変性ダラ フト共重合体などが挙げられる。 [0043] As the 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) and alkylbenzeneformaldehyde resin, alkylphenol-modified benzeneformaldehyde resin block obtained by reacting alkylphenol such as talesol, and poly-phenoloxide block as the main structure A modified poly-phenylene oxide copolymer composed of styrene-based polymer and Z-unsaturated carboxylic acid or anhydride ((meth) acrylic acid, maleic anhydride, etc.) Examples of the modified modified graft copolymer include grafting.
[0044] (ポリフエ-レンスルフイド系榭脂） [0044] (Polyphenol-sulfuric resin)
ポリフエ-レンスルフイド系榭脂（ポリフエ-レンチォエーテル系榭脂）としては、フエ 二レンスルフイド骨格 (Ar— S) [式中、 Arはフエ-レン基を示す]を有する単独重 合体及び共重合体が含まれる。フエ-レン基（一 Ar—）としては、例えば、 p―、 m— 又は o—フエ-レン基の他、置換フエ-レン基（例えば、 C アルキル基などの置換  Polyphenylene sulfide resin (polyphenol-lentioether resin) is a homopolymer and copolymer having a phenylsulfide skeleton (Ar— S) [wherein Ar represents a phenol group] Is included. Examples of the phenylene group (one Ar—) include p-, m-, or o-phenylene groups, and substituted phenylene groups (for example, C alkyl groups).
1-6  1-6
基を有するアルキルフヱ-レン基や、フヱ-ル基などの置換基を有するァリールフエ 二レン基）、 Ar— A1— Ar— [式中、 Arはフエ-レン基、 A1は直接結合、 0、 CO、 又は SOを示す]などであってもよい。ポリフエ-レンスルフイド系榭脂は、このようなAlkylaryl group having a group or arylene diphenylene group having a substituent such as a phenyl group), Ar— A 1 — Ar— [wherein Ar is a phenylene group, A 1 is a direct bond, It may be 0, CO, or SO]. Polyphenol-sulfide-based fats are
2 2
フエ-レン基で構成されるフヱ-レンスルフイド単位のうち、同一の繰返し単位を用い たホモポリマーであってもよぐ異種の繰返し単位を含むコポリマーであってもよい。  Of the 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.
[0045] ホモポリマーとしては、 p—フエ-レンスルフイド基を繰返し単位とする実質上線状の ポリマーが好ましい。コポリマーは、前記フエ-レンスルフイド基の中で相異なる 2種 以上を組み合わせて使用できる。コポリマーとしては、 p フエ-レンスルフイド基を主 な繰返し単位とし、 m—フエ-レンスルフイド基を含む組み合わせが好ましぐ p フエ 二レンスルフイド基を 60モル％ (好ましくは 70モル0 /0)以上含む実質上線状のコポリ マーであってもよい。 [0045] 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. Copolymers, p Hue - the Rensurufuido group as the main repeating unit, m- Hue - combination comprising a Rensurufuido group preferably tool p-phenylene Rensurufuido based on 60 mole% substantially (preferably 70 mol 0/0) containing more It may be an overlying copolymer.
[0046] ポリフエ-レンスルフイド系榭脂は、低分子量の線状ポリマーを酸化架橋又は熱架 橋したポリマーであってもよぐ 2官能性モノマーを主体とするモノマー力 縮重合に よって得られる実質的に線状構造のポリマーであってもよい。また、ポリフエ-レンス ルフイド榭脂には、 3個以上の官能基を有するモノマーを組み合わせて重合した分岐 又は架橋ポリフエ-レンスルフイド榭脂や、この榭脂を前記の線状ポリマーにブレンド した榭脂組成物も含まれる。 [0046] 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.
[0047] ポリフエ-レンスルフイド系榭脂としては、ポリフエ-レンスルフイドやポリビフエ-レン スルフイド（PBPS)の他、ポリフエ-レンスルフイドケトン（PPSK)、ポリビフエ-レンス ルフイドスルホン（PBSS)等も使用できる。  [0047] As polyphenylene sulfide-based resin, polyphenylene sulfide, polybiphenylene sulfide (PBPS), polyphenylene sulfide ketone (PPSK), polybiphenyl sulfide sulfone (PBSS) and the like can be used.
[0048] (スチレン系榭脂）  [0048] (Styrene resin)
スチレン系榭脂としては、スチレン系単量体 (スチレン、ビュルトルエンなど）の単独 又は共重合体；スチレン系単量体とビニル系単量体 [ (メタ)アクリル系単量体 (例え ば、（メタ）アクリロニトリル、（メタ)アクリル酸エステル、（メタ)アクリル酸など）、無水マレ イン酸などの α , β モノォレフィン性不飽和カルボン酸又は酸無水物又はエステ ルなど]との共重合体;スチレン系グラフト共重合体、スチレン系ブロック共重合体な どが挙げられる。  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.), α, β 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.
[0049] 好まし!/、スチレン系榭脂としては、ポリスチレン（GPPS)、スチレン一メタクリル酸メ チル共重合体、スチレン (メタ)アクリル酸共重合体、スチレン アクリロニトリル共重 合体 (AS榭脂）、ゴム成分 (ポリブタジエン、アクリルゴム、スチレン—ブタジエン共重 合体ゴム、 EPDM、 EVAなど）にスチレン系単量体と必要により共重合性単量体 (ァ クリロ-トリル、メタクリル酸メチルなど）が重合したグラフト共重合体 [耐衝撃性ポリス チレン（HIPS)、 ABS榭脂、 MBS榭脂など]、ポリスチレンブロックとジェン又はォレ フィンブロックとで構成された共重合体 [例えば、スチレン ブタジエン スチレン（S [0049] Preferable! / As 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 ( S
BS)ブロック共重合体、スチレン イソプレンブロック共重合体、スチレン イソプレン スチレン（SIS)ブロック共重合体、水素添加スチレン ブタジエン スチレン（SE BS)ブロック共重合体、水素添加スチレン イソプレン スチレン（SEPS)ブロック共 重合体、エポキシィ匕 SBS、エポキシ化 SISなど]などが挙げられる。 BS) block copolymer, styrene isoprene block copolymer, styrene isoprene styrene (SIS) block copolymer, hydrogenated styrene butadiene styrene (SE BS) block copolymer, hydrogenated styrene isoprene styrene (SEPS) block copolymer Union, epoxy SBS, epoxidized SIS, etc.].
[0050] (ピ ル系榭脂） [0050] (pill-based fat)
ビュル系榭脂としては、ビュル系単量体（例えば、酢酸ビュルなどのビュルエステ ル;塩素含有ビュル単量体 (例えば、塩ィ匕ビュルなど）；ビニルケトン類;ビニルエーテ ル類； N ビ-ルカルバゾールなどのビュルアミン類など）の単独又は共重合体、あ るいは他の共重合可能なモノマーとの共重合体などが含まれる。前記ビニル系榭脂 の誘導体（例えば、ポリビュルアルコール、ポリビュルホルマール、ポリビュルブチラ ールなどのポリビュルァセタール、エチレン 酢酸ビュル共重合体など）も使用でき る。 As for the bull-based resin, 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. Derivatives of the vinyl-based rosin (for example, polybulacetal such as polybulal alcohol, polybul formal, polybulbutyral, and ethylene acetate bur copolymer) can also be used.
[0051] これらの榭脂又は高分子化合物は、単独で又は二種以上組合わせて使用してもよ い。  [0051] These rosins or polymer compounds may be used alone or in combination of two or more.
[0052] 好ま 、ベース榭脂としては、液晶ポリエステルであってもよ!/ヽポリエステル系榭脂 、スチレン系榭脂、ポリアミド系榭脂、ポリフエ-レンォキシド系榭脂などの熱可塑性 榭脂 (特にポリアミド系榭脂及びポリエステル系榭脂から選択された少なくとも一種の 熱可塑性榭脂）が挙げられ、さらに好ましくはポリエステル系榭脂 (PBT系榭脂、 PP T系榭脂、 PET系榭脂など)などが挙げられる。  [0052] Preferably, 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.
[0053] ベース榭脂の数平均分子量は、特に制限されず、榭脂の種類や用途に応じて適 宜選択され、例えば、 5 103〜200 104、好ましくは1 104〜150 104、さらに 好ましくは 1 X 104〜： LOO X 104程度の範囲力も選択できる。また、ベース榭脂がポリ エステル系榭脂の場合、数平均分子量は、例えば、 5 X 103〜： LOO X 104、好ましく は1 104〜70 104、さらに好ましくは 1. 2 X 104〜30 X 104程度であってもよい。 [0053] 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. When 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 .
[0054] [ハロゲン系難燃剤 (B) ]  [0054] [Halogen flame retardant (B)]
ノ、ロゲン系難燃剤 (B)としては、有機ハロゲンィ匕物が使用できる。有機ハロゲンィ匕 物は、通常、塩素、臭素及びヨウ素原子力 選択された少なくとも一種を含有してい る。  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.
[0055] ハロゲン系難燃剤としては、例えば、ハロゲン含有アクリル系榭脂 [ハロゲン化ポリ ベンジル (メタ）アタリレート系榭脂、例えば、ポリ（ペンタブロモベンジル (メタ）アタリレ ート）などの臭素化ポリベンジル (メタ）アタリレート、ポリ（ペンタクロロべンジル (メタ）ァ タリレート）などのハロゲンィ匕べンジル (メタ）アタリレートの単独又は共重合体など]、 ノ、ロゲン含有スチレン系榭脂 [例えば、スチレン系榭脂 (スチレンの単独又は共重合 体)をハロゲンィ匕処理 (例えば、塩素、臭素、塩化臭素処理など）して得られるスチレ ン系榭脂のハロゲンィ匕物（臭素化ポリスチレン、塩素化ポリスチレンなど）、ハロゲン ィ匕スチレン系単量体の単独又は共重合体など]、ハロゲン含有ポリカーボネート系榭 脂（臭素化ポリカーボネート、塩素化ポリカーボネートなどハロゲンィ匕ポリカーボネー トなど)、ハロゲン含有エポキシィ匕合物 (臭素化エポキシ榭脂、塩素化エポキシ榭脂 などのハロゲンィ匕エポキシ榭脂；臭素化フエノキシ榭脂などのハロゲンィ匕フエノキシ榭 脂など）、ハロゲンィ匕ポリアリールエーテルィ匕合物 [例えば、ォクタ乃至デカブ口モジ フエ-ルエーテル、ォクタ乃至デカクロロジフエ-ルエーテルなどのビス（ハロゲンィ匕 ァリール)エーテル (例えば、ビス (ノヽロゲンィ匕フエ-ル)エーテルなど）；臭素化ポリフ ェ-レンエーテルなどのハロゲン含有ポリフエ-レンォキシド系榭脂など]、ハロゲン 化芳香族イミドィ匕合物 [例えば、アルキレンビス臭素化フタルイミド (例えば、エチレン ビス臭素化フタルイミドなどの c アルキレンビス臭素化フタルイミドなど）などの臭素 [0055] Examples of the halogen-based flame retardant 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), halogen-containing epoxy compound (halogenated epoxy resin such as brominated epoxy resin and chlorinated epoxy resin; brominated phenoxy resin, etc. 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)
2-6  2-6
化芳香族イミドィ匕合物 (例えば、ビスイミド化合物など)など]、ハロゲンィ匕ビスァリール 化合物 [例えば、臭素化ジフエ-ルなどのビス (ハロゲンィ匕 C ァリール）；臭素化ジ Aromatic imide compounds (such as bisimide compounds)], halogenated biaryl compounds [eg, bis (halogenated C aryl) such as brominated diphenyls;
6-10  6-10
フエ-ルメタンなどのビス（ノヽロゲン化 C ァリール） C アルカン；臭素化ビスフエノ Bis, such as phenol methane (Norogenated C aryl) C Alkane; Brominated bisphenol
6-10 1-4  6-10 1-4
ール Aなどのハロゲン化ビスフエノール類又はその誘導体（ノヽロゲン化ビスフエノール 類のエチレンォキシド付加体を重合した臭素化ポリエステルなど)など]、ハロゲンィ匕 脂環族炭化水素 (架橋環式飽和又は不飽和ハロゲン化脂環族炭化水素、例えば、ド デカクロロペンタシクロォクタデカー 7, 15—ジェンなどのハロゲン化ポリシクロアル力 ジェンなど）、ハロゲン化トリ（ァリールォキシ）トリァジン化合物 [例えば、臭素化トリフ エノキシトリアジンなどの臭素化トリ（ァリールォキシ）トリアジンィ匕合物など]などが挙 げられる。ハロゲン系難燃剤は、単独で又は二種以上組み合わせて使用できる。 ハロゲン系難燃剤としては、塩素原子及び Z又は臭素原子を含有する化合物が好 ましぐ特に臭素原子を含有する有機臭素化物 [臭素含有アクリル系樹脂、臭素含有 スチレン系榭脂、臭素含有ポリカーボネート系榭脂（例えば、臭素化ビスフエノール A 型ポリカーボネート榭脂などの臭素化ビスフエノール型ポリカーボネート榭脂）、臭素 含有エポキシ化合物（例えば、臭素化ビスフエノール型エポキシ榭脂（臭素化ビスフ ヱノール A型エポキシ榭脂など)などの臭素化エポキシ榭脂；臭素化ビスフエノール 型フエノキシ榭脂（臭素化ビスフエノール A型フエノキシ榭脂など）などの臭素化フエノ キシ榭脂など）、臭素化ポリアリールエーテルィ匕合物 (オタタブロモジフエ-ルエーテ ルなどのビス (臭素化ァリール)エーテルィ匕合物など）、臭素化芳香族イミドィ匕合物、 臭素化ビスァリールイ匕合物、臭素化トリ（ァリールォキシ）トリァジン化合物など]など の臭素原子含有難燃剤]が好ましい。これらの臭素原子含有難燃剤のうち、特に、臭 素化ポリベンジル (メタ)アタリレート系榭脂、臭素化スチレン系榭脂 [例えば、臭素化 ポリスチレンなどのスチレン系榭脂の臭素化物（又はスチレン系榭脂を臭素化処理し た臭素化物）、臭素化スチレン系単量体の単独又は共重合体 (例えば、ポリ臭素化ス チレンなど)など]、臭素化ビスフエノール型ポリカーボネート榭脂、臭素化ビスフエノ ール型エポキシ榭脂、臭素化ビスフエノール型フエノキシ榭脂およびアルキレンビス 臭素化フタルイミド（例えば、エチレンビス臭素化フタルイミドなどの C アルキレンビ 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. As 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. Among these 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
2-6  2-6
ス臭素化フタルイミドなど）、力も選択された少なくとも一種などが好ましい。  Subbrominated phthalimide and the like) and at least one kind of selected force are preferable.
[0057] ハロゲン系難燃剤の割合は、ベース榭脂 100重量部に対して、例えば、 1〜30重 量部、好ましくは 2〜25重量部（例えば、 2〜20重量部）、さらに好ましくは 3〜20重 量部（例えば、 5〜18重量部)程度である。 [0057] 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).
[0058] [有機'無機酸塩 (C) ] [0058] [Organic 'inorganic acid salt (C)]
有機 ·無機酸塩 (C)は、有機ホスフィン酸塩 (C1)および塩基性窒素含有化合物の ォキソ酸塩 (C2) (ォキソ酸と塩基性窒素含有化合物との塩)から選択された少なくと も 1種で構成されている。  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.
[0059] (有機ホスフィン酸塩 (C1) ) [0059] (Organic phosphinate (C1))
有機ホスフィン酸塩 (C1)としては、例えば、ホスフィン酸に有機基 (置換基を有して V、てもよ 、炭化水素基など）が置換した有機基置換ホスフィン酸、多価ホスフィン酸（ 多価有機基で複数のホスフィン酸が連結された多価ホスフィン酸など)などの有機ホ スフイン酸の塩 [金属、ホウ素、アンモ-ゥム及び塩基性窒素含有ィ匕合物力 選択さ れた少なくとも一種の塩形成成分との塩 (金属塩、ホウ素塩 (ボリルイ匕合物など）、ァ ンモ -ゥム塩、アミノ基含有窒素含有ィ匕合物との塩など)など]などが使用できる。な お、有機ホスフィン酸塩は、ハロゲン系難燃剤を用いても、榭脂の電気特性を改善す ることができる。そのため、有機ホスフィン酸塩は電気特性向上剤として機能するよう である。有機ホスフィン酸塩において、有機ホスフィン酸は、置換基 {例えば、ヒドロキ シル基、不飽和基 [例えば、カルボキシル基、ァシル基、アルコキシカルボ-ル基 (メ トキシカルボニル基など)などの炭素 酸素不飽和結合含有基など]、炭化水素基（ 例えば、メチル基などのアルキル基など）、アルコキシ基 (例えば、メトキシ基など）な ど }を有していてもよい。有機ホスフィン酸は、これらの置換基を単独で又は 2種以上 組み合わせて有して 、てもよ！/、。 Examples of the organic phosphinic acid salt (C1) 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. In addition, 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. In 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. /.
有機ホスフィン酸塩 (C1)において、代表的な有機ホスフィン酸としては、例えば、 置換基を有して 、てもよ 、モノ又はジアルキルホスフィン酸 [ジアルキルホスフィン酸 類（ジ C アルキルホスフィン酸など）、例えば、ジメチルホスフィン酸、メチルェチル In the 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
1 - 10 1-10
ホスフィン酸、ジェチルホスフィン酸、ェチルブチルホスフィン酸（ェチル n—ブチルホ スフイン酸、ェチルイソブチルホスフィン酸、ェチル t ブチルホスフィン酸など）、ジプ 口ピルホスフィン酸（ジ n—プロピルホスフィン酸、ジイソプロピルホスフィン酸など）、ジ ブチルホスフィン酸（ジ n ブチルホスフィン酸、ジイソブチルホスフィン酸、ジ tーブチ ルホスフィン酸など）、ジォクチルホスフィン酸などのジアルキルホスフィン酸；（ヒドロ キシメチル）メチルホスフィン酸、（ヒドロキシェチル）メチルホスフィン酸、ビス（ヒドロキ シメチル）ホスフィン酸、ビス（ヒドロキシェチル）ホスフィン酸などのヒドロキシル基含有 ジアルキルホスフィン酸；（2—カルボキシェチル）メチルホスフィン酸などのカルボキ シル基含有ジアルキルホスフィン酸；（メトキシメチル)メチルホスフィン酸、ビス（メトキ シメチル）ホスフィン酸などのアルコキシ基含有ジアルキルホスフィン酸；（2—カルボ キシェチル）メチルホスフィン酸、（2—カルボキシプロピル）メチルホスフィン酸、ビス（ 2—カルボキシェチル）ホスフィン酸、ビス（2—カルボキシプロピル）ホスフィン酸など のカルボキシ基含有ジアルキルホスフィン酸；（2—メトキシカルボ-ルェチル）メチル ホスフィン酸、 [2— ( j8—ヒドロキシェチルカルボ-ル）ェチル]メチルホスフィン酸、（ 2—メトキシカルボ-ルプロピル）メチルホスフィン酸、ビス（2—メトキシカルボ-ルェ チル）ホスフィン酸、ビス（2—メトキシカルボ-ルプロピル）ホスフィン酸などのアルコ キシカルボ-ル基含有ジアルキルホスフィン酸など]、置換基を有して!/、てもよ 、モノ 又はジシクロアルキルホスフィン酸 [例えば、モノシクロアルキルホスフィン酸（例えば 、シクロへキシルメチルホスフィン酸などのシクロアルキルアルキルホスフィン酸）、ジ シクロアルキルホスフィン酸（例えば、ジシクロへキシルホスフィン酸など）などのモノ 又はジシクロアルキルホスフィン酸（モノ又はジ C シクロアルキルホスフィン酸など Phosphinic acid, Jetylphosphinic acid, Ethylbutylphosphinic acid (Ethyl n-butylphosphinic acid, Ethylisobutylphosphinic acid, Ethyl-butylbutylphosphinic acid, etc.), Dipropylpyruphosphinic acid (Din-propylphosphinic acid, Diisopropylphosphine) Acid), dibutylphosphinic acid (di-n-butylphosphinic acid, diisobutylphosphinic acid, di-tert-butylphosphinic acid, etc.), dialkylphosphinic acid such as dioctylphosphinic acid; (hydroxymethyl) methylphosphinic acid, (hydroxyl Hydroxyl group-containing dialkylphosphinic acids such as til) methylphosphinic acid, bis (hydroxymethyl) phosphinic acid, bis (hydroxyethyl) phosphinic acid; and carboxyl groups such as (2-carboxyethyl) methylphosphinic acid Dialkylphosphinic acids; alkoxy group-containing dialkylphosphinic acids such as (methoxymethyl) methylphosphinic acid and bis (methoxymethyl) phosphinic acid; (2-carboxetyl) methylphosphinic acid, (2-carboxypropyl) methylphosphinic acid, bis ( Carboxy group-containing dialkylphosphinic acids such as 2-carboxyethyl) phosphinic acid and bis (2-carboxypropyl) phosphinic acid; (2-methoxycarbo-ethyl) methylphosphinic acid, [2- (j8-hydroxyethylcarbo- Alkoxycarbons such as (l) ethyl] methylphosphinic acid, (2-methoxycarbopropyl) methylphosphinic acid, bis (2-methoxycarboruyl) phosphinic acid, bis (2-methoxycarbopropyl) phosphinic acid Group-containing dialkylphosphine Phosphonic acid etc.], having a substituent! /, 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.)
5- 10  5- 10
)など]、置換基を有していてもよいモノ又はジァリールホスフィン酸 [例えば、フエ-ル ホスフィン酸などの c ァリールホスフィン酸；ジフエ-ルホスフィン酸などのジ CEtc.], mono- or diarylphosphinic acid which may have a substituent [for example, phenol C-arylphosphinic acid such as phosphinic acid; di-C such as diphenylphosphinic acid
6-10 6-10 ァリールホスフィン酸；アルキルァリールホスフィン酸（メチルフエ-ルホスフィン酸など のじ アルキル— C ァリール—ホスフィン酸など）などのモノ又はジァリールホス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.)
1-4 6-10 1-4 6-10
フィン酸]、置換基を有していてもよいアルキレンホスフィン酸 (例えば、 1—ヒドロキシ ホスホラン 1ーォキシド、 1ーヒドロキシ 3 メチルホスホスホラン 1ーォキシド、 2—力 ノレボキシ 1ーヒドロキシー 1H—ホスホラン 1一才キシドなどの C ァノレキレンホスフ Finic acid], an optionally substituted alkylene phosphinic acid (for example, 1-hydroxy phosphorane 1-oxide, 1-hydroxy 3 methyl phosphophosphorane 1-oxide, 2—force noreboxy 1-hydroxy 1H-phosphorane 1 C Anolekirenphos
3-8  3-8
イン酸など）、置換基を有していてもよいァルケ-レンホスフィン酸 (例えば、 1ーヒドロ キシ 2, 3 ジヒドロー 1H—ホスホール 1ーォキシド、 1ーヒドロキシ 2, 5 ジヒド 口一 1H ホスホール 1—ォキシド、 1—ヒドロキシ一 3—メチル 2, 5 ジヒドロ一 1H —ホスホール 1—ォキシドなどのシクロ C ァルケ-レンホスフィン酸など）、置換基 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
3-8  3-8
を有していてもよい（ビ）シクロアルキレンホスフィン酸（例えば、 1, 3 シクロブチレン ホスフィン酸、 1, 3 シクロペンチレンホスフィン酸、 1, 4 シクロオタチレンホスフィ ン酸、 1, 5 シクロオタチレンホスフィン酸などの（ビ） C シクロアルキレンホスフィ (Bi) cycloalkylenephosphinic acid (for example, 1,3 cyclobutylene phosphinic acid, 1,3 cyclopentylenephosphinic acid, 1,4 cyclooctylenephosphinic acid, 1,5 cyclooctylene (Bi) C cycloalkylene phosphines such as phosphinic acid
4-10  4-10
ン酸など）、置換基を有していてもよいビシクロアルケ-レンホスフィン酸、複数のホス フィン酸 (又は有機ホスフィン酸）が多価有機基で連結された多価ホスフィン酸 {例え ば、置換基を有していてもよいァノレカンビスホスフィン酸 [ェタン一 1, 2—ビス（ホスフ イン酸）などの C アルカンビス（ホスフィン酸）など]、置換基を有して!/、てもよ！/ヽァ 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. ! /
1-10  1-10
ノレカンビス（ァノレキノレホスフィン酸） [ェタン一 1, 2—ビス（メチノレホスフィン酸）などの C アルカンビス（C アルキルホスフィン酸）など]など }などが挙げられる。 Nolecanbis (anolequinolephosphinic acid) [Calkanebis (C alkylphosphinic acid) such as ethane-1,2-bis (methinolephosphinic acid)], etc.}.
1 -10 1-6  1 -10 1-6
有機ホスフィン酸塩を形成する金属としては、周期表第 1族金属 (アルカリ金属）（リ チウム、カリウム、ナトリウムなど）、周期表第 2族金属 (アルカリ土類金属）（マグネシゥ ム、カルシウム、ノ リウムなど）、周期表第 4族金属（チタン、ジルコニウムなど）、遷移 金属 (マンガンなどの周期表第 7族金属；鉄などの周期表第 8族金属；コバルトなどの 周期表第 9族金属;ニッケルなどの周期表第 10族金属;銅などの周期表第 11族金 属など)、亜鉛などの周期表第 12族金属、アルミニウムなどの周期表第 13族金属、 スズなどの周期表第 14族金属、アンチモンなどの周期表第 15族金属などが挙げら れる。これらの金属は、単独で又は二種以上組み合わせて使用できる。なお、金属 塩は、含水塩、例えば、含水マグネシウム塩、含水カルシウム塩、含水アルミニウム塩 、含水亜鉛塩などであってもよい。また、金属塩には、金属が部分的に酸化された塩 (例えば、チタ-ル塩、ジルコ-ル塩など)も含まれる。また、塩を形成する塩基性窒 素含有ィ匕合物としては、例えば、アミノ基を有する窒素含有化合物 [アミノトリアジン 化合物 (メラミン、グアナミン、ベンゾグアナミン及び Z又はその縮合物 (メラム、メレム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. These metals can be used alone or in combination of two or more. 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.). In addition, as 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)
、メロンなどのメラミン縮合物など）など）、グァ-ジンィ匕合物（グァ二ジンなど)など]、 尿素化合物 (尿素など)などが挙げられる。塩基性窒素含有化合物は、単独で又は 二種以上組み合わせて使用できる。これらの塩形成成分は、単独で又は二種以上 組合せて塩を形成していてもよい。例えば、有機ホスフィン酸塩には、有機ホスフィン 酸と複数種の塩形成成分との複塩、例えば、メラミン'メラム'メレム複塩、メラミン 'メラ ム 'メレム'メロン複塩なども含まれる。 , Melamine condensates such as melon), etc.), guanidine compounds (eg guanidine etc.)], urea compounds (urea etc.) and the like. The basic nitrogen-containing compounds can be used alone or in combination of two or more. These salt-forming components may be used alone or in combination of two or more to form a salt. For example, 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.
[0062] これらの塩を形成する金属および窒素含有化合物のうち、周期表第 1族金属、第 2 族金属、第 4族金属、第 7族金属、第 8族金属、第 10族金属、第 11族金属、第 12族 金属、第 13族金属、第 14族金属、第 15族金属及びアミノトリアジン化合物 (メラミン、 メラミン縮合物など）が好まし ヽ。  [0062] Among the metals and nitrogen-containing compounds that form these salts, 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 (melamine, melamine condensates, etc.) are preferred.
[0063] なお、前記有機ホスフィン酸塩にぉ 、て、置換基として酸基 (カルボキシ基など）を 有する有機ホスフィン酸の酸基の一部又は全てが塩 (前記例示の塩、例えば、ホスフ イン酸と同一の金属や窒素含有ィ匕合物などの塩)を形成していてもよい（例えば、力 ルボキシレート化して!/、てもよ!/、）。  [0063] Note that 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! /).
[0064] 好ま 、有機ホスフィン酸塩としては、置換基を有して!/ヽてもよ ヽ脂肪族ホスフィン 酸塩及び Z又は置換基を有していてもよい脂環族ホスフィン酸塩、例えば、置換基 を有して!/、てもよ ヽジアルキルホスフィン酸、置換基を有して!/、てもよ 、ジシクロアル キルホスフィン酸、置換基を有していてもよいアルキレンホスフィン酸、置換基を有し て！、てもよ ヽァルケ-レンホスフィン酸、置換基を有して!/、てもよ ヽ（ビ）シクロアルキ レンホスフィン酸、及び置換基を有して!/、てもよ 、アルカンビス（アルキルホスフィン酸 [0064] Preferably, 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! Also, alk-alkene phosphinic acid, having a substituent! /, Or ヽ (bi) cycloalkylene phosphinic acid, and having a substituent! /, Alkanebis (alkylphosphine) acid
)から選択された有機ホスフィン酸と、周期表第 1族金属、第 2族金属、第 4族金属、 第 7族金属、第 8族金属、第 10族金属、第 11族金属、第 12族金属、第 13族金属、 第 14族金属、第 15族金属及びアミノトリアジン化合物から選択された少なくとも一種 との塩 {例えば、置換基を有して 、てもよ ヽジアルキルホスフィン酸塩 [ジメチルホスフ イン酸 Ca塩、メチルェチルホスフィン酸 Ca塩、ジェチルホスフィン酸 Ca塩、ェチルブ チルホスフィン酸 Ca塩、ジブチルホスフィン酸 Ca塩、（2—カルボキシェチル）メチル ホスフィン酸 Ca塩、（2—カルボキシプロピル）メチルホスフィン酸 Ca塩、ビス（2—力 ルボキシェチル）ホスフィン酸 Ca塩、ビス（2—カルボキシプロピル）ホスフィン酸及び これらのカルシウム塩に対応する Mg塩などのアルカリ土類金属塩；ジメチルホスフィ ン酸 A1塩、メチルェチルホスフィン酸 A1塩、ジェチルホスフィン酸 A1塩、ェチルブチ ルホスフィン酸 A1塩、ジブチルホスフィン酸 A1塩、（2—カルボキシェチル）メチルホス フィン酸 A1塩、（2—カルボキシプロピル)メチルホスフィン酸 A1塩、ビス（2—カルボキ シェチル）ホスフィン酸 A1塩、ビス（2—カルボキシプロピル）ホスフィン酸 A1塩などの アルミニウム塩;メチルェチルホスフィン酸 Ti塩、ジェチルホスフィン酸 Ti塩、ェチル ブチルホスフィン酸 Ti塩、ジブチルホスフィン酸 Ti塩及びこれらの塩に対応するチタ -ル塩などのチタン塩；ジェチルホスフィン酸 Zn塩、ェチルブチルホスフィン酸 Zn塩 、ジブチルホスフィン酸 Zn塩、メチルェチルホスフィン酸 Zn塩、（2—カルボキシェチ ル)メチルホスフィン酸 Zn塩などの亜鉛塩など]、アミノトリアジン化合物の塩（ジメチ ルホスフィン酸メラミン塩、メチルェチルホスフィン酸メラミン塩、ジェチルホスフィン酸 メラミン塩、ェチルブチルホスフィン酸メラミン塩、ジブチルホスフィン酸メラミン塩、こ れらのメラミン塩に対応するメラミン'メラム'メレム複塩などのアミノトリアジンィ匕合物と の塩など）など]、置換基を有していてもよいアルキレンホスフィン酸塩 [例えば、 1—ヒ ドロキシホスホラン 1—ォキシドのアルカリ土類金属塩（Ca塩、 Mg塩など）、 A1塩、 Ti 塩、チタ-ル塩、 Zn塩などの金属塩;メラミン塩、メラミン'メラム'メレム複塩などのアミ ノトリアジン塩など]などが挙げられる。 ) Selected from the group 1 metal, Group 2 metal, Group 4 metal, Group 7 metal, Group 8 metal, Group 10 metal, Group 11 metal, Group 12 A salt with at least one selected from a metal, a Group 13 metal, a Group 14 metal, a Group 15 metal and an aminotriazine compound (for example, a dialkylphosphinic acid salt having a substituent [dimethylphosphine In-acid Ca salt, methylethylphosphinic acid Ca salt, jetylphosphinic acid Ca salt, ethylbutyphosphinic acid Ca salt, dibutylphosphinic acid Ca salt, (2-carboxyethyl) methylphosphinic acid Ca salt, (2-carboxyl Propyl) methylphosphinic acid Ca salt, bis (2-force ruboxhetyl) phosphinic acid Ca salt, bis (2-carboxypropyl) phosphinic acid and alkaline earth metal salts such as Mg salt corresponding to these calcium salts; dimethylphosphite Acid A1 salt, methylethylphosphinic acid A1 salt, jetylphosphinic acid A1 salt, ethylbutyphosphinic acid A1 salt, dibutylphosphinic acid A1 salt, (2-carboxyethyl) methylphosphinic acid A1 salt, (2-carboxyl Propyl) methylphosphinic acid A1 salt, bis (2-carbochetyl) phosphinic acid A1 salt, bis (2-carbohydrate) Cypropyl) Phosphinic acid A1 salts, etc. 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. Titanium salt of: Zetylphosphine acid Zn salt, Ethylbutylphosphinic acid Zn salt, Dibutylphosphinic acid Zn salt, Methylethylphosphinic acid Zn salt, (2-Carboxyethyl) methylphosphinic acid Zn salt, 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 (Ca salt, Mg salt, etc.), A1 Metal salts such as salts, Ti salts, titanium salts and Zn salts; and aminotriazine salts such as melamine salts and melamine 'melam' melem double salts].
特に好まし!/、有機ホスフィン酸塩には、置換基を有して!/、てもよ 、ジアルキルホスフ イン酸、置換基を有していてもよいジシクロアルキルホスフィン酸、置換基を有してい てもよ 、アルキレンホスフィン酸、置換基を有して!/、てもよ ヽァルケ-レンホスフィン酸 、及び置換基を有して 、てもよ 、アルカンビス（アルキルホスフィン酸）から選択され た有機ホスフィン酸と、周期表第 2族金属 (カルシウムなど)、周期表第 13族金属 (ァ ルミ-ゥムなど）、アミノトリアジンィ匕合物 (メラミン、メラム、メレム、メロンなど）から選択 された少なくとも一種との塩が含まれる。有機ホスフィン酸塩は単独で又は 2種以上 組みあわせてもよい。 Particularly preferred! / 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.
[0066] 有機ホスフィン酸塩の具体例としては、例えば、特開昭 55— 5979号公報、特開平 8— 73720号公報、特開平 9— 278784号公報、特開平 11— 236392号公報、特 開 2001— 2686号公報、特開 2004— 238378号公報、特開 2004— 269526号公 報、特開 2004— 269884号公報、特開 2004— 346325号公報、特表 2001— 513 784号公報、特表 2001— 525327号公報、特表 2001— 525328号公報、特表 20 01— 525329号公報、特表 2001— 540224号公報、米国特許 4180495号公報、 米国特許 4208321号公報、米国特許 4208322号公報、米国特許 6229044号公 報、米国特許 6303674号公報に記載されている化合物が挙げられる。  [0066] Specific examples of the organic phosphinic acid salt include, for example, JP-A-55-5979, JP-A-8-73720, JP-A-9-278784, and JP-A-11-236392. 2001-2686, JP 2004-238378, JP 2004-269526, JP 2004-269884, JP 2004-346325, Special 2001-513 784, Special 2001-525327, Special Table 2001-525328, Special Table 20 01-525329, Special 2001-540224, US Patent 4180495, US Patent 4208321, US Patent 4208322, US Examples thereof include compounds described in Japanese Patent No. 6229044 and US Pat. No. 6303674.
[0067] (塩基性窒素含有化合物のォキソ酸塩 (C2) )  [0067] (Oxo salt of basic nitrogen-containing compound (C2))
ォキソ酸塩 (C2)を構成するォキソ酸 (前記有機ホスフィン酸以外のォキソ酸）として は、例えば、硝酸、塩素酸 (過塩素酸、塩素酸、亜塩素酸、次亜塩素酸など）、リン酸 [オルトリン酸、メタリン酸、亜リン酸、次亜リン酸などの非縮合リン酸;ピロリン酸、三リ ン酸、四リン酸、ポリメタリン酸、無水リン酸 (五酸ィ匕ニリン)などの縮合リン酸 (ポリリン 酸)など]、有機リン酸 (前記リン酸 (次亜リン酸以外のリン酸）と、アル力ノール、アルキ レングリコールなどのアルコール類との部分エステル（例えば、リン酸ジメチルなどのリ ン酸モノ又はジアルキルなど）、硫酸 (ペルォクソ一硫酸、硫酸、亜硫酸などの非縮合 硫酸;ペルォクソ二硫酸、ピロ硫酸などの縮合硫酸など）、ホウ酸 (オルトホウ酸、メタ ホウ酸などの非縮合ホウ酸；四ホウ酸、無水ホウ酸などの縮合ホウ酸など）、クロム酸、 アンチモン酸、モリブデン酸、タングステン酸などが含まれる。これらのォキソ酸は、単 独で又は二種以上組み合わせて使用できる。これらのォキソ酸のうち、縮合リン酸 (ピ 口リン酸、ポリリン酸、ポリメタリン酸など）、硫酸、縮合硫酸 (ピロ硫酸など）などが好ま しい。  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 匕 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. These oxo acids can be used alone or in combination of two or more. Of the oxoacids, condensed phosphoric acid (pyrophosphoric acid, polyphosphoric acid, polymetaphosphoric acid, etc.), sulfuric acid, condensed sulfuric acid (pyrosulfuric acid, etc.) are preferred.
[0068] ォキソ酸塩 (C2)を構成する塩基性窒素含有化合物 (窒素含有化合物）としては、 例えば、窒素原子に結合した水素原子 (ァミノ基（-NH )又はイミノ基（-NH-)の  [0068] 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.
2  2
水素原子、すなわち、活性水素原子)を有する窒素含有化合物 (鎖状又は環状化合 物）、例えば、アンモニア、尿素化合物（尿素など）、グァ-ジンィ匕合物（ジシアンジァ ミド、グァ-ジン、グァ-ル尿素など）、アミノトリアジン化合物 [メラミン、グアナミン、ベ ンゾグアナミン及び z又はその縮合物 (メラム、メレム、メロンなどのメラミン縮合物など )など]などが挙げられる。これらの窒素含有ィ匕合物は、単独で又は二種以上組み合 わせて使用できる。前記窒素含有ィ匕合物のうち、アンモニア、尿素、グァ-ジン、ジシ アンジアミド、メラミン、メラミン縮合物 (メラム、メレム、メロンなど）が好ましい。 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.
[0069] ォキソ酸塩 (C2)は、ォキソ酸と塩基窒素含有化合物との反応 (および焼成)生成 物である限り、重縮合物などであってもよい。ォキソ酸と前記窒素含有化合物との重 縮合物としては、前記ォキソ酸、及び Z又はォキソ酸と前記窒素含有化合物との塩と 、シアナミド誘導体（― N = C = N—又は— N = C (— N< )で表されるユニットを有す  [0069] 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. Examples of the polycondensation product of oxo acid and the nitrogen-containing compound include the oxo acid, Z or a salt of oxo acid and the nitrogen-containing compound, and a cyanamide derivative (—N = C = N— or —N = C ( — Has a unit represented by N <)
2  2
る化合物、例えば、メラミンなどの前記トリァジン化合物、前記グァニジンィ匕合物など） との重縮合物が挙げられる。このような重縮合物は、例えば、前記ォキソ酸と前記シ アナミド誘導体とを、必要により結合剤 (尿素及び Z又はォキソ酸尿素など）の存在 下、焼成、縮合することにより得ることができ、アミド結合を有する高分子化合物であ る場合が多い。このような重縮合物としては、通常、前記ォキソ酸として、前記例示の リン酸、有機リン酸の他、前記窒素含有ィ匕合物のリン酸塩 (ポリリン酸アンモ-ゥム、リ ン酸尿素など）（特に、有機リン酸及び Z又は縮合リン酸)を用いた縮合リン酸アミド（ 又はポリリン酸アミド)などが使用できる。なお、ポリリン酸アミドでは、前記結合剤とし て、尿素及び Z又はリン酸尿素を用いる場合が多い。前記重縮合物は、単独で又は 二種以上組み合わせて使用できる。なお、ポリリン酸アミドについては、例えば、特開 平 7— 138463号公報を参照できる。このようなポリリン酸アミドは、特公昭 51— 392 71号公報及び特公昭 53— 2170号公報などに記載の方法などにより製造できる。ポ リリン酸アミドは、例えば、「スミセーフ PM」 [住友化学工業 (株）]、「タイェン S」 [太平 化学産業 (株) ]などとして市販されて!ヽる。  Compounds, for example, 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. As such 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. In polyphosphate 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. As for polyphosphoric acid amide, for example, 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.
[0070] 好ましいォキソ酸塩としては、例えば、ポリリン酸とアミノトリアジンィ匕合物との塩 [例 えば、ポリリン酸メラミン、ポリリン酸メラム、ポリリン酸メレムなどのポリリン酸とメラミン及 び Z又はメラミン縮合物（特にメラミン又はメラミン縮合物）との塩]、硫酸とアミノトリア ジンィヒ合物との塩 [例えば、硫酸 (ジ)メラミン、硫酸 (ジ)メラム、硫酸 (ジ)メレム、硫酸 メラミン'メラム'メレム複塩などの硫酸とメラミン及び/又はメラミン縮合物との塩など] 、ピロ硫酸とアミノトリアジンィ匕合物との塩 [例えば、ピロ硫酸 (ジ)メラミン、ピロ硫酸 (ジ )メラム、ピロ硫酸 (ジ)メレム、ピロ硫酸メラミン'メラム'メレム複塩などのピロ硫酸とメラ ミン及び Z又はメラミン縮合物との塩]、縮合リン酸アミド (又はポリリン酸アミド)などが 挙げられる。 [0070] 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 pyrosulfuric acid such as melamine pyrosulfate 'melam' melem double salt and melamine and Z or melamine condensate], condensed phosphoric acid amide (or polyphosphoric acid amide) It is done.
[0071] ォキソ酸塩にぉ 、て、ォキソ酸と前記窒素含有ィ匕合物との割合 (モル比）は、例え ば、ォキソ酸 Z窒素含有化合物 = 1Z0. 5〜lZ5、好ましくは lZO. 7〜lZ4、さら に好ましくは ΙΖΟ. 8〜： LZ3程度であってもよい。  [0071] The ratio (molar ratio) of oxoacid to the nitrogen-containing compound in the oxoacid salt is, for example, oxoacid Z nitrogen-containing compound = 1Z0.5 to lZ5, preferably lZO. 7 to lZ4, more preferably VIII. 8 to: about LZ3.
[0072] このようなォキソ酸塩は、ハロゲン系難燃剤を用いても、榭脂の電気特性を改善す ることができる。そのため、前記ォキソ酸塩は電気特性向上剤として機能するようであ る。 [0072] 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.
[0073] 有機 ·無機酸塩 (C)は、単独で又は 2種以上組み合わせてもよい。特に、有機 '無 機酸塩 (C)は、電気特性をより一層向上するため、有機ホスフィン酸塩 (C1)および ォキソ酸塩 (C2)で構成してもよ!/ヽ。有機ホスフィン酸塩 (C1)とォキソ酸塩 (C2)とを 組み合わせる場合、前者 Ζ後者 (重量比） = 99Zl〜lZ99、好ましくは 95Ζ5〜5 Ζ95、さらに好ましくは 90ZlO〜10Z90程度であってもよい。  [0073] The organic / inorganic acid salt (C) may be used alone or in combination of two or more. In particular, organic 'organic acid salts (C) may be composed of organic phosphinic acid salts (C1) and oxo acid salts (C2) to further improve electrical properties! / ヽ. When combining organic phosphinate (C1) and oxoacid salt (C2), the former Ζ latter (weight ratio) = 99Zl to lZ99, preferably 95Ζ5 to 5Ζ95, more preferably about 90ZlO to 10Z90 .
[0074] 有機 ·無機酸塩 (C)の割合は、ベース榭脂 100重量部に対して、例えば、 1〜60重 量部（例えば、 2〜50重量部）、好ましくは 3〜40重量部（例えば、 4〜35重量部）、 さらに好ましくは 3〜30重量部（例えば、 8〜25重量部)程度である。また、有機-無 機酸塩 (C)の割合は、ハロゲン系難燃剤（Β) 100重量部に対して、例えば、 5〜500 重量部、好ましくは 10〜350重量部、さらに好ましくは 20〜300重量部（例えば、 30 〜280重量部）、特に 40〜270重量部程度であってもよぐ通常 20〜500重量部程 度であってもよい。  [0074] 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 (剤). 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.
[0075] [電気特性向上剤 (D) ]  [0075] [Electrical property improver (D)]
電気特性向上剤 (D)は、ハロゲン系難燃剤 (および有機'無機酸塩)との組み合わ せにより、ベース榭脂の電気特性を高いレベルで向上するための成分であり、ォレフ イン系榭脂、フッ素系榭脂および第 4族金属化合物から選択された少なくとも 1種で 構成されている。なお、榭脂状の電気特性向上剤 (ォレフイン系榭脂、フッ素系榭脂) は、前記ベース榭脂 (Α)とは異なる榭脂である。  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).
[0076] (ォレフイン系榭脂） ォレフィン系榭脂としては、例えば、ォレフィン系単量体 [エチレン、プロピレン、 1 ブテン、 3—メチルー 1 ペンテン、 4ーメチルー 1ーブテン、 1一へキセン、 1 ォクテ ンなどの a—ォレフイン（特に、 a— C ォレフィン）；環状ォレフイン {例えば、シク [0076] (Olefin-based resin) Examples of olefin resins 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.
2- 10  2- 10
ロブテン、シクロペンテン、シクロへキセンなどのシクロアルケン（C シクロアルケン Cycloalkenes such as lobene, cyclopentene, cyclohexene (C cycloalkene
3- 10  3- 10
など）；シクロペンチン、シクロへキシンなどの C シクロアルキン；架橋環式ォレフィ C) cycloalkynes such as cyclopentine and cyclohexyne; bridged cyclic olefins
3-10  3-10
ン（ノルボルネン、テトラジシクロドデセンなどのポリシクロアルケン、ジシクロペンタジ ェンなどのジシクロアルカジエンなど）；又はこれらの誘導体（アルキル置換体、アル キリデン置換体、アルコキシ置換体、ァシル置換体、カルボキシ置換体など）など }な ど]の単独又は共重合体、前記ォレフィン系単量体又は重合体と、共重合性単量体 [ ビュル系単量体、例えば、（メタ)アクリル酸又はその塩 (金属塩など）、（メタ)アクリル 酸エステル（（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸グリシジルエステル など）などのアクリル系単量体；酢酸ビュルなどの有機酸ビュルエステル系単量体；フ マル酸、（無水）マレイン酸、（無水）ィタコン酸、（無水）シトラコン酸、（無水）ナジック 酸などの α , β 不飽和ジカルボン酸系単量体；（メタ）アクリロニトリルなどのシアン 化ビニル系単量体など]との共重合体 (ランダム共重合体、ブロック共重合体、グラフ ト共重合体など)などが挙げられる。 (Polycycloalkenes such as norbornene and tetradicyclododecene, dicycloalkadienes such as dicyclopentadiene); or derivatives thereof (alkyl substituted, alkylidene substituted, alkoxy substituted, acyl substituted, carboxy Etc.] alone or as a copolymer, the olefin-based monomer or polymer, and a copolymerizable monomer [bull-based monomer, for example, (meth) acrylic acid or a salt thereof Acrylic monomers such as (metal salts), (meth) acrylic acid esters (such as (meth) acrylic acid alkyl esters, (meth) acrylic acid glycidyl esters); organic acid bull ester monomers such as butyl acetate Α, β unsaturated, such as fumaric acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, (anhydrous) citraconic acid, (anhydrous) nadic acid Carboxylic acid monomer; (meth) vinyl cyanide monomers such as acrylonitrile, etc.], copolymers (random copolymers, block copolymers, such as graphs preparative copolymer) and the like.
代表的なォレフィン系榭脂としては、例えば、 α—ォレフイン系榭脂 [例えば、ポリ エチレン、ポリプロピレン、プロピレン エチレン共重合体などの a—C ォレフィン  Typical olefin-based resins include, for example, α-olefin-based resins [for example, a-C olefins such as polyethylene, polypropylene, and propylene-ethylene copolymers.
2-3 の単独又は共重合体;エチレン （メタ)アクリル酸共重合体、プロピレン （メタ）ァク リル酸共重合体、エチレン （メタ)アクリル酸共重合体の金属塩 (アイオノマーなど） などの a— C ォレフィン—（メタ）アクリル酸共重合体、 a— C ォレフィン—（メタ）  2-3 homo- or copolymers; ethylene (meth) acrylic acid copolymer, propylene (meth) acrylic acid copolymer, ethylene (meth) acrylic acid copolymer metal salts (such as ionomers), etc. a—C olefin- (meth) acrylic acid copolymer, a—C olefin- (meth)
2-3 2-3  2-3 2-3
アクリル酸エステル共重合体（エチレン ェチルアタリレート共重合体などの (X C Acrylate ester copolymers (such as ethylene ethyl acrylate copolymer (X C
2- ォレフィン （メタ）アクリル酸アルキルエステル共重合体、エチレン （メタ）アクリル 2-Olefin (meth) acrylic acid alkyl ester copolymer, ethylene (meth) acrylic
3 Three
酸グリシジルエステル共重合体など)などの α— C ォレフィンと共重合性単量体と Α-C olefin and copolymerizable monomers such as acid glycidyl ester copolymers)
2-3  2-3
の共重合体など]、変性ォレフィン系榭脂 [例えば、ォレフィン系榭脂 (ォレフインの単 独又は共重合体)を、酸成分 (例えば、 a , j8—不飽和カルボン酸（(メタ)アクリル酸 、マレイン酸、フマル酸、ィタコン酸、シトラコン酸、ナジック酸など)及び Z又はその 酸無水物など)で変性した酸変性ォレフィン系榭脂など]、環状ォレフィン系榭脂 (例 えば、環状ォレフィンの単独重合体、 a— C ォレフィン一環状ォレフイン共重合 A modified olefinic resin (for example, an olefinic resin (single or copolymer of olefin)) and an acid component (for example, a, j8-unsaturated carboxylic acid ((meth) acrylic acid)). , Maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, etc.) and 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
2-10  2-10
体など)などが挙げられる。ォレフィン系榭脂は、単独で又は 2種以上組み合わせて 使用できる。  Body etc.). Olefin-based resin can be used alone or in combination of two or more.
[0078] これらのォレフィン系榭脂のうち、 α— C ォレフィンの単独又は共重合体（ポリエ  [0078] Among these olefinic resins, α-C olefins are homopolymers or copolymers (polyethylene).
2-3  2-3
チレン、ポリプロピレン、エチレン ζプロピレン共重合体など、特にポリプロピレン、ェ チレン Ζプロピレン共重合体）、 a C ォレフィン （メタ）アクリル酸共重合体、 a  Tylene, polypropylene, ethylene ζ-propylene copolymer, etc., especially polypropylene, ethylene-propylene copolymer), a C olefin (meth) acrylic acid copolymer, a
2-3  2-3
-C ォレフィン （メタ）アクリル酸エステル共重合体 [例えば、 α—C ォレフィン -C olefin (meth) acrylic ester copolymer [eg α-C olefin
2-3 2-3 2-3 2-3
- (メタ）アクリル酸 C アルキルエステル共重合体 (特に、エチレン—アクリル酸ェ  -(Meth) acrylic acid C alkyl ester copolymer (especially ethylene-acrylic acid)
1-4  1-4
チル共重合体）、 ひ C ォレフィン—（メタ）アクリル酸グリシジルエステル共重合体  Chill copolymer), C-olefin- (meth) acrylic acid glycidyl ester copolymer
2-3  2-3
(特に、エチレン （メタ)アクリル酸グリシジルエステル共重合体)など]、酸変性ォレ フィン系榭脂 [例えば、 α— C ォレフィンの単独又は共重合体を酸成分で変性し  (Especially ethylene (meth) acrylic acid glycidyl ester copolymer), etc.], acid-modified olefin-based resin [for example, α-C olefin homopolymer or copolymer is modified with an acid component.
2-3  2-3
たォレフイン系榭脂（特に、無水マレイン酸変性ポリプロピレンなどの酸変性ポリプロ ピレン)など]などが好まし!/、。  Preferred are olefin-based resins (particularly acid-modified polypropylene such as maleic anhydride-modified polypropylene)!
[0079] ォレフィン系榭脂の数平均分子量は、特に制限されないが、例えば、 300-20 X 1 05、好ましくは 500〜10 X 104程度である。 [0079] 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 .
[0080] (フッ素系榭脂）  [0080] (Fluororesin)
フッ素系榭脂 (フッ素含有榭脂）には、フッ素含有単量体の単独又は共重合体、例 えば、フッ素含有単量体（テトラフルォロエチレン、クロ口トリフルォロエチレン、ビ-リ デンフルオライド、へキサフルォロプロピレン、パーフルォロアルキルビニルエーテル など）の単独又は共重合体や、前記フッ素含有単量体と他の共重合性単量体 (ェチ レン、プロピレンなどのォレフィン系単量体、（メタ）アタリレートなどのアクリル系単量 体など)との共重合体などが含まれる。このようなフッ素系榭脂としては、具体的には 、ポリテトラフルォロエチレン、ポリクロ口トリフルォロエチレン、ポリビニリデンフルオラ イドなどの単独重合体；テトラフルォロエチレン一へキサフルォロプロピレン共重合体 、テトラフルォロエチレン パーフルォロアルキルビュルエーテル共重合体、ェチレ ンーテトラフルォロエチレン共重合体、エチレン クロ口トリフルォロエチレン共重合 体などの共重合体が例示できる。好ま 、フッ素系榭脂には、フッ化 α— C ォレフ  Fluorine-based resins (fluorine-containing resins) include fluorine-containing monomers alone or as copolymers, such as fluorine-containing monomers (tetrafluoroethylene, black trifluoroethylene, beryllium). A single or copolymer of denfluoride, hexafluoropropylene, perfluoroalkyl vinyl ether, etc., or the above fluorine-containing monomer and other copolymerizable monomers (ethylene, propylene, etc.) And olefin monomers and copolymers with (acrylic monomers such as (meth) acrylate). Specific examples of such fluorinated resins include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene monohexafluoro. Examples include copolymers such as propylene copolymer, tetrafluoroethylene perfluoroalkyl butyl ether copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene-chlorotrifluoroethylene copolymer. it can. Preferably, fluorinated α-C reef
2-3 イン (特にテトラフルォロエチレン)の単独又は共重合体が含まれる。フッ素系榭脂は 、単独で又は二種以上組み合わせて使用できる。 2-3 in (especially tetrafluoroethylene) homopolymer or copolymer is included. Fluororesin These can be used alone or in combination of two or more.
[0081] なお、前記フッ素含有榭脂は、粒子状で使用してもよぐ平均粒径は、例えば、 10 〜5000 μ m程度、好ましくは 100〜1000 μ m程度、さらに好ましくは 100〜700 μ m程度であってもよい。  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 μm, preferably about 100 to 1000 μm, and more preferably 100 to 700. It may be about μm.
[0082] (周期表第 4族金属化合物）  [0082] (Group 4 metal compounds of the periodic table)
周期表第 4族金属化合物は、例えば、チタン、ジルコニウム、ハフニウムなどの金属 化合物が含まれ、通常、チタン又はジルコニウム (特に、チタン)化合物である場合が 多い。代表的な周期表第 4族金属化合物には、チタンィ匕合物 [例えば、チタン酸ィ匕 物又は水酸化物（例えば、二酸ィ匕チタンなどの酸ィ匕チタン）、ハロゲンィ匕チタン (フッ 化チタンなど）、チタンのォキソ酸塩 (硫酸チタンなど）、これらの水和物（酸ィ匕チタン 一又は二水和物など)など]、これらのチタンィ匕合物に対応するジルコニウム化合物（ 酸ィ匕ジルコニウムなど)などが挙げられる。好ましい周期表第 4族金属化合物には、 酸化チタンが含まれる。これらの周期表第 4族金属化合物は単独で又は 2種以上組 み合わせてもよい。  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.
[0083] 周期表第 4族金属化合物は、粒子状 (又は粉粒状)で使用してもよぐ粉粒状の周 期表第 4族金属化合物の平均粒径は、例えば、 0. 01〜20 /ζ πι、好ましくは 0. 02〜 10 ^ m,さらに好ましくは 0. 05〜5 m程度であってもよい。  [0083] 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 / ζ πι, preferably 0.02 to 10 ^ m, more preferably about 0.05 to 5 m.
[0084] 電気特性向上剤 (D)は、単独で又は 2種以上組み合わせてもよ 、。好ま 、態様 では、電気特性向上剤 (D)は、ォレフィン系榭脂及び Z又は周期表第 4族金属化合 物 (特にォレフィン系榭脂)で少なくとも構成してもよい。特に、有機 ·無機酸塩 (C)が 有機ホスフィン酸塩であるとき、電気特性向上剤 (D)は、少なくともォレフィン系榭脂 及び Z又は周期表第 4族金属化合物で構成する場合が多い。  [0084] The electrical property improver (D) may be used alone or in combination of two or more. Preferably, in the embodiment, 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). In particular, when 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.
[0085] 電気特性向上剤 (D)の割合は、ベース榭脂 100重量部に対して、例えば、 0. 5〜 30重量部（例えば、 1〜25重量部）、好ましくは 2〜20重量部（例えば、 3〜18重量 部）、さらに好ましくは 3〜15重量部程度であってもよい。また、電気特性向上剤（D) の割合は、ハロゲン系難燃剤 100重量部に対して、例えば、 3〜300重量部、好まし くは 5〜200重量部、さらに好ましくは 10〜150重量部（例えば、 15〜130重量部） 程度であってもよぐ通常 30〜180重量部（例えば、 40〜160重量部、好ましくは 50 〜 140重量部）程度であってもよ 、。 [0085] 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).
[0086] [電気特性向上助剤 (E) ] [0086] [Electrical property improvement aid (E)]
本発明の榭脂組成物は、さらに電気特性向上助剤を含んでいてもよい。電気特性 向上助剤 (E)としては、前記成分 (B)〜（D)の 、ずれでもな 、化合物であって電気 特性を向上するための助剤として作用する化合物、例えば、窒素含有ィ匕合物 [ァミノ トリアジンィ匕合物 (メラミン;グアナミン;メラム、メレムなどのメラミン縮合物など）、ァミノ トリアジン化合物の塩 (前記アミノトリアジンィ匕合物の有機酸又は無機酸塩、例えば、 メラミンシァヌレートなどのシァヌール酸塩など）など]、無機酸金属化合物 {例えば、 無機酸金属塩 [例えば、（含水)ケィ酸金属塩 (タルク、カオリン、シリカ、ケイソゥ土、 クレー、ウォラストナイトなど）、（含水)ホウ酸金属塩 (例えば、（含水)ホウ酸亜鉛、（含 水）ホウ酸カルシウム、（含水）ホウ酸アルミニウムなど）、（含水)スズ酸金属塩 (例え ば、（含水)スズ酸亜鉛など）、硫酸金属塩 (硫酸カルシウム、硫酸マグネシウム、硫酸 ノ リウムなど)など]、金属酸ィ匕物（酸ィ匕マグネシウム、酸化鉄、酸化亜鉛、アルミナな ど）、金属水酸化物（水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム 、アルミナ水和物（ベーマイト)など）、金属硫ィ匕物 (硫ィ匕亜鉛、硫化モリブデン、硫ィ匕 タングステンなど）、アルカリ土類金属化合物（例えば、アルカリ土類金属塩 (例えば、 炭酸カルシウム、リン酸水素カルシウムなどのアルカリ土類金属炭酸塩)など)など]な どが挙げられる。これらのうち、好ましい電気特性向上助剤には、アミノトリアジンィ匕合 物の有機酸塩 (特にシァヌル酸塩）、ケィ酸金属塩、ホウ酸金属塩、アルカリ土類金 属化合物などが含まれる。これらの電気特性向上助剤は、単独で又は二種以上組み 合わせて使用できる。  The resin composition of the present invention may further contain an electrical property improving aid. As the electrical property improving aid (E), 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. Compound [Aminotriazine compound (melamine; guanamine; melamine condensate such as melam, melem, etc.), salt of aminotriazine compound (organic acid or inorganic acid salt of the aminotriazine compound, such as melamine cyanurate Etc.), inorganic acid metal compounds {eg, inorganic acid metal salts [eg, (hydrous) metal silicates (eg, talc, kaolin, silica, diatomaceous earth, clay, wollastonite, etc.), ( (Hydrous) metal borate (for example, (hydrous) zinc borate, (hydrous) calcium borate, (hydrous) aluminum borate, (hydrous) metal stannate (eg, (hydrous) stannic acid Lead), metal sulfates (calcium sulfate, magnesium sulfate, sodium sulfate, etc.), metal oxides (acid magnesium, iron oxide, zinc oxide, alumina, etc.), metal hydroxides (water) Aluminum oxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate (boehmite, etc.), metal sulfate (zinc sulfate, molybdenum sulfide, tungsten sulfate, etc.), alkaline earth metal compounds (for example, Alkaline earth metal salts (for example, alkaline earth metal carbonates such as calcium carbonate and calcium hydrogen phosphate) and the like. Among these, 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.
[0087] 電気特性向上助剤 (E)の割合は、ベース榭脂 100重量部に対して、例えば、 0〜3 0重量部、好ましくは 0. 5〜20重量部、さらに好ましくは 1〜15重量部（例えば、 1. 5 〜： LO重量部)程度であってもよ 、。  [0087] 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).
[0088] [難燃助剤 (F) ]  [0088] [Flame Retardant (F)]
本発明の榭脂組成物は、さらに難燃助剤 (F)を含んでいてもよい。難燃助剤 (F)と しては、芳香族化合物（フエノール系榭脂、ァ-リン系榭脂、ポリフエ-レンォキシド系 榭脂、芳香族エポキシ榭脂 (ビスフエノール型エポキシ榭脂、ノボラック型エポキシ榭 脂など）、フエノキシ榭脂、ポリフエ二レンスルフイド系榭脂、ポリカーボネート系榭脂、 ポリアリレート樹脂、芳香族ポリアミド系榭脂、芳香族ポリエステル系榭脂（例えば、液 晶性であってもよい芳香族ポリエステル系榭脂）、芳香族ポリエステルアミド系榭脂（ 例えば、液晶'性であってもよ!、芳香族ポリエステルアミド系榭脂）などの芳香族榭脂）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)
、リン含有ィ匕合物 (有機ホスフィン酸などの前記有機'無機酸塩 (C)の範疇に属さな いリン含有ィ匕合物）、アンチモン含有ィ匕合物、モリブデン含有化合物（酸化モリブデ ンなど）、タングステン含有ィ匕合物（酸ィ匕タングステンなど）、ビスマス含有化合物（酸 化ビスマスなど)、スズ含有化合物 (酸化スズなど）、鉄含有化合物 (酸化鉄など)、銅 含有化合物 (酸化銅など）、ケィ素含有化合物 [ (ポリ）オルガノシロキサン (ポリジメチ ルシロキサン、ポリメチルフエ-ルシロキサンなどのシリコーン榭脂、シリコーンオイル 、ポリシルセスキォキサンなど）、層状ケィ酸塩 (モンモリロナイトなどのスメクタイト系 層状ケィ酸塩、 Li型フッ素テ-オライト、 Na型フッ素テ-オライト、 Li型四ケィ素フッ 素雲母、 Na型四ケィ素フッ素雲母などの膨潤性合成フッ素雲母、バーミュライト、ハ ロイサイトなど)など]、ィォゥ含有ィ匕合物（有機スルホン酸ィ匕合物、パーフルォロアル カンスルホン酸の金属塩、スルフアミン酸ィ匕合物又はその塩など）などが例示できる。 これらの難燃助剤は、単独で又は二種以上組み合わせて使用できる。 , 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 fluoride mica, Na-type tetracathenium fluorine mica Which swellable synthetic fluorine mica, vermulite, halloysite, etc.)], thio-containing compounds (organic sulfonic acid compounds, perfluoroalkanesulfonic acid metal salts, sulfamic acid compounds, or the like) Salt) and the like. These flame retardant aids can be used alone or in combination of two or more.
リン含有化合物としては、（縮合)リン酸エステル [例えば、レゾルシノールビス (ジフ ェニノレホスフェート）、ノヽイドキノンビス（ジフエ-ノレホスフェート）、ビフエニノレビス（ジフ ェ-ノレホスフェート）、ビスフエノーノレ A (ジフエ-ノレホスフェート）、レゾルシノールビ ス（ジ一 2, 6 キシリルホスフェート）、ハイドキノンビス（ジ一 2, 6 キシリルホスフエ 一ト）、ビフエ-ルビス（ジ一 2, 6 キシリルホスフェート）、ビスフエノール一 Aビス（ジ —2, 6—キシリノレホスフェート）、ペンタエリスリトールジフエ-ノレホスフェート、ペンタ エリスリトールジー 2, 6 キシリルホスフェート、 2, 6, 7 トリオキサ 1ーホスフアビ シクロ [2. 2. 2]オクタンー4 メタノール 1ーォキシド、及び米国特許 4154775号 公報及び米国特許 4801625号に記載のリン酸エステルイ匕合物など]、（縮合)リン酸 エステルアミド [例えば、 1, 4 ピぺラジンジィルテトラフエ-ルホスフェート、 1, 4— ピぺラジンジィルテトラ一 2, 6 キシリルホスフェート、 N, Ν'—ビス（ネオペンチレン ジォキシホスフィエル）ピぺラジン、及び特開平 10— 175985号公報、特開 2001— 139823号公報及び特開 2001— 354689号公報記載のリン酸エステルアミド (ホス ホルアミドなど）など]、ホスホ-トリル化合物 [例えば、ァリールォキシホスファゼン（フ エノキシホスファゼン、トリルォキシホスファゼン、キシリルォキシホスファゼン、フエノキ シトリルォキシホスファゼン、フエノキシキシリルホスファゼンなど）などの環状及び/ 又は鎖状のホスファゼンィ匕合物、それらの架橋ホスファゼン化合物（例えば、ビスフエ ノール類残基で架橋されたフエノキシホスファゼンなど）、及び W099Z19383号公 報、 WO00Z9518号公報、 WO02Z98886号公報及び WO04Z24844号公報 に記載のホスファゼンィ匕合物など]、有機（亜)ホスホン酸ィ匕合物 [例えば、有機ホス ホン酸エステル、有機（亜）ホスホン酸金属塩（Li、 Na、 K、 Mg、 Ca、 Al、 Sb、 Sn、 G e、 Ti、 Zn、 Fe、 Zr、 Ce、 Bi、 Sr、 Mnなどの金属塩）、有機（亜）ホスホン酸の塩基性 窒素化合物塩 (メラミン塩、グアナミン塩、ベンゾグアナミン塩及び Z又はそれらの縮 合物塩 (メラム、メレム、メロンなどのメラミン縮合物など）など）、及び無機リンィ匕合物 [ 例えば、赤燐、（亜）リン酸金属塩（亜リンカルシウム、次亜リン酸カルシウム、亜リン酸 アルミニウム、リン酸.亜リン酸アルミニウム複塩、リン酸ホウ素など）、次亜リン酸金属 塩 (次亜リン酸カルシウム、次亜リン酸アルミニウムなど)など]などが挙げられる。特に 、好ま 、有機（亜)ホスホン酸ィ匕合物はリン含有ィ匕合物である。 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. Pat.No. 4154775 and U.S. Pat. Phosphate ester compounds, etc.], (condensed) phosphate ester amides [eg, 1,4-piperazinediyltetraphenyl phosphate, 1,4-piperazinediyltetra-1,2,6 xylylphosphate N, N'-bis (neopentylenedioxyphosphier) piperazine, and JP-A-10-175985 and JP-A-2001- Phosphoric ester amides (phosformamide etc.) described in Japanese Patent No. 139823 and JP 2001-354689], 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). Phosphazene compounds described in W099Z19383, WO00Z9518, WO02Z98886, and WO04Z24844], 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 phosphate, etc.), metal hypophosphite (calcium hypophosphite, aluminum hypophosphite, etc.) and the like. In particular, the organic (phosphorous) phosphonic acid compound is preferably a phosphorus-containing compound.
有機（亜)ホスホン酸ィ匕合物の具体例としては、例えば、メチルホスホン酸、ェチル ホスホン酸、 n—プロピルホスホン酸、イソプロピルホスホン酸、 n—ブチルホスホン酸 、イソブチルホスホン酸、ォクチルホスホン酸、ヒドロキシアルキルホスホン酸（ヒドロキ シメチルホスホン酸、ヒドロキシェチルホスホン酸、ヒドロキシプロピルホスホン酸など） 、ァノレコキシァノレキノレホスホン酸（メトキシメチノレホスホン酸、エトキシェチノレホスホン 酸など）、カノレボキシァノレキノレホスホン酸（カノレボキシメチノレホスホン酸、 2—力ノレボキ シェチルホスホン酸など）、メチル亜ホスホン酸、ェチル亜ホスホン酸、 n—プロピル 亜ホスホン酸、イソプロピル亜ホスホン酸、 n—ブチル亜ホスホン酸、イソブチル亜ホ スホン酸、ォクチル亜ホスホン酸などの置換基を有して 、てもよ 、アルキル（亜）ホス ホン酸（C アルキル（亜）ホスホン酸など）；ェタン一 1, 2—ジホスホン酸、ヒドロキ  Specific examples of the organic (sub) phosphonic acid compound 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, isobutyl phosphite It may have a substituent such as an acid, octylphosphonous acid, etc., but may be an alkyl (sulfur) phosphonic acid (C alkyl (phosphorous) phosphonic acid, etc.); ethane-1,2-diphosphonic acid, hydroxy
1-16  1-16
シエタンジホスホン酸などの置換基を有して 、てもよ 、アルキレンジホスホン酸 (C It may be substituted with alkylenediphosphonic acid (C
2-6 アルキレンジホスホン酸など）； 1—ヒドロキシェチリデン一 1, 1—ジホスホン酸などの 置換基を有して 、てもよ 、アルキリデンジホスホン酸 (C アルキリデンジホスホン酸 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).
1-4  1-4
など）；二トリロトリス (メチルホスホン酸)などの置換基 (ヒドロキシル基など）を有して!/ヽ てもよ 、二トリロトリス（アルキルホスホン酸） [二トリロトリス（C アルキルホスホン酸） Etc .; have substituents (such as hydroxyl groups) such as nitrilotris (methylphosphonic acid)! / ヽ, nitrilotris (alkylphosphonic acid) [nitrilotris (C alkylphosphonic acid)
1-4  1-4
など]；ォキシジメチルホスホン酸などの置換基 (ヒドロキシル基など）を有して!/、てもよEtc.]; have a substituent such as oxydimethylphosphonic acid (such as a hydroxyl group)! /
V、ォキシジ（アルキルホスホン酸） [ォキシジ（C アルキルホスホン酸）など]；ポリビ V, oxydi (alkylphosphonic acid) [oxydi (C alkylphosphonic acid), etc.];
1 -4  14
-ルホスホン酸、ポリアリルホスホン酸などの高分子型ホスホン酸；これらの有機（亜） ホスホン酸のエステル [メチルホスホン酸モノメチルエステル、 2 -カルボキシェチル ホスホン酸ェチル、カルボキシメチルホスホン酸トリエチル、カルボキシェチルホスホ ン酸トリェチルなどの置換基を有して 、てもよ 、アルキル（亜）ホスホン酸のモノ又は ポリアルキルエステル（C アルキル（亜）ホスホン酸のモノ又はジ C アルキルェ  -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).
1-16 1-16 ステルなど）；メチルホスホン酸のペンタエリスリトールエステル、メチルホスホン酸の 2 ーェチルー 2 ヒドロキシメチルー 1, 3 プロパンジオールエステル、ヒドロキシェチ ルポリ（ォキシェチル）ホスホン酸エステルなどの置換基を有して 、てもよ 、アルキル (亜）ホスホン酸の多価アルコールとのエステルなど]；これらの有機（亜）ホスホン酸の 塩 [メチル（亜）ホスホン酸 Ca塩、ェチル（亜）ホスホン酸 Ca塩、 n プロピル（亜）ホス ホン酸 Ca塩、イソプロピル（亜）ホスホン酸 Ca塩、 n ブチル（亜）ホスホン酸 Ca塩、ィ ソブチル（亜）ホスホン酸 Ca塩、ォクチル（亜）ホスホン酸 Ca塩、メチル（亜）ホスホン 酸 Mg塩、ェチル（亜）ホスホン酸 Mg塩、 n プロピル（亜）ホスホン酸 Mg塩、イソプロ ピル（亜）ホスホン酸 Mg塩、 n—ブチル（亜）ホスホン酸 Mg塩、イソブチル（亜）ホスホ ン酸 Mg塩、ォクチル（亜）ホスホン酸 Mg塩、 1ーヒドロキシェチリデン 1, 1ージホス ホン酸 Ca塩、二トリロトリス（メチルホスホン酸） Ca塩、二トリロトリス（メチルホスホン酸） Mg塩などのアルカリ土類金属塩;メチル（亜）ホスホン酸 Ti塩、ェチル（亜）ホスホン 酸 Ti塩、 n—プロピル（亜）ホスホン酸 Ti塩、イソプロピル（亜）ホスホン酸 Ti塩、 n—ブ チル（亜）ホスホン酸 Ti塩、イソブチル（亜）ホスホン酸 Ti塩、ォクチル（亜）ホスホン酸 Ti塩、 1—ヒドロキシェチリデン— 1, 1—ジホスホン酸 Ti塩、二トリロトリス（メチルホス ホン酸) Ti塩及びこれらの Ti塩に対応するチタ-ル塩などのチタン塩（チタ-ル塩も 含む）；メチル（亜）ホスホン酸 A1塩、ェチル（亜）ホスホン酸 A1塩、 n—プロピル（亜） ホスホン酸 A1塩、イソプロピル（亜）ホスホン酸 A1塩、 n—ブチル（亜）ホスホン酸 A1塩 、イソブチル（亜）ホスホン酸 Al塩、ォクチル（亜）ホスホン酸 A1塩、エタンー 1, 2 ジ ホスホン酸 A1塩、カノレボキシメチノレホスホン酸 A1塩、 2—カノレボキシェチノレホスホン 酸 A1塩、メチルホスホン酸モノメチルエステルの A1塩、 1ーヒドロキシェチリデン 1, 1 ジホスホン酸 A1塩、二トリロトリス (メチルホスホン酸) A1塩などのアルミニウム塩;メ チル（亜）ホスホン酸 Zn塩、ェチル（亜）ホスホン酸 Zn塩、 n—プロピル（亜）ホスホン 酸 Zn塩、イソプロピル（亜）ホスホン酸 Zn塩、 n—ブチル（亜）ホスホン酸 Zn塩、イソブ チル（亜）ホスホン酸 Zn塩、ォクチル（亜）ホスホン酸 Zn塩、 1 ヒドロキシェチリデン - 1, 1ージホスホン酸 Zn塩、二トリロトリス（メチルホスホン酸） Zn塩などの亜鉛塩など の有機（亜）ホスホン酸金属塩;メチル（亜）ホスホン酸メラミン塩、ェチル（亜）ホスホン 酸メラミン塩、 n—プロピル（亜）ホスホン酸メラミン塩、イソプロピル（亜）ホスホン酸メラ ミン塩、 n ブチル（亜）ホスホン酸メラミン塩、イソブチル（亜）ホスホン酸メラミン塩、 ォクチル（亜)ホスホン酸メラミン塩、これらのメラミン塩に対応するメラム塩、メレム塩、 メロン塩、メラミン'メラム'メレム複塩、メラミン 'メラム 'メレム'メロン複塩、 1ーヒドロキシ ェチリデン— 1, 1—ジホスホン酸モノ乃至テトラメラミン塩、二トリロトリス (メチルホスホ ン酸)モノ乃至へキサンメラミン塩などのアミノトリアジンィ匕合物 (メラミン又はその縮合 物など）との塩 (有機（亜)ホスホン酸アミノトリアジン塩)など]などが挙げられる。これ らのうち、特に、有機（亜)ホスホン酸塩が好ましい。 1-16 1-16 steal, etc.); having a substituent such as pentaerythritol ester of methylphosphonic acid, 2-ethyl-2-hydroxymethyl-1,3-propanediol ester of methylphosphonic acid, hydroxyethyl poly (oxetyl) phosphonic acid ester, However, esters of alkyl (sub) phosphonic acid with polyhydric alcohols, etc .; salts of these organic (sub) phosphonic acids [methyl (sub) phosphonic acid Ca salt, ethyl (sub) phosphonic acid Ca salt, n Propyl (phosphorous) phosphonic acid Ca salt, Isopropyl (phosphorous) phosphonic acid Ca salt, n-Butyl (phosphorous) phosphonic acid Ca salt, Isobutyl (phosphorous) phosphonic acid Ca salt, Octyl (sub) phosphonic acid Ca salt, Methyl ( Sub-) phosphonic acid Mg salt, ethyl (sub-) phosphonic acid Mg salt, n-propyl (sub-) phosphonic acid Mg salt, isopropyl (sub-) phosphonic acid Mg salt, n —Butyl (sub) phosphonic acid Mg salt, isobutyl (sub) phosphonic acid Mg salt, octyl (sub) phosphonic acid Mg salt, 1-hydroxyethylidene 1,1-diphosphonic acid Ca salt, nitrilotris (methylphosphonic acid) Ca salts, alkaline earth metal salts such as nitrilotris (methylphosphonic acid) Mg salt; methyl (sulfurous) phosphonic acid Ti salt, ethyl (phosphorous) phosphonic acid Ti salt, n-propyl (phosphorous) phosphonic acid Ti salt, isopropyl ( Sub-) phosphonic acid Ti salt, n-butyl (sub-) phosphonic acid Ti salt, isobutyl (sub-) phosphonic acid Ti salt, octyl (sub-) phosphonic acid Ti salt, 1-hydroxyethylidene-1,1-diphosphonic acid Ti salts, nitrilotris (methylphosphonic acid) Ti salts and titanium salts (including tital salts) corresponding to these Ti salts; methyl (sub) phosphonic acid A1 salt, ethyl (sub) Phosphonic acid A1 salt, n-propyl (sub) phosphonic acid A1 salt, isopropyl (sub) phosphonic acid A1 salt, n-butyl (sub) phosphonic acid A1 salt , Isobutyl (phosphorous) phosphonic acid Al salt, octyl (phosphorous) phosphonic acid A1 salt, ethane-1,2 diphosphonic acid A1 salt, canoleboxymethinorephosphonic acid A1 salt, 2-canoleboxhetinorephosphonic acid A1 Salts, aluminum salts such as methylphosphonic acid monomethyl ester A1 salt, 1-hydroxyethylidene 1,1 diphosphonic acid A1 salt, nitrilotris (methylphosphonic acid) A1 salt; methyl (sub) phosphonic acid Zn salt, ethyl (suboxide) ) Phosphonic acid Zn salt, n-propyl (sub-) phosphonic acid Zn salt, isopropyl (sub-) phosphonic acid Zn salt, n-butyl (sub-) phosphonic acid Zn salt, isobutyl (sub-) phosphonic acid Zn salt, octyl (sub- ) Phosphonic acid Zn salt, 1-hydroxyethylidene-1,1-diphosphonic acid Zn salt, nitrilotris (methylphosphonic acid) Zinc salt, etc. 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), etc.]. Of these, organic (sub) phosphonates are particularly preferable.
[0091] また、有機（亜)ホスホン酸ィ匕合物として、例えば、特開昭 48— 57988号公報、特 開昭 55— 5979号公報、特開昭 56— 84750号公報、特開昭 63— 22866号公報、 特開平 1— 226891号公報、特開平 2— 180875号公報、特開平 4— 234893号公 報、特開平 7— 224078号公報、特開平 7— 247112号公報、特開平 8— 59679号 公報、特開平 8— 245659号公報、特開平 9— 272759号公報、特開 2000— 6384 3号公報、特開 2001— 2688号公報、特開 2001— 64438号公報、特開 2001— 64 521号公報、特開 2001— 98161号公報、特開 2001— 98273号公報、特開 2001 — 106919号公報、 WO00Z11108号公報、 WO01Z57134号公報、米国特許 3 789091号公報、米国特許 3849368号公報、米国特許 4390477号公報に記載の 化合物も挙げられる。 [0091] Examples of 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. 59679, JP-A-8-245659, JP-A-9-272759, JP-A-2000-63843, JP-A-2001-2688, JP-A-2001-64438, JP-A-2001-64 No.521, JP2001-98161, JP2001-98273, JP2001-106919, WO00Z11108, WO01Z57134, US Pat. No. 3,78,9091, US Pat. No. 3849368, US The compounds described in Japanese Patent No. 4390477 are also included.
[0092] これらの有機（亜)リン酸ィ匕合物又はその塩は単独で又は二種以上組み合わせて 使用できる。 [0092] These organic (sub) phosphate compounds or salts thereof may be used alone or in combination of two or more. Can be used.
[0093] 好ま ヽ難燃助剤 (F)には、（縮合)リン酸エステル、（縮合)リン酸エステルアミド、 ( 架橋)ァリールォキシホスファゼン、（亜)リン酸金属塩、次亜リン酸金属塩、有機（亜） ホスホン酸エステル、有機（亜)ホスホン酸金属塩、有機（亜)ホスホン酸アミノトリアジ ン塩カゝら選択された少なくとも一種が含まれ、特に好ましい難燃助剤 (F)には、アル キル（亜)ホスホン酸金属塩、（亜）リン酸金属塩及び次亜リン酸金属塩から選択され た少なくとも一種が含まれる。  [0093] Preferably, 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.
[0094] アンチモン含有ィ匕合物としては、例えば、酸ィ匕アンチモン [三酸ィ匕アンチモン（Sb  [0094] Antimony-containing compounds include, for example, acid-antimony [antiacid trimonate (Sb
2 2
Oなど）、五酸化アンチモン（xNa O- Sb O -yH O (x = 0〜： L、 y=0〜4)など）なO), antimony pentoxide (xNaO-SbO-yH2O (x = 0 ~: L, y = 0 ~ 4), etc.)
3 2 2 5 2 3 2 2 5 2
ど]、アンチモン酸塩 [アンチモン酸金属塩 (例えば、アンチモン酸ナトリウムなどのァ ルカリ金属塩、アンチモン酸マグネシウムなどのアルカリ土類金属塩など）、アンチモ ン酸アンモ-ゥムなど]などが挙げられる。これらのアンチモン含有化合物は、単独で 又は二種以上組み合わせて使用できる。前記アンチモン含有ィ匕合物のうち、酸ィ匕ァ ンチモン及びアンチモン酸のアルカリ金属塩などが好ましい。  Etc.], antimonate [metal antimonate (for example, alkali metal such as sodium antimonate, alkaline earth metal such as magnesium antimonate), ammonium antimonate, etc.) . These antimony-containing compounds can be used alone or in combination of two or more. Of the antimony-containing compounds, acid diantimones and alkali metal salts of antimonic acid are preferred.
[0095] また、アンチモン含有ィ匕合物は、必要により、エポキシィ匕合物、シラン化合物、イソ シァネート化合物及び Z又はチタネート化合物などの表面処理剤で表面処理して用 いてもよい。 [0095] Further, 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.
[0096] なお、アンチモン含有化合物の平均粒子径は、例えば、 0. 02〜5 μ m、好ましくは 0. 1〜3 111程度であってもよい。  [0096] The average particle size of the antimony-containing compound may be, for example, about 0.02 to 5 μm, preferably about 0.1 to 3111.
[0097] これらの難燃助剤のうち、特に、芳香族化合物、リン含有ィ匕合物およびアンチモン 含有ィ匕合物から選択された少なくとも一種を用いるのが好ましい。特に、有機'無機 酸塩 (C)として、塩基性窒素含有化合物のォキソ酸塩 (C2)を用いる場合に、アンチ モン含有ィ匕合物を用いると難燃性をさらに向上させることができる。なお、本発明の 榭脂組成物は、前記成分 (B)〜(D)を組み合わせることにより、このような難燃助剤 を含有して ヽなくても、高 ヽレベルで確実に難燃性と優れた電気特性とを両立できる  [0097] Among these flame retardant aids, it is particularly preferable to use at least one selected from aromatic compounds, phosphorus-containing compounds and antimony-containing compounds. In particular, when 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. In addition, 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
[0098] 難燃助剤 (F)の割合は、ベース榭脂 (A) 100重量部に対して、例えば、 0〜30重 量部（例えば、 0. 05〜20重量部）、好ましくは 0. 1〜20重量部（例えば、 0. 3〜10 重量部）、さらに好ましくは 0. 5〜5重量部程度である。 [0098] 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.
[0099] (他の添加剤） [0099] (Other additives)
本発明の難燃性榭脂組成物は、さらに他の添加剤、例えば、他の難燃剤 (窒素系 、リン系難燃剤など)、充填剤、安定剤 (紫外線吸収剤、耐候 (光)安定剤、耐熱安定 剤、加工安定剤、リン系安定剤、反応性安定剤など)、帯電防止剤、滑剤、離型剤、 結晶化核剤、可塑剤、着色剤 (染料、顔料など)、潤滑剤、ドリツビング防止剤などを 含有してもよい。これらの他の添加剤は、単独で又は二種以上組み合わせて使用で きる。  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.
[0100] 前記榭脂組成物は、これらの添加剤のうち、特に、充填剤、耐熱安定剤、加工安定 剤などを含有してもよい。  [0100] Among these additives, the resin composition may contain, in particular, a filler, a heat stabilizer, a processing stabilizer, and the like.
[0101] (充填剤） [0101] (Filler)
充填剤としては、慣用の繊維状、板状、粉粒状などの充填剤が挙げられる。繊維状 充填剤としては、無機繊維 (ガラス繊維、炭素繊維、ボロン繊維、チタン酸カリウム繊 維 (ウイスカー)等)、有機繊維 (アミド繊維など)等が例示できる。板状充填剤としては 、ガラスフレーク、マイ力、グラフアイト、各種金属箔などが例示できる。粉粒状充填剤 としては、金属酸化物（酸化亜鉛、アルミナなど）、硫酸塩 (硫酸カルシウム、硫酸マグ ネシゥムなど）、炭酸塩 (炭酸カルシウムなど）、ガラス類 (ミルドファイバー、ガラスビー ズ、ガラスバルーンなど）、硫ィ匕物（二硫ィ匕モリブデン、二硫ィ匕タングステンなど）、炭 化物 (フッ化黒鉛、炭化ケィ素など)、活性炭、窒化ホウ素などが例示できる。好まし い充填剤には、無機繊維 (特にガラス繊維）が含まれる。充填剤は、単独で又は 2種 以上組みあわせて使用できる。  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. Examples of particulate fillers 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.
[0102] 充填剤の使用量は、ベース榭脂 100重量部に対して、例えば、 0〜： LOO重量部、好 ましくは 1〜80重量部（例えば、 5〜75重量部）、さらに好ましくは 10〜70重量部（例 えば、 20〜65重量部）程度であってもよい。 [0102] 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).
[0103] (耐熱安定剤） [0103] (Heat resistance stabilizer)
耐熱安定剤としては、ヒンダードフエノール系化合物（ヒンダードフエノール系酸ィ匕 防止剤） [例えば、 2, 6 ジ tーブチルー p クレゾール、 2, 2' ーメチレンビス（4 ーメチルー 6 t—ブチルフエノール）、 2, 2' ーチォビス（4ーメチルー 6—t—ブチ ルフエノール）、 4, 4' ーチォビス（6—t—ブチルー m クレゾール）、トリエチレング リコール—ビス— (3- (3— t—ブチル—5—メチル—4—ヒドロキシフエ-ル）プロピオ ネート）、ペンタエリスリトールーテトラキス（3— (3, 5—ジ tーブチルー 4ーヒドロキ シフエ-ル）プロピオネート）などの分岐 C アルキルフエノール類など]、リン系化合 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
3-6  3-6
物（リン系酸化防止剤） [ホスファイト類（ビス（2, 4 ジー t ブチルフエ-ル）ペンタ エリスリトールジホスフアイトなどのビス（C アルキル—ァリール）ペンタエリスリトール  Products (phosphorus antioxidants) [Phosphites (bis (2,4-diethylbutylbutyl) pentaerythritol diphosphite and other bis (C alkyl-aryl) pentaerythritol
1-9  1-9
ジホスフアイトなど）、ホスフォナイト類（テトラキス（2, 4 ジ一 t—ブチルフエ-ル） 4 , 4' —ビフエ-レンジホスフォナイトなど)など]、ィォゥ系化合物 (ィォゥ系酸ィ匕防止 剤） [ジラウリルチオジプロピオネートなど]、アミン系酸ィ匕防止剤 (ァミン系酸ィ匕防止 剤） [例えば、ナフチルァミン、フエ-ルナフチルァミン、 1, 4 フエ-レンジァミン、ビ ス（2, 2, 6, 6—テトラメチル— 4 ピペリジル）セノ ケート、ビス（1, 2, 2, 6, 6 ぺ ンタメチル一 4—ピペリジル）セバケートなどのヒンダードアミン類など]、ヒドロキノン系 化合物（ヒドロキノン系酸ィ匕防止剤） [例えば、 2, 5 ジ tーブチルヒドロキノンなど] 、キノリン系化合物（キノリン系酸ィ匕防止剤） [例えば、 6 エトキシ一 2, 2, 4 トリメチ ルー 1, 2—ジヒドロキノリンなど]などの慣用の酸ィ匕防止剤；アルカリ又はアルカリ土 類金属化合物 [例えば、リン酸水素アルカリ又はアルカリ土類金属塩 (例えば、リン酸 二水素マグネシウム、リン酸二水素カルシウム、リン酸一水素カルシウム (第二リン酸 カルシウム， CaHPO )、リン酸二水素バリウム、リン酸一水素バリウムなどのリン酸水  Diphosphites, etc.), phosphonites (tetrakis (2, 4 di-tert-butylphenol) 4, 4 '— biphenol-diphosphoric phosphinite, etc.)], io-type compounds (io-type acid oxidants) Lauryl thiodipropionate, etc.], 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 1,2-dihydroquinoline, etc.] Anti-oxidation agent; alkali or alkaline earth metal compound [for example, alkali hydrogen phosphate or alkaline earth metal salt (for example, magnesium dihydrogen phosphate, calcium dihydrogen phosphate, calcium monohydrogen phosphate (second Phosphate water such as calcium phosphate (CaHPO), barium dihydrogen phosphate, and barium monohydrogen phosphate
4  Four
素 (又は一水素又は二水素)アルカリ土類金属塩など） ]；無機金属又は鉱物系安定 剤 (ハイド口タルサイト、ゼォライトなど)などが挙げられる。  Elemental (or monohydrogen or dihydrogen) alkaline earth metal salts, etc.]; inorganic metal or mineral stabilizers (hydride talcite, zeolite, etc.).
[0104] これらの耐熱安定剤は、単独で又は二種以上組み合わせて使用できる。  [0104] These heat stabilizers can be used alone or in combination of two or more.
[0105] 特に少なくともヒンダードフエノール系化合物を耐熱安定剤として使用してもよい。 [0105] In particular, at least a hindered phenol compound may be used as a heat stabilizer.
例えば、耐熱安定剤は、ヒンダードフエノール系化合物単独で構成してもよぐヒンダ ードフエノール系化合物と他の耐熱安定剤（例えば、リン系化合物、アルカリ又はァ ルカリ土類金属化合物、およびハイド口タルサイトから選択された少なくとも 1種）とで 構成してちょい。  For example, 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).
[0106] 耐熱安定剤の割合は、ベース榭脂 100重量部に対して、例えば、 0〜15重量部（ 例えば、 0. 001〜： L0重量部）、好ましくは 0. 01〜5重量部、さらに好ましくは（特に 0 . 05〜2重量部)程度の範囲から選択できる。また、ヒンダードフエノール系化合物と 他の耐熱安定剤とを組みあわせる場合、ヒンダードフエノール系化合物と他の耐熱安 定剤との割合は、前者 Z後者 (重量比） =99Zl〜lZ99、好ましくは 98Z2〜10 Z90、さらに好ましくは 95Z5〜20Z80程度であってもよい。 [0106] 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). When a hindered phenol compound is combined with another heat stabilizer, the ratio of the hindered phenol compound to another heat stabilizer is the former Z latter (weight ratio) = 99Zl to lZ99, preferably It may be about 98Z2 to 10Z90, more preferably about 95Z5 to 20Z80.
[0107] (加工安定剤） [0107] (Processing stabilizer)
加工安定剤としては、例えば、長鎖脂肪酸 (例えば、力プリン酸、ラウリン酸、ミリス チン酸、ペンタデシル酸、パルミチン酸、ステアリン酸、ァラキン酸、ベヘン酸、モンタ ン酸、ォレイン酸、リノール酸、リノレン酸、ァラキドン酸、エル力酸、セバシン酸、ドデ カン二酸、テトラデカン二酸などの C 飽和又は不飽和脂肪酸)、長鎖脂肪酸アミ  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
10-34  10-34
ド (例えば、力プリン酸アミド、ラウリン酸アミド、ミリスチン酸アミド、パルミチン酸アミド、 ステアリン酸アミド、ァラキン酸アミド、ベヘン酸アミド、ォレイン酸アミド、ステアリルス テアリン酸アミド、ステアリルォレイン酸アミド、エチレンジァミン ジステアリン酸アミド (エチレンビスステアリルアミド）、へキサメチレンジァミン一ジステアリン酸アミド、ェチ レンジアミンージォレイン酸アミド、エチレンジアミンージエル力酸アミド、エチレンジ アミンー（ステアリン酸アミド)ォレイン酸アミドなど）、長鎖脂肪酸エステル (例えば、ェ チレングリコールジステアリン酸エステル、グリセリンモノステアリン酸エステル、トリメ チロールプロパンモノステアリン酸エステル、ペンタエリスリトールステアリン酸エステ ル、ソルビタンモノステアリン酸エステル、ポリアルキレングリコール（ポリエチレングリ コールなど）のモノステアリン酸エステル、これらに対応するパルミチン酸エステル、ラ ゥリン酸エステル、ベヘン酸エステル、モンタン酸エステル、ォレイン酸エステルなど の前記例示の長鎖脂肪酸のエステル）、ポリアルキレングリコール (ポリエチレングリコ ール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリオキシエチレン ポリオキシプロピレン共重合体など）、シリコーン系化合物、ワックス類 [例えば、天然 パラフィン、合成パラフィン、マイクロワックス、ポリオレフイン系ワックス（ポリエチレンヮ ッタス、ポリプロピレンワックスなど)など]などが挙げられる。加工安定剤は、単独で又 は二種以上組み合わせて使用できる。  (E.g., force purinic acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, araquinic acid amide, behenic acid amide, oleic acid amide, stearyl stearic acid amide, stearyl oleic acid amide, ethylenediamine Distearic acid amide (ethylene bisstearyl amide), hexamethylenediamine monodistearic acid amide, ethylenediamine-dioleic acid amide, ethylenediamine-dierlic acid amide, ethylenediamine- (stearic acid amide) oleic acid amide, etc. ), 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), polyalkylene glycols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene copolymers, etc.), 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.
[0108] 加工安定剤の割合は、ベース榭脂 100重量部に対して、例えば、 0〜20重量部、 好ましくは 0. 1〜： LO重量部、さらに好ましくは 0. 5〜5重量部程度であってもよい。 [0109] (反応性安定剤） [0108] 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. [0109] (Reactive stabilizer)
反応性安定剤としては、例えば、エポキシ系反応性安定剤 [グリシジルエーテルィ匕 合物（ビスフエノールー Aジグリシジルエーテル、フエ-ルグリシジルエーテルなど）、 グリシジルエステル化合物（安息香酸グリシジルエステル、バーサティック酸グリシジ ルエステルなど）、エポキシ基含有アクリル系重合体など]、ォキセタン系反応性安定 剤 [1, 4 ビス { [3 ェチルー 3—ォキセタ -ルメトキシ]メチル }ベンゼン、ジ [1ーェ チル（3—ォキセタニル)メチル]エーテルなど]、ォキサゾリン系反応性安定剤 [1, 3 フエ-レンビス（2—ォキサゾリン）、 1, 4 フエ-レンビス（2—ォキサゾリン）など]、 カルポジイミド系反応性安定剤 [ポリアリールカルポジイミド、ポリアルキルァリール力 ミド]などのポリカルボイミド]などが挙げられる。これらの反応性安定剤は、単独で又 は 2種以上組み合わせてもよ 、。  Examples of reactive stabilizers 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). ), Epoxy group-containing acrylic polymers, etc.], 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.
[0110] 反応性安定剤の割合は、ベース榭脂 100重量部に対して、例えば、 0〜20重量部 、好ましくは 0. 05〜8重量部、さらに好ましくは 0. 1〜5重量部程度の範囲から選択 できる。 [0110] 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
[0111] 本発明の難燃性榭脂組成物は、粉粒体混合物や溶融混合物であってもよぐベー ス榭脂 (A)と、ハロゲン系難燃剤 (B)と、有機'無機酸塩 (C)と、電気特性向上剤 (D )と、必要により他の成分 (電気特性向上助剤、難燃助剤、添加剤など)とを慣用の方 法で混合することにより調製できる。また、本発明には、前記難燃性榭脂組成物で形 成された成形体 (例えば、前記溶融混合物を固化することにより形成された榭脂組成 物 (成形体)）も含まれる。  [0111] 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).
[0112] 難燃性榭脂組成物及び成形体は、例えば、（1)各成分を混合して、一軸又は二軸 の押出機により混練し押出してペレットを調製した後、成形する方法、（2)—旦、組成 の異なるペレット (マスターバッチ）を調製し、そのペレットを所定量混合 (希釈）して成 形に供し、所定の組成の成形体を得る方法、（3)成形機に各成分の 1又は 2以上を 直接仕込み、成形する方法などが採用できる。なお、ベース榭脂以外の成分の全て 又は一部を予め混合し、ベース榭脂と混合してもよぐベース榭脂以外の成分同士を 予め混合することなぐベース榭脂と直接混合してもよい。また、ベース榭脂以外の成 分の添加順序も特に制限されず、ベース榭脂に、ベース榭脂以外の成分の全てを 一度に添加してもよぐ一部の成分を添加して混合した後、残る成分を (必要により複 数回に分割して）添加してもよ ヽ。 [0112] 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. In addition, all or a part of the components other than the base resin may be mixed in advance and mixed with the base resin. Alternatively, the components other than the base resin may be mixed directly with the base resin without mixing them in advance. Good. In addition, 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).
[0113] なお、成形体は、難燃性榭脂組成物を、慣用の方法により溶融混練し、押出成形、 射出成形、圧縮成形などの慣用の方法で成形することにより製造できる。  [0113] 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.
[0114] 本発明の難燃性榭脂組成物 (及び成形体)は、成形性を損なうことなぐしかも、ハ ロゲン系難燃剤を含有するにも拘わらず、難燃性と電気特性とを高 ヽレベルで確実 に両立できる。例えば、本発明の榭脂組成物 (及び成形体）は、試験片の厚み 1. 6 mmで測定したとき、 UL94燃焼性試験に準拠した難燃性力 SV— 2以上、好ましくは V — 1以上、さらに好ましくは V—0以上である。また、本発明の榭脂組成物 (及び成形 体）において、 IEC112 (UL746A)に準拠した比較トラッキング指数（CTI)は、 400 V以上（例えば、 400〜1000V程度）、好ましくは 450V以上（例えば、 450〜900V 程度）、さらに好ましくは 500V以上（例えば、 500〜850V程度）である。特に、本発 明の榭脂組成物では、ハロゲン系難燃剤と特定の有機'無機酸塩と特定の電気特性 向上剤とを組み合わせるので、著しく高いレベルで確実に電気特性を改善でき、例 えば、前記比較トラッキング指数 (CTI)を、 600V以上 (例えば、 600〜850V程度） 、好ましくは 650V以上（例えば、 650〜750V程度）にすることもできる。  [0114] 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. For example, 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. Further, in the resin composition (and molded product) of the present invention, 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). In particular, 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).
[0115] また、本発明の榭脂組成物 (及び成形体）は、試験片の厚み 0. 8mmで測定したと き、 UL94燃焼性試験に準拠した難燃性が V— 1以上、好ましくは V— 0以上で、力 つ IEC112 (UL746A)に準拠した比較トラッキング指数 (CTI)は、 350V以上 (例え ば、 350〜1000V程度）、好ましくは 400V以上（例えば、 400〜900V程度）、さら に好ましくは 450V以上（例えば、 450〜850V程度）であってもよい。  [0115] Further, 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).
産業上の利用可能性  Industrial applicability
[0116] 本発明の難燃性榭脂組成物 (及び成形体)は、難燃性及び電気特性に優れており 、種々の用途、例えば、電気'電子部品、オフィスオートメーション (OA)機器部品、 家電機器部品、自動車部品、機械機構部品などに好適に用いることができる。 [0116] 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.
実施例  Example
[0117] 以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実 施例によって限定されるものではない。 [0117] Hereinafter, the present invention will be described in more detail based on examples. It is not limited by the examples.
[0118] なお、下記の試験により、榭脂組成物の難燃性及び電気特性 (比較トラッキング指 数)を評価した。  [0118] The flame retardancy and electrical properties (comparative tracking index) of the resin composition were evaluated by the following tests.
[0119] [燃焼性試験] [0119] [Flammability test]
UL94に準拠して、試験片の厚み 1. 6mm又は 0. 8mmで燃焼性を評価した。  In accordance with UL94, the flammability was evaluated at a test piece thickness of 1.6 mm or 0.8 mm.
[0120] [比較トラッキング指数 (CTI) ] [0120] [Comparison Tracking Index (CTI)]
IEC112 (UL746A)に準拠して、塩化アンモ-ゥム 0. 1%水溶液を用いて比較ト ラッキング指数 (CTI) [単位: V]を評価した。  Based on IEC112 (UL746A), a comparative tracking index (CTI) [unit: V] was evaluated using a 0.1% aqueous solution of ammonium chloride.
[0121] また、実施例及び比較例で使用したベース榭脂 (A)、ハロゲン系難燃剤 (B)、有機[0121] Further, the base resin (A), the halogenated flame retardant (B), and the organic used in Examples and Comparative Examples
•無機酸塩 (C)、電気特性向上剤 (D)、電気特性向上助剤 (E)、難燃助剤 (F)、充 填剤 (G)、耐熱安定剤 (H)、加工安定剤 (I)、反応性安定剤 ωは以下の通りである 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 ω is as follows
[0122] 1.ベース榭脂 (Α) [0122] 1. Base fat (Α)
(A- 1)：ポリブチレンテレフタレー卜 [固有粘度 =0. 85]  (A-1): Polybutylene terephthalate [Intrinsic viscosity = 0.85]
(Α- 2)：ポリプロピレンテレフタレート [固有粘度 =0. 85]  (Α-2): Polypropylene terephthalate [Intrinsic viscosity = 0.85]
(Α- 3)：ポリエチレンテレフタレート [固有粘度 =0. 75]  (Α-3): Polyethylene terephthalate [Intrinsic viscosity = 0.75]
(Α-4)：ポリアミド 66  (Α-4): Polyamide 66
(Α- 5) : 12. 5モル0 /0イソフタル酸変性ポリブチレンテレフタレート [固有粘度 =0. 80]。 (Α- 5): 12. 5 mole 0/0 isophthalic acid modified polybutylene terephthalate [. Intrinsic viscosity = 0 80].
[0123] 2.ハロゲン系難燃剤 (Β)  [0123] 2. Halogen flame retardant (剤)
(B- 1)：ポリ（ペンタブロモベンジルアタリレート） [FR1025,ブロムケムファーイ一 スト社製、 ]  (B-1): Poly (pentabromobenzyl atallylate) [FR1025, manufactured by Bromchemfarist Corp.]
(Β- 2)：臭素化ポリスチレン [パイ口チェック 68ΡΒ,フエ口ケミカルズ社製] (Β— 3)：臭素化ポリスチレン [SYTEX HP- 7010P,アルべマール社製] (Β— 4)：エチレンビステトラブロモフタルイミド [SYTEX ΒΤ- 93,アルべマール 社製]。  (Β-2): Brominated polystyrene (Pie check 68ΡΒ, manufactured by Hueguchi Chemicals) (Β—3): Brominated polystyrene [SYTEX HP-7010P, manufactured by Albemarle Corp.] (] —4): Ethylenebis Tetrabromophthalimide [SYTEX 93-93, manufactured by Albemarle].
[0124] (Β- 5) :臭素化ビスフエノール Α型エポキシ榭脂 [SRT5000、阪本薬品工業 (株） 製] (B-6)：臭素化ビスフエノール A型ポリカーボネート榭脂 [フアイャガード FG— 75 00、帝人化成 (株)製]。 [0124] (Β-5): Brominated bisphenol Α type epoxy resin [SRT5000, Sakamoto Pharmaceutical Co., Ltd.] (B-6): Brominated bisphenol A type polycarbonate resin [Fiaguard FG-7500, manufactured by Teijin Chemicals Ltd.].
[0125] 3.有機'無機酸塩 (C) [0125] 3. Organic 'inorganic acid salts (C)
有機ホスフィン酸塩 (C1)  Organophosphinate (C1)
(C1-1)：メチルェチルホスフィン酸アルミニウム塩  (C1-1): Methylethylphosphinic acid aluminum salt
(C1-2)：メチルェチルホフイン酸カルシウム塩  (C1-2): Methylethyl phosphinate calcium salt
(C1-3)：ジメチルホスフィン酸アルミニウム塩  (C1-3): Aluminum dimethylphosphinate
(C1-4)： 1—ヒドロキシホスホラン 1—ォキシドのアルミニウム塩  (C1-4): Aluminum salt of 1-hydroxyphosphorane 1-oxide
(C1-5)：ジメチルホスフィン酸メラミン塩  (C1-5): Dimethylphosphinic acid melamine salt
(C1-6)： (2—カルボキシェチル)メチルホスフィン酸のアルミニウム塩  (C1-6): Aluminum salt of (2-carboxyethyl) methylphosphinic acid
(C1-7)：ジェチルホスフィン酸アルミニウム塩  (C1-7): Jetylphosphinic acid aluminum salt
ォキソ酸塩 (C2)  Oxoate (C2)
(C2-1)：ポリリン酸メラミン [Melapur200, DSM社製]  (C2-1): Melamine polyphosphate [Melapur200, manufactured by DSM]
(C2-2)：縮合リン酸アミド [タイェン S,太平化学産業 (株)製]  (C2-2): Condensed phosphoramide [Taien S, Taihei Chemical Industry Co., Ltd.]
(C2-3)：硫酸ジメラミン [アビノン— 901, (株）三和ケミカル製]  (C2-3): Dimelamine sulfate [Abinon 901, manufactured by Sanwa Chemical Co., Ltd.]
酸性ピロリン酸金属塩 (C3：比較例で使用）  Acidic pyrophosphate metal salt (C3: used in comparative examples)
(C3-1)：酸性ピロリン酸ナトリウム。  (C3-1): Sodium acid pyrophosphate.
[0126] 4.電気特性向上剤 (D) [0126] 4. Electrical property improver (D)
ォレフィン系榭脂（D1)  Olefin-based resin (D1)
(D1-1)：エチレン Zアクリル酸ェチル共重合体 [NUC— 6570, 日本ュ-カー（ 株)製]  (D1-1): Ethylene Z Ethyl acrylate copolymer [NUC-6570, manufactured by Nippon Car Co., Ltd.]
(D1-2)：エチレン Zメタクリル酸グリシジル共重合体 [ボンドファースト E,住友化 学工業 (株)製]  (D1-2): Ethylene Z glycidyl methacrylate copolymer [Bond First E, manufactured by Sumitomo Chemical Co., Ltd.]
(D1-3)：無水マレイン酸変性ポリオレフイン [タフマー MP,三井化学 (株)製] (D1-4)：ポリプロピレン [ノーブレン J,住友化学工業 (株)製]  (D1-3): Maleic anhydride modified polyolefin [Tafmer MP, manufactured by Mitsui Chemicals, Inc.] (D1-4): Polypropylene [Noblen J, manufactured by Sumitomo Chemical Co., Ltd.]
(D1-5)：エチレン Zプロピレン共重合体 QF707ZB,三井化学 (株)製] フッ素系榭脂 (D2)  (D1-5): Ethylene Z-propylene copolymer QF707ZB, manufactured by Mitsui Chemicals, Inc.] Fluorinated resin (D2)
(D2-1)：ポリテトラフルォロエチレン [テフロン 6J,三井デュポンフロロケミカル (株 )製] (D2-1): Polytetrafluoroethylene [Teflon 6J, Mitsui DuPont Fluorochemical Co., Ltd. )]
周期表第 4族金属含有化合物 (D3)  Periodic table Group 4 metal-containing compounds (D3)
(D3— 1):酸ィ匕チタン [TITONE SR-1,堺化学工業 (株)製]。  (D3-1): Titanium acid [TITONE SR-1, manufactured by Sakai Chemical Industry Co., Ltd.].
[0127] 5.電気特性向上助剤 (E) [0127] 5. Electric property improvement aid (E)
(E-1)：タノレク  (E-1): Tanorek
ー2):含水ホゥ酸亜鉛[? 6 &1^ ZB,ボラックス.ジャパン (株)製]  -2): Hydrous zinc folate [? 6 & 1 ^ ZB, Borax Japan Co., Ltd.]
(E-3)：メラミンシァヌレート  (E-3): Melamine cyanurate
(E— 4):炭酸カルシウム。  (E—4): Calcium carbonate.
[0128] 6.難燃助剤 (F) [0128] 6. Flame retardant aid (F)
芳香族化合物 (F1)  Aromatic compounds (F1)
(F1-1)：ビスフエノール A型エポキシ榭脂 [ェピコート 1004K,油化シェルェポキ シ (株)製]  (F1-1): Bisphenol A type epoxy resin [Epicoat 1004K, manufactured by Yuka Shell Epoxy Co., Ltd.]
(F1-2)：ノボラック型エポキシ榭脂 [EPPN— 201, 日本化薬 (株)製] (F1-3)：ポリカーボネート榭脂 [パンライト L1225、帝人化成 (株)製] リン含有化合物 (F2)  (F1-2): Novolac epoxy resin [EPPN-201, manufactured by Nippon Kayaku Co., Ltd.] (F1-3): Polycarbonate resin [Panlite L1225, manufactured by Teijin Chemicals Ltd.] Phosphorus-containing compound (F2 )
(F2— 1)：レゾルシノールビス（ジ— 2, 6—キシリルホスフェート） [PX200,大八化 学工業 (株)製]  (F2-1): Resorcinol bis (di-2,6-xylyl phosphate) [PX200, manufactured by Daihachi Chemical Industry Co., Ltd.]
(F2-2)：フエノキシトリルォキシホスファゼン [KEMIDANT302S,ケミプロ化成（ 株)製]  (F2-2): Phenoxytriloxyphosphazene [KEMIDANT302S, manufactured by Chemipro Kasei Co., Ltd.]
(F2- -3) ：環状フエノキシホスファゼン（3〜4 体混合物）  (F2- -3): Cyclic phenoxyphosphazene (3-4 mixture)
(F2- -4) :1, 4ーピペラジンジィルテトラフヱ- ：ルホスフェート  (F2- -4): 1, 4-piperazine diyltetraphenyl-: ruphosphate
(F2- ■5) ：ェチルホスホン酸アルミニウム塩  (F2- ■ 5): Ethylphosphonic acid aluminum salt
(F2- -6) ：ェチル亜ホスホン酸アルミニウム塩  (F2- -6): Ethylphosphonous acid aluminum salt
(F2- ■7) ：亜リン酸アルミニウム塩  (F2- ■ 7): Aluminum phosphite
(F2- -8) ：次亜リン酸カルシウム  (F2- -8): Calcium hypophosphite
アンチモン含有ィ匕合物 (F3)  Antimony-containing compound (F3)
(F3-1)：三酸化アンチモン  (F3-1): Antimony trioxide
(F3-2)：アンチモン酸ナトリウム, [0129] 7.充填剤（G) (F3-2): Sodium antimonate, [0129] 7. Filler (G)
(G- l)：ガラス繊維（直径 13 /ζ πι、長さ 3mmのチョップドストランド）  (G- l): Glass fiber (Diameter 13 / ζ πι, length 3mm chopped strand)
(G- 2)：ガラス繊維（直径 10 μ m、長さ 3mmのチョップドストランド）。  (G-2): Glass fiber (chopped strand having a diameter of 10 μm and a length of 3 mm).
[0130] 8.耐熱安定剤 (H)  [0130] 8. Heat-resistant stabilizer (H)
ヒンダードフエノール系耐熱安定剤 (H I)  Hindered phenol heat-resistant stabilizer (HI)
(HI— 1)：ペンタエリスリトールテトラキス [3— (3, 5 ジ一 t—ブチル 4 ヒドロキ シフエ二ノレ）プロピオネート]  (HI-1): Pentaerythritol tetrakis [3— (3,5 Di-tert-butyl 4-hydroxyphenenoyl) propionate]
耐熱安定剤 (H2)  Heat stabilizer (H2)
(H2- 1)：ビス（2, 6 ジ—tーブチルー 4 メチルフエ-ル）ペンタエリスリトールジ ホスファイト  (H2-1): Bis (2, 6 di-tert-butyl-4-methylphenol) pentaerythritol diphosphite
(H2- 2)：テトラキス（2, 4 ジ一 t—ブチルフエ-ル） 4, 4，一ビフエ-レンホス ホナイト  (H2-2): Tetrakis (2, 4 di-t-butylphenol) 4, 4, 1-biphenolene phosphonite
(H2- 3)：リン酸二水素カルシウム  (H2-3): Calcium dihydrogen phosphate
(H2-4)：ハイド口タルサイト [DHT— 4A、協和化学工業 (株)製]。  (H2-4): Hyde mouth talcite [DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.].
[0131] 9.加工安定剤 (I) [0131] 9. Processing stabilizer (I)
(1- 1)：ポリエチレンワックス [サンワックス、三洋化成工業 (株)製]  (1-1): Polyethylene wax [Sunwax, Sanyo Chemical Industries, Ltd.]
(1- 2) :モンタン酸エステル [LUZA WAX,東洋ペトロライト (株)製] 10.反応性安定剤 ω  (1-2): Montanic acid ester [LUZA WAX, manufactured by Toyo Petrolite Co., Ltd.] 10. Reactive stabilizer ω
(J- 1)：ビスフエノール— Αジグリシジルエーテル [ェピコート 828、油化シェルェポ キシ (株)製]  (J-1): Bisphenol-Α diglycidyl ether [Epicoat 828, manufactured by Yuka Shellepoxy Co., Ltd.]
Q- 2) :ポリカルジイミド [カルポジライト HMV— 8CA、 日清紡績 (株)製]。  Q- 2): Polycardiimide [Carpolite HMV—8CA, manufactured by Nisshinbo Industries, Inc.].
[0132] (実施例 1〜32、比較例 1〜12) [0132] (Examples 1-32 and Comparative Examples 1-12)
ベース樹脂 (A)に、ハロゲン系難燃剤 (B)、有機'無機酸塩 (C)、電気特性向上剤 (D)、電気特性向上助剤 (E)、難燃助剤 (F)、充填剤 (G)、耐熱安定剤 (H)、加工 安定剤 (I)を表 1〜4に示す割合で混合した後、 30mm径の 2軸押出機により溶融混 合し榭脂組成物を調製した。この榭脂組成物を用いて射出成形機により所定の試験 片を成形し、難燃性（1. 6mm)及び電気特性を測定した。なお、比較例 10において は、酸性ピロリン酸ナトリウムによって樹脂組成物の押出調製時及び成型時に樹脂の 表 1 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 After mixing the agent (G), the heat stabilizer (H), and the processing stabilizer (I) in the ratios shown in Tables 1 to 4, a resin composition was prepared by melt mixing with a 30 mm diameter twin screw extruder. . Predetermined specimens were molded by an injection molding machine using this resin composition, and flame retardancy (1.6 mm) and electrical characteristics were measured. In Comparative Example 10, the resin composition was extruded with sodium acid pyrophosphate during extrusion preparation and molding of the resin composition. table 1
Figure imgf000044_0001
Figure imgf000044_0001
〔〕0133 [] 0133
。。都^^r ^¾^: l ύ〜, ^ . . Capital ^^ r ^ ¾ ^: l ύ ~, ^
表 2 Table 2
Figure imgf000045_0001
Figure imgf000045_0001
^ 表 3 ^ Table 3
Figure imgf000046_0001
Figure imgf000046_0001
4] Four]
表 4 Table 4
Figure imgf000047_0001
Figure imgf000047_0001
(実施例 33〜48)  (Examples 33 to 48)
ベース樹脂 (Α)に、ハロゲン系難燃剤 (Β)、有機'無機酸塩 (C)、電気特性向上剤 (D)、電気特性向上助剤 (Ε)、難燃助剤 (F)、充填剤 (G)、耐熱安定剤 (Η)、加工 安定剤 (1)、反応性安定剤 ωを表 5に示す割合 (重量部)で混合し、押出機により混 練押出してペレット状の榭脂組成物を調製した。得られたペレットを用いて、射出成 形により試験用成形品を作製し、燃焼性（1. 6mm)及び耐トラッキング性 (比較トラッ キング指数)を評価した。結果を表 5に示す。  Filling base resin (Α) with halogen flame retardant (Β), organic 'inorganic acid salt (C), electrical property improver (D), electrical property improver (Ε), flame retardant aid (F), Mixing agent (G), heat-resistant stabilizer (、), processing stabilizer (1), reactive stabilizer ω in the proportions (parts by weight) shown in Table 5, and kneading and extruding with an extruder, pelletized resin A composition was prepared. Using the obtained pellets, test molded articles were produced by injection molding and evaluated for flammability (1.6 mm) and tracking resistance (comparative tracking index). The results are shown in Table 5.
[表 5] 室室) it 49581314〜〜 [Table 5] (Room) it 49581314 ~
表 5
Figure imgf000048_0001
Table 5
Figure imgf000048_0001
ベース樹脂 (A)に、ハロゲン系難燃剤 (B)、有機'無機酸塩 (C)、電気特性向上剤 (D)、電気特性向上助剤 (E)、難燃助剤 (F)、充填剤 (G)、耐熱安定剤 (H)、加工 安定剤 (I)を表 6に示す割合 (重量部)で混合し、押出機により混練押出してペレット 状の榭脂組成物を調製した。得られたペレットを用いて、射出成形により試験用成形 品を作製し、燃焼性 (0. 8mm)及び耐トラッキング性 (比較トラッキング指数)を評価 した。結果を表 6に示す。 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.
[表 6][Table 6]
Figure imgf000049_0001
Figure imgf000049_0001

Claims

請求の範囲 The scope of the claims
[1] ベース榭脂 (A)と、ハロゲン系難燃剤 (B)と、有機ホスフィン酸塩 (C1)および塩基 性窒素含有化合物のォキソ酸塩 (C2)から選択された少なくとも 1種の有機'無機酸 塩 (C)と、電気特性向上剤 (D)とで構成され、カゝっ電気特性の向上した難燃性樹脂 組成物であって、前記電気特性向上剤 (D)が、ォレフィン系榭脂、フッ素系榭脂およ び周期表第 4族金属化合物から選択された少なくとも 1種で構成されて!ヽる難燃性榭 脂組成物。  [1] At least one organic selected from a base resin (A), a halogenated flame retardant (B), an organic phosphinate (C1) and an oxo acid salt of a basic nitrogen-containing compound (C2) A flame retardant resin composition comprising an inorganic acid salt (C) and an electrical property improver (D), wherein the electrical property enhancer (D) is an olefin-based resin composition. A flame retardant resin composition comprising at least one selected from a resin, a fluorine-based resin, and a Group 4 metal compound of the periodic table!
[2] ベース榭脂 (A)が、ポリエステル系榭脂、ポリアミド系榭脂、ポリカーボネート系榭 脂、ポリフエ二レン才キシド系榭脂、ポリフエ二レンスルフイド系榭脂、スチレン系榭脂 、及びビュル系榭脂から選択された少なくとも 1種の熱可塑性榭脂で構成されている 請求項 1記載の榭脂組成物。  [2] Base resin (A) is polyester-based resin, polyamide-based resin, polycarbonate-based resin, polyphenylene-oxide-based resin, polyphenylene sulfide-based resin, styrene-based resin, and bull-based resin The rosin composition according to claim 1, which is composed of at least one thermoplastic rosin selected from rosin.
[3] ベース榭脂（A)が、 1, 4—シクロへキサンジメチレンテレフタレート、 C アルキレ  [3] Base resin (A) is 1,4-cyclohexanedimethylene terephthalate, C alkylene
2-4 ンテレフタレート及び C アルキレンナフタレートから選択された少なくとも 1種の単  2-4 At least one simple substance selected from terephthalate and C alkylene naphthalate
2-4  2-4
位を有するホモ又はコポリエステルで構成されている請求項 1記載の榭脂組成物。  The rosin composition according to claim 1, which is composed of a homo- or copolyester having a position.
[4] ベース榭脂 (A)力 ポリブチレンテレフタレート、ブチレンテレフタレート単位を主成 分とするコポリエステル、ポリプロピレンテレフタレート、プロピレンテレフタレート単位 を主成分とするコポリエステル、ポリエチレンテレフタレート、およびエチレンテレフタ レート単位を主成分とするコポリエステルカゝら選択された少なくとも 1種で構成されて V、る請求項 1記載の榭脂組成物。 [4] Base resin (A) Strength Polybutylene terephthalate, copolyester mainly composed of butylene terephthalate units, polypropylene terephthalate, copolyester mainly composed of propylene terephthalate units, polyethylene terephthalate, and ethylene terephthalate units 2. The resin composition according to claim 1, comprising at least one selected from the group consisting of copolyesters as a main component.
[5] ハロゲン系難燃剤 (B)が、臭素含有アクリル系榭脂、臭素含有スチレン系榭脂、臭 素含有ポリカーボネート系榭脂、臭素含有エポキシ化合物、臭素化ポリアリールエー テル化合物、臭素化芳香族イミド化合物、臭素化ビスァリール化合物および臭素化ト リ（ァリールォキシ)トリアジンィ匕合物力も選択された少なくとも一種の臭素原子含有 難燃剤である請求項 1記載の榭脂組成物。 [5] Halogen-based flame retardant (B) contains bromine-containing acrylic resin, bromine-containing styrene resin, odor-containing polycarbonate resin, bromine-containing epoxy compound, brominated polyarylether compound, brominated aroma 2. The resin composition according to claim 1, which is at least one bromine atom-containing flame retardant having a selected group imide compound, brominated biaryl compound, and brominated triaryl compound.
[6] ハロゲン系難燃剤 (B)が、臭素化ポリベンジル (メタ)アタリレート系榭脂、臭素化ス チレン系榭脂、臭素化ビスフエノール型ポリカーボネート榭脂、臭素化ビスフエノール 型エポキシ榭脂、臭素化ビスフエノール型フエノキシ榭脂及びアルキレンビス臭素化 フタルイミドから選択された少なくとも一種である請求項 1記載の榭脂組成物。 [6] Halogen flame retardant (B) is a brominated polybenzyl (meth) acrylate resin, brominated styrene resin, brominated bisphenol type polycarbonate resin, brominated bisphenol type epoxy resin, 2. The resin composition according to claim 1, wherein the resin composition is at least one selected from brominated bisphenol type phenoxy resin and alkylenebisbrominated phthalimide.
[7] 有機ホスフィン酸塩 (C1)が、置換基を有して!/、てもよ 、脂肪族ホスフィン酸塩、及 び Z又は置換基を有して 、てもよ 、脂環族ホスフィン酸塩である請求項 1記載の榭 脂組成物。 [7] The organic phosphinate (C1) has a substituent! /, May be an aliphatic phosphinate, and Z or may have an alicyclic phosphine The resin composition according to claim 1, which is an acid salt.
[8] 有機ホスフィン酸塩（C1)力 置換基を有して!/、てもよ 、ジアルキルホスフィン酸、 置換基を有して 、てもよ 、ジシクロアルキルホスフィン酸、置換基を有して!/、てもよ！/ヽ アルキレンホスフィン酸、置換基を有していてもよいアルケ-レンホスフィン酸、置換 基を有して 、てもよ 、（ビ）シクロアルキレンホスフィン酸、及び置換基を有して ヽても よ!、アルカンビス（アルキルホスフィン酸）力 選択された有機ホスフィン酸と、周期表 第 1族金属、周期表第 2族金属、周期表第 4族金属、周期表第 7族金属、周期表第 8 族金属、周期表第 10族金属、周期表第 11族金属、周期表第 12族金属、周期表第 13族金属、周期表第 14族金属、周期表第 15族金属及びアミノトリアジンィ匕合物力も 選択された少なくとも一種との塩であり、ォキソ酸塩 (C2)が、縮合リン酸、硫酸および ピロ硫酸力 選択された少なくとも 1種のォキソ酸と、アンモニア、尿素化合物、グァ 二ジンィ匕合物及びアミノトリアジンィ匕合物力も選択された少なくとも一種の塩基性窒 素含有ィヒ合物との塩である請求項 1記載の榭脂組成物。  [8] Organic phosphinic acid salt (C1) having a substituent! /, Or dialkylphosphinic acid, having a substituent, dicycloalkylphosphinic acid, having a substituent /! / ヽ Alkylenephosphinic acid, optionally substituted alkene-phosphinic acid, having a substituent, (bi) cycloalkylenephosphinic acid, and having a substituent Yo !, Alkanebis (alkylphosphinic acid) force Selected organic phosphinic acid and periodic table Group 1 metal, Periodic table Group 2 metal, Periodic table Group 4 metal, Periodic table Group 7 metal, Periodic table Group 8 Group metal, Periodic table Group 10 metal, Periodic table Group 11 metal, Periodic table Group 12 metal, Periodic table Group 13 metal, Periodic table Group 14 metal, Periodic table Group 15 metal and Aminotriazine combination It is also a salt with at least one selected physical strength, and oxoacid salt (C2) is condensed phosphoric acid, sulfuric acid and pyrosulfuric acid power, at least one selected oxoacid, ammonia, urea compound, guanidine Select compound and aminotriazine compound power榭脂 composition according to claim 1, wherein a has been at least one basic nitrogen-containing I salt with human compounds.
[9] 有機ホスフィン酸塩（C1)力 置換基を有して!/、てもよ 、ジアルキルホスフィン酸、 置換基を有して 、てもよ 、ジシクロアルキルホスフィン酸、置換基を有して!/、てもよ！/ヽ アルキレンホスフィン酸、置換基を有していてもよいアルケ-レンホスフィン酸、及び 置換基を有して 、てもよ 、アルカンビス (アルキルホスフィン酸)から選択された有機 ホスフィン酸と、周期表第 2族金属、周期表第 13族金属、メラミン、メラム、メレム、お よびメロン力も選択された少なくとも一種との塩であり、ォキソ酸塩 (C2) 1S ポリリン酸 とアミノトリアジンィ匕合物との塩、硫酸とアミノトリアジンィ匕合物との塩、ピロ硫酸とァミノ トリアジンィ匕合物との塩、及び縮合リン酸アミドから選択された少なくとも 1種である請 求項 1記載の榭脂組成物。  [9] Force of organic phosphinate (C1) having a substituent! /, May be a dialkylphosphinic acid, having a substituent, may be a dicycloalkylphosphinic acid, having a substituent /! / ヽ Alkylenephosphinic acid, alkene phosphinic acid optionally having substituent, and organic phosphinic acid having substituent and selected from alkanebis (alkylphosphinic acid), and periodic table Group 2 metal, Group 13 metal of periodic table, melamine, melam, melem, and at least one salt selected with melon power, and oxo acid salt (C2) 1S polyphosphoric acid and aminotriazine compound The resin composition according to claim 1, which is at least one selected from the group consisting of a salt of sulfuric acid and an aminotriazine compound, a salt of pyrosulfuric acid and an aminotriazine compound, and a condensed phosphoric acid amide. object.
[10] 有機 ·無機酸塩 (C)が、有機ホスフィン酸塩 (C1)およびォキソ酸塩 (C2)で構成さ れて 、る請求項 1記載の榭脂組成物。  [10] The resin composition according to claim 1, wherein the organic / inorganic acid salt (C) comprises an organic phosphinic acid salt (C1) and an oxo acid salt (C2).
[11] 電気特性向上剤 (D)が、ォレフィン系榭脂及び Z又は周期表第 4族金属化合物で 少なくとも構成されている榭脂組成物。 [11] A resin composition in which the electrical property improver (D) comprises at least olefin-based resin and Z or a Group 4 metal compound of the periodic table.
[12] 電気特性向上剤（D)が、 a— C ォレフィンの単独又は共重合体、 a—C ォレ [12] The electrical property improver (D) is an a-C olefin or a copolymer of a-C olefin.
2-3 2-3 フィン （メタ）アクリル酸共重合体、 α -C ォレフィン （メタ）アクリル酸 C アル  2-3 2-3 Fin (meth) acrylic acid copolymer, α-C olefin (meth) acrylic acid C Al
2-3 1-4 キルエステル共重合体、 a C ォレフィン—（メタ）アクリル酸グリシジルエステル 2-3 1-4 Kill ester copolymer, a C olefin-(meth) acrylic acid glycidyl ester
2-3  2-3
共重合体、酸変性ォレフィン系榭脂、フッ化 α— C ォレフィンの単独又は共重合  Copolymer, acid-modified olefin fin resin, fluorinated α-C olefin, homopolymer or copolymer
2-3  2-3
体、および酸ィ匕チタン力 選択された少なくとも 1種である請求項 1記載の榭脂組成 物。  2. The rosin composition according to claim 1, wherein the body and at least one selected from the group consisting of acid and titanium are selected.
[13] ベース榭脂 (A) 100重量部に対して、ハロゲン系難燃剤 (B)の割合が 2〜20重量 部であり、有機 ·無機酸塩 (C)の割合が 3〜30重量部である請求項 1記載の榭脂組 成物。  [13] Base resin (A) The proportion of halogenated flame retardant (B) is 2 to 20 parts by weight and the proportion of organic / inorganic acid salt (C) is 3 to 30 parts by weight with respect to 100 parts by weight of base resin The resin composition according to claim 1, wherein
[14] ハロゲン系難燃剤 (Β) 100重量部に対して、有機 ·無機酸塩 (C)の割合が 20〜50 0重量部であり、電気特性向上剤 (D)の割合が 10〜150重量部である請求項 1記載 の榭脂組成物。  [14] Halogen flame retardant (i) The proportion of organic / inorganic acid salt (C) is 20 to 500 parts by weight with respect to 100 parts by weight, and the proportion of electrical property improver (D) is 10 to 150. 2. The resin composition according to claim 1, wherein the composition is parts by weight.
[15] さらに、アミノトリアジンィ匕合物の塩、（含水)ケィ酸金属塩、（含水)ホウ酸金属塩、 ( 含水)スズ酸金属塩、金属酸化物、金属硫化物、及びアルカリ土類金属化合物から 選択された少なくとも一種の電気特性向上助剤 (Ε)を含む請求項 1記載の榭脂組成 物。  [15] In addition, aminotriazine compound salts, (hydrous) metal silicate, (hydrous) metal borate, (hydrous) metal stannate, metal oxides, metal sulfides, and alkaline earths 2. The resin composition according to claim 1, comprising at least one electrical property improving aid (Ε) selected from metal compounds.
[16] さらに、メラミンシァヌレート、タルク、カオリン、（含水）ホウ酸亜鉛、（含水）ホウ酸力 ルシゥム、（含水)スズ酸亜鉛、酸化亜鉛、硫化亜鉛、炭酸カルシウム、およびリン酸 水素カルシウム力 選択された少なくとも一種の電気特性向上助剤 (E)を含む請求 項 1記載の榭脂組成物。  [16] In addition, melamine cyanurate, talc, kaolin, (hydrous) zinc borate, (hydrous) boric acid power Lucium, (hydrous) zinc stannate, zinc oxide, zinc sulfide, calcium carbonate, and calcium hydrogen phosphate power The rosin composition according to claim 1, comprising at least one selected electrical property improving aid (E).
[17] さらに、芳香族化合物、リン含有化合物及びアンチモン含有化合物から選択された 少なくとも一種の難燃助剤 (F)を含む請求項 1記載の榭脂組成物。 [17] The resin composition according to claim 1, further comprising at least one flame retardant aid (F) selected from an aromatic compound, a phosphorus-containing compound, and an antimony-containing compound.
[18] 難燃助剤 (F)が、フエノール系榭脂、ポリフエ-レンォキシド系榭脂、芳香族ェポキ シ榭脂、フエノキシ榭脂、ポリフエ二レンスルフイド系榭脂、ポリカーボネート系榭脂、 ポリアリレート系樹脂、芳香族ポリアミド系榭脂、芳香族ポリエステル系榭脂及び芳香 族ポリエステルアミド系榭脂から選択された少なくとも一種である請求項 17記載の榭 脂組成物。 [18] The flame retardant aid (F) is a phenolic resin, a poly-phenoxide resin, an aromatic epoxy resin, a phenoxy resin, a polyphenylene sulfide resin, a polycarbonate resin, or a polyarylate type. 18. The resin composition according to claim 17, wherein the resin composition is at least one selected from a resin, an aromatic polyamide-based resin, an aromatic polyester-based resin, and an aromatic polyesteramide-based resin.
[19] 難燃助剤 (F)が、（縮合)リン酸エステル、（縮合)リン酸エステルアミド、（架橋)ァリ ールォキシホスファゼン、（亜）リン酸金属塩、次亜リン酸金属塩、有機（亜)ホスホン 酸エステル、有機（亜)ホスホン酸金属塩、及び有機（亜)ホスホン酸アミノトリアジン塩 から選択された少なくとも一種である請求項 17記載の榭脂組成物。 [19] Flame retardant aid (F) contains (condensed) phosphate ester, (condensed) phosphate ester amide, Selected from oxyphosphazenes, (phosphite) metal phosphates, hypophosphite metal salts, organic (phosphite) phosphonates, organic (phosphorous) phosphonate metal salts, and organic (phosphite) phosphonic acid aminotriazine salts 18. A resin composition according to claim 17, which is at least one kind.
[20] 難燃助剤 (F)力 アルキル (亜)ホスホン酸金属塩、（亜)リン酸金属塩及び次亜リン 酸金属塩から選択された少なくとも一種である請求項 17記載の榭脂組成物。 [20] The flame retardant composition according to claim 17, wherein the flame retardant aid (F) is at least one selected from an alkyl (phosphite) metal salt, a (phosphite) metal salt, and a hypophosphite metal salt. object.
[21] さらに、充填剤、耐熱安定剤、加工安定剤及び反応性安定剤カゝら選択された少な くとも一種の添加剤を含む請求項 1記載の榭脂組成物。 21. The resin composition according to claim 1, further comprising at least one additive selected from a filler, a heat stabilizer, a processing stabilizer and a reactive stabilizer.
[22] (i)試験片の厚み 0. 8mmで測定したとき、 UL94燃焼試験に準拠した難燃性が V[22] (i) Test piece thickness When measured at 0.8 mm, the flame resistance in accordance with UL94 flame test is V
— 1以上であり、かつ（ii) IEC 112に準拠した比較トラッキング指数が 350V以上であ る請求項 1記載の榭脂組成物。 — The resin composition according to claim 1, which is 1 or more and (ii) a comparative tracking index according to IEC 112 is 350 V or more.
[23] (0試験片の厚み 1. 6mmで測定したとき、 UL94燃焼性試験に準拠した難燃性が[23] (0 Test piece thickness When measured at 1.6 mm, the flame retardancy is in accordance with UL94 flammability test.
V—2以上であり、かつ G0IEC112に準拠した比較トラッキング指数が 500V以上で ある請求項 1記載の榭脂組成物。 2. The resin composition according to claim 1, wherein V is 2 or more and a comparative tracking index according to G0IEC112 is 500 V or more.
[24] (0試験片の厚み 1. 6mmで測定したとき、 UL94燃焼性試験に準拠した難燃性が[24] (0 Test piece thickness: When measured at 6 mm, the flame retardancy conforms to UL94 flammability test.
V - 0以上であり、かつ (ii)IEC 112に準拠した比較トラッキング指数が 650V以上で ある請求項 1記載の榭脂組成物。 2. The resin composition according to claim 1, wherein the composition is V-0 or more and (ii) the comparative tracking index according to IEC 112 is 650V or more.
[25] 請求項 1記載の榭脂組成物で形成された成形体。 [25] A molded body formed from the greave composition according to claim 1.
[26] 電気 ·電子部品、オフィスオートメーション機器部品、家電機器部品、自動車部品、 又は機械機構部品である請求項 25記載の成形体。  26. The molded body according to claim 25, which is an electrical / electronic part, an office automation equipment part, a household electrical equipment part, an automobile part, or a mechanical mechanism part.
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