JP2007070615A - Flame-retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin which is excellent in flame retardancy and moldability, and has improved electric characteristics. <P>SOLUTION: This flame-retardant resin composition having improved electric characteristics comprises a base resin (such as a polyester-based resin), a halogen-based flame retardant (such as a brominated polybenzyl (meth)acrylate-based resin, a brominated styrenic resin, or an alkylene bis brominated phthalimide), and at least one phosphate (C) selected from the polyphosphate (C1) of an amine compound comprising at least an aminotriazine condensation product, the polymetaphosphate (C2) of an aminotriazine and/or an aminotriazine condensation product, the salt (C3) of polyphosphoric acid having a number-average condensation degree of ≥20 with an aminotriazine and/or an aminotriazine condensation product, and the (poly)phosphate (C4) of a (poly)alkylene polyamine compound. In order to further improve electric characteristics, an olefinic resin [such asα-2 or 3C olefin-(meth)acrylate copolymer] may be contained. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition having excellent flame retardancy and improved electrical characteristics, and a molded body formed from the composition.

  Among thermoplastic resins, polyester resins such as polybutylene terephthalate (PBT) and polyamide resins have excellent mechanical properties, electrical properties, weather resistance, water resistance, chemical resistance, and solvent resistance. It is used for various applications such as electrical / electronic parts, mechanical mechanism parts, and automobile parts. On the other hand, as the application field expands, the thermoplastic resin is required to be flame retardant for safety as well as improved mechanical properties. In general, a method of making a flame retardant by adding a halogen-based flame retardant, a non-halogen-based flame retardant such as a phosphorus compound or a nitrogen-containing compound to a thermoplastic resin is known. Halogen-based flame retardants have higher flame retardancy than non-halogen-based flame retardants, can make the resin flame-retardant in a small amount, and can maintain the moldability of the resin.

  On the other hand, such a thermoplastic resin (composition) is required to have high electrical characteristics depending on the application in addition to flame retardancy. In order to improve the electrical characteristics of such a resin, for example, Japanese Patent Application Laid-Open No. 10-114854 (Patent Document 1) and Japanese Patent Application Laid-Open No. 10-273589 (Patent Document 2) include polyester resins, polyamide resins, halogens, and the like. Disclosed is a flame retardant resin molding composition having improved electrical properties containing an effective amount of pyro / polyphosphate metal salt to improve electrical properties (such as comparative tracking index) in a composition comprising a modified flame retardant Has been. However, even when a halogen-based flame retardant and pyro / polyphosphate are used in combination, the effect of improving the comparative tracking index is insufficient, and it is difficult to achieve both flame retardancy and electrical characteristics.

JP-A-10-251528 (Patent Document 3) discloses (a) a thermoplastic resin and (a) 100 parts by weight of the thermoplastic resin, and (b) 0.5 to 50 parts by weight of ammonium polyphosphate. And (c) 5-50 parts by weight of a halogen-based polymer flame retardant such as bromine-based polystyrene flame retardant, (d) 0-15 parts by weight of antimony trioxide, and (e) 0-50 parts by weight of an inorganic filler. There is disclosed a flame retardant thermoplastic resin composition having excellent tracking resistance, characterized by comprising: Further, JP-A-11-343389 (Patent Document 4) discloses (A) 100 parts by weight of a thermoplastic resin and (B) 0.5 to 50 parts by weight of a melamine salt of inorganic acid and / or condensed phosphoric acid amide. (C) 5-50 parts by weight of a flame retardant such as a halogen-based flame retardant such as a bromine-based polymer flame retardant, (D) 0-15 parts by weight of antimony trioxide, and (E) an inorganic filler 0-50 A flame retardant thermoplastic resin composition having excellent tracking resistance characteristics, characterized by comprising: parts by weight. However, the component (B) described in these documents, that is, ammonium polyphosphate, melamine salt of inorganic acid and condensed phosphoric acid amide have insufficient heat resistance, so that ammonia, melamine and the like are released during processing, Workability during material extrusion preparation and molding is significantly reduced.
JP-A-10-11854 (Claim 1 and Example) JP-A-10-273589 (Claim 1 and Example) JP-A-10-251528 (Claim 1) JP 11-343389 A (Claim 1)

  Accordingly, an object of the present invention is to provide a flame retardant resin composition that is excellent in flame retardancy and moldability and that can improve electrical characteristics, and a molded product thereof.

  Another object of the present invention is to provide a flame retardant resin composition having further improved electrical characteristics such as tracking resistance and a molded product thereof.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have improved the flame retardancy and electrical characteristics of the base resin without impairing moldability when a halogen-based flame retardant is combined with a specific phosphate. I found what I could do and completed the present invention.

  That is, the flame retardant resin composition of the present invention comprises a base resin (A), a halogen flame retardant (B), and a phosphate (C), and has improved electrical characteristics. A composition wherein the phosphate (C) is an aminotriazine condensate polyphosphate (C1), an aminotriazine and / or an aminotriazine condensate polymetaphosphate (C2), a number average condensation of 20 or more. It comprises at least one selected from a salt (C3) of a polyphosphoric acid having a degree and an aminotriazine and / or aminotriazine condensate and a (poly) phosphate (C4) of a (poly) alkylenepolyamine.

The base resin (A) is composed of at least one thermoplastic resin selected from polyester resins, polyamide resins, polycarbonate resins, polyphenylene oxide resins, polyphenylene sulfide resins, styrene resins, and vinyl resins. May be. In particular, the base resin (A) is composed of a homo- or copolyester having at least one unit selected from 1,4-cyclohexanedimethylene terephthalate, C _2-4 alkylene terephthalate and C _2-4 alkylene naphthalate. Typically, a polybutylene terephthalate, a copolyester having a butylene terephthalate unit as a main component, a polypropylene terephthalate, a copolyester having a propylene terephthalate unit as a main component, a polyethylene terephthalate unit, and an ethylene terephthalate unit as a main component. It may be composed of at least one selected from copolyesters.

  The halogen-based flame retardant (B) includes a bromine-containing acrylic resin (for example, brominated polybenzyl (meth) acrylate resin), a bromine-containing styrene resin (for example, a brominated product of a styrene resin, a brominated styrene-based monomer) Brominated styrene resins such as homopolymers or copolymers), bromine-containing polycarbonate resins (brominated bisphenol-type polycarbonate resins, etc.), bromine-containing epoxy compounds (brominated bisphenol-type epoxy resins, brominated bisphenol-type phenoxy resins) Brominated polyaryl ether compounds, brominated aromatic imide compounds [for example, alkylene bis brominated phthalimide (for example, ethylene bis brominated phthalimide), etc.], brominated bisaryl compounds and brominated tri (aryloxy) triazines Selected from compounds It may be at least one bromine-containing flame retardant.

The phosphate (C) is a melamine polyphosphate / melam / melem double salt (C1), a melamine polymetaphosphate (C2) which may contain a sulfur component, a melamine polyphosphate having a number average condensation degree of 40 or more ( C3) and (poly) phosphates (C4) of dialkylenediamines may be composed of at least one selected from melamine and typically from 0.05 to 1 per mol of phosphorus atom. Mole, Melam 0.3-0.6 mol and Melem 0.05-0.8 mol Melamine Melam-Melam-Melem Double Salt (C1a), phosphoric acid and 0 per mol of phosphoric acid A calcined product (C1b) obtained by calcining a reaction product of 0.05 to 20 mol of sulfuric acid and 1 to 4 mol of melamine with respect to 1 mol of phosphoric acid and sulfuric acid in total; 0 to 1.1 Polymetaphosphate melamine containing (C2), it has more than 40 number average degree of condensation, and melamine polyphosphate (C3) comprising melamine 1.1-2.0 mol per phosphorus atom 1 mol, and di _{C 2- It} may be composed of at least one selected from (poly) phosphates (C4) of _4- alkylenediamines.

  The proportion of the halogen flame retardant (B) may be about 3 to 30 parts by weight with respect to 100 parts by weight of the base resin (A), and the proportion of the phosphate (C) is 100 parts by weight of the base resin (A). It may be about 1 to 30 parts by weight with respect to parts. Moreover, about 30-250 weight part may be sufficient as the ratio of a phosphate (C) with respect to 100 weight part of halogenated flame retardants (B).

  The resin composition further includes an aromatic resin (an aromatic resin other than the base resin (A)), an antimony-containing compound, a fluorine-containing resin, and a phosphorus-containing compound other than the silicon-containing compound and the phosphate (C). It may contain at least one flame retardant aid (D) selected from Such flame retardant aids (D) include, for example, phenol resins, polyphenylene oxide resins, aromatic epoxy resins, phenoxy resins, polyphenylene sulfide resins, polycarbonate resins, polyarylate resins, aromatic polyamide resins. , Aromatic polyester resins and aromatic polyester amide resins, antimony oxides, antimonates, (poly) organosiloxanes, layered silicates, fluorine-containing monomers alone or copolymers, (condensed) phosphate esters (Or phosphate ester which may be condensed) [Used to mean phosphate ester (non-condensed phosphate ester) and condensed phosphate ester. In the same description, the same shall apply hereinafter), (condensed) phosphoric ester amide (or optionally condensed phosphoric ester amide) [phosphoric ester amide (non-condensed phosphoric ester amide) and condensed phosphoric ester amide] Use. The same applies to the same description. ], (Bridged) aryloxyphosphazenes (or aryloxyphosphazenes that may be bridged) [aryloxyphosphazenes (non-bridged aryloxyphosphazenes) and bridged aryloxyphosphazenes. The same shall apply hereinafter in the same description], (phosphite) metal phosphate (used to mean metal phosphite and metal phosphate, the same shall apply hereinafter), metal hypophosphite, organic (suboxide) ) Phosphonic acid compounds (used to mean organic phosphonic acid compounds and organic phosphonous acid compounds. The same applies hereinafter. In particular, organic (phosphorous) phosphonic acid metal salts, organic (phosphorous) phosphonic acid aminotriazine salts, organic ( Phosphinic acid esters) and organic phosphinic acid compounds (particularly, organic phosphinic acid salts such as organic phosphinic acid metal salts and organic phosphinic acid aminotriazine salts). The ratio of the flame retardant aid (D) may be about 1 to 150 parts by weight with respect to 100 parts by weight of the halogen flame retardant (B).

The resin composition further includes an olefin resin (E) [for example, α-C _2-3 olefin homo- or copolymer, α-C _2-3 olefin- (meth) acrylic acid ester copolymer (for example, , Α-C _2-3 olefin- (meth) acrylic acid C _1-4 alkyl ester copolymer, α-C _2-3 olefin- (meth) -acrylic acid glycidyl ester copolymer, etc., particularly α-C _{2 -3} olefin- (meth) acrylic ester copolymer) and at least one selected from acid-modified olefin resins]. The resin composition may further include at least selected from an electrical property improving aid (F), a filler (G), a heat stabilizer (H), a processing stabilizer (I), and a reactive stabilizer (J). A kind of additive may be included. For example, the resin composition further includes a salt of an aminotriazine compound (a salt other than the phosphate (C) such as melamine cyanurate), a (hydrated) metal silicate (a metal silicate (non-hydrated) In the same description, for example, talc, kaolin, etc.), (hydrous) metal borate (eg, (hydrous) zinc borate, (hydrous) ) Calcium borate), (hydrous) metal stannate (eg, (hydrous) zinc stannate), metal oxide (eg, zinc oxide), metal sulfide (eg, zinc sulfide), and alkali It may contain at least one electrical property improving aid (F) selected from earth metal compounds (for example, calcium carbonate, calcium hydrogen phosphate, etc.).

  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 flame retardancy based on the UL94 combustion test is V. -1 or more (particularly V-0 or more), and (ii) a comparative tracking index based on IEC (International Electrotechnical Commission, the same shall apply hereinafter) 112 may be 350 V or more (particularly 400 V or more). The resin composition of the present invention has [B] (i) flame retardancy based on UL94 flammability test of V-2 or higher (preferably V-1 or higher when measured with a test piece thickness of 1.6 mm. And (ii) the comparative tracking index based on IEC112 may be 400 V or more (particularly 600 V or more). The molded body formed with the said resin composition is also contained in this invention. Such a molded body may be an electric / electronic component, an office automation device component, a home appliance component, an automobile component, or a mechanical mechanism component.

  Since the flame retardant resin composition of the present invention combines a base resin, a halogen-based flame retardant, and a specific phosphate, it is excellent in flame retardancy and moldability and can improve electrical characteristics. Moreover, in the flame-retardant resin composition containing an olefin resin or the like, electrical characteristics such as tracking resistance can be further improved.

  The flame retardant resin composition of the present invention comprises at least a base resin (A), a halogen flame retardant (B), and a specific phosphate (C). In such a resin composition, not only flame retardancy and moldability (molding processability) but also electrical characteristics (such as tracking resistance) are improved.

(Base resin (A))
The base resin (A) is not particularly limited, and various resins such as thermoplastic resins [for example, polyester resins, polyamide resins, polycarbonate resins, polyphenylene oxide resins, polyphenylene sulfide resins, polyacetal resins, Ketone resin, polysulfone resin (for example, polysulfone), polyether ketone resin (polyether ketone, etc.), polyetherimide, polyurethane resin, polyimide, polyoxybenzylene, acrylic resin, styrene resin, vinyl Resin, thermoplastic elastomer, etc.], thermosetting resin (phenol resin, amino resin, thermosetting polyester resin, epoxy resin, silicone resin, vinyl ester resin, polyurethane resin, etc.). Hereinafter, typical base resins will be described in detail.

(Polyester resin)
The polyester-based resin is a homopolyester or a copolyester obtained by polycondensation of a dicarboxylic acid component and a diol component, polycondensation of oxycarboxylic acid or lactone, or polycondensation of these components. Preferred polyester resins usually include saturated polyester resins, particularly aromatic saturated polyester resins.

Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, dimer acid and other C _4-40 dicarboxylic acids, preferably C _4-14 dicarboxylic acid etc.), alicyclic dicarboxylic acid (C _8-12 dicarboxylic acid such as hexahydrophthalic acid, hexahydroterephthalic acid, hymic acid etc.), aromatic dicarboxylic acid [C _8-16 arene dicarboxylic acid (Phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc.), bisphenyldicarboxylic acid (4,4'-biphenyldicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylalkanedicarboxylic acid (4 , 4'-Diphenylmethanedicarboxylic Acid, etc.), 4,4′-diphenylketone dicarboxylic acid etc.]], derivatives thereof (derivatives capable of forming esters such as lower alkyl esters, acid anhydrides, etc.) and the like. The dicarboxylic acid components may be used alone or in combination of two or more. Furthermore, you may use together polyvalent carboxylic acid, such as trimellitic acid and a pyromellitic acid, as needed.

  Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid.

Examples of the diol component include aliphatic diols [for example, alkylene glycol (for example, C _2-12 alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, hexanediol, preferably C _{2 -10} alkylene glycol), polyalkylene glycol {glycols having a plurality of oxy C _2-4 alkylene units, such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, polytetramethylene glycol, etc.}, fats alicyclic diol [for example, 1,4-cyclohexanediol, _{C 5-6} cycloalkane _{C 1-2} alkanol such as cycloalkane alkanol (1,4 Le etc.), and hydrogenated bisphenol A], and the like. Hydroquinone, resorcinol, biphenol, bisphenols or their C _2-3 alkylene oxide adducts [2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4- (2-hydroxyethoxy) phenyl] ]) Propane or brominated derivatives thereof], or aromatic diols such as xylylene glycol may be used in combination. The diol components may be used alone or in combination of two or more. Furthermore, you may use together polyols, such as glycerol, a trimethylol propane, a trimethylol ethane, a pentaerythritol, as needed.

Preferred diol components include C _2-6 alkylene glycol (linear alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol), and oxyalkylene units having about 2 to 4 repetitions. Polyalkylene glycols [glycols containing poly (oxy-C _2-4 alkylene) units such as diethylene glycol], 1,4-cyclohexanedimethanol, and the like.

  Examples of the oxycarboxylic acid include oxybenzoic acid, oxynaphthoic acid, 4-carboxy-4'-hydroxybiphenyl, hydroxyphenylacetic acid, glycolic acid, D-, L- or D / L-lactic acid, oxycaproic acid, and the like. Oxycarboxylic acids or their derivatives are included.

Lactones include C _3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (eg, ε-caprolactone, etc.), and the like.

Preferred polyester-based resins include cycloalkane dialkylene arylate units (such as 1,4-cyclohexanedimethylene terephthalate units) and alkylene arylate units (alkylene terephthalate and / or alkylene naphthalate units such as C _2-4 alkylene terephthalate units, A homopolyester or copolymer having at least one unit selected from C _2-4 alkylene naphthalate units and the like [for example, having as a main component (for example, about 50 to 100% by weight, preferably about 75 to 100% by weight)] Polyester [for example, poly 1,4-cyclohexanedimethylene terephthalate, polyalkylene terephthalate (for example, polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybuty Terephthalate (PBT) poly C _2-4 alkylene terephthalate such as), polyalkylene naphthalate (e.g., polyethylene naphthalate, polypropylene naphthalate, poly C _2-4 alkylene naphthalate and polybutylene naphthalate) homopolymer polyesters such as 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 resins include polybutylene terephthalate resins containing butylene terephthalate units as main components [for example, polybutylene terephthalate, copolyesters having butylene terephthalate units as main components (polybutylene terephthalate copolyesters: for example, isophthalic acid Modified polybutylene terephthalate, etc.)], polypropylene terephthalate resin containing propylene terephthalate unit as a main component [for example, polypropylene terephthalate, copolyester having propylene terephthalate unit as main component (polypropylene terephthalate copolyester)], and ethylene terephthalate unit Polyethylene terephthalate resin contained as a main component [for example, polyethylene terephthalate, Copolyesters mainly composed of alkylene terephthalate units (polyethylene terephthalate copolyester: for example, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, 4-hydroxybenzoic acid-modified polyethylene terephthalate and the like). Polyester resins can be used alone or in combination of two or more.

In the copolyester, as a copolymerizable monomer, C _2-6 alkylene glycol (such as linear alkylene glycol such as ethylene glycol), polyalkylene having an oxyalkylene unit having about 2 to 4 repetitions Glycols (eg, glycols containing poly (oxy C _2-4 alkylene) units such as diethylene glycol and polytetramethylene glycol), C _4-12 aliphatic dicarboxylic acids (eg, glutaric acid, adipic acid, sebacic acid), alicyclic diols (Such as 1,4-cyclohexanedimethanol), aromatic diol [for example, C _2-3 alkylene oxide adducts of bisphenols such as 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, hydroquinone, Resorcin, 3,3'- or 4,3'- 4,4'-dihydroxydiphenyl, 1,4- or 2,6-dihydroxynaphthalene, etc.], aromatic dicarboxylic acid [(non) symmetric aromatic dicarboxylic acid (phthalic acid, isophthalic acid, 5-sulfoisophthalic acid monosodium salt ), Diphenyldicarboxylic acid (such as 4,4′-diphenyldicarboxylic acid), naphthalenedicarboxylic acid (such as 2,6-naphthalenedicarboxylic acid)], oxycarboxylic acid (oxybenzoic acid (3- or 4-hydroxybenzoic acid, etc.) And oxynaphthoic acid (6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, etc.), 4-carboxy-4'-hydroxybiphenyl, etc.). The polyester resin may be not only linear but also branched or crosslinked as long as the melt moldability is not impaired. The polyester resin may be a liquid crystal polyester. Further, polyester-based resins include amino group-containing monomers (for example, 3- or 4-aminophenol, 3- or 4-aminobenzoic acid, tetramethylene diamine, hexamethylene diamine, nonamethylene diamine, m-xylylene diamine. Also included are (liquid crystal) polyesteramide resins modified with amines).

  The polyester 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.

(Polyamide resin)
Polyamides include polyamides derived from diamines and dicarboxylic acids; aminocarboxylic acids, polyamides obtained by using diamines and / or dicarboxylic acids in combination; lactams, and optionally diamines and / or dicarboxylic acids; Polyamide derived by the combined use of. Polyamide includes copolyamide. Diamine, dicarboxylic acid, aminocarboxylic acid, and lactam can be used alone or in combination of two or more.

Examples of the diamine include C _3-10 aliphatic diamines such as tetramethylene diamine, hexamethylene diamine, and nonamethylene diamine, bis (4-aminocyclohexyl) methane, and bis (4-amino-3-methylcyclohexyl) methane. Semi-aromatic diamines (or aromatic fats) such as alicyclic diamines (such as bis (amino C _5-8 cycloalkyl) C _1-4 alkanes _optionally having substituents such as alkyl groups), metaxylylene diamines Group diamine). If necessary, an aromatic diamine such as phenylenediamine may be used in combination. Examples of the dicarboxylic acid include C _4-20 aliphatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, and dodecanedioic acid (C _6-16 alkane dicarboxylic acid and the like); dimerized fatty acid (dimer acid); Alicyclic dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid It is done. Examples of aminocarboxylic acids include C _4-20 aminocarboxylic acids such as aminoheptanoic acid, aminononanoic acid, and aminoundecanoic acid. Examples of the lactam include C _4-20 lactams such as caprolactam and dodecalactam.

Examples of polyamide resins include aliphatic polyamides such as polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11 and polyamide 12, and alicyclic diamines such as bis (aminocyclohexyl) C _1-3 alkanes. Alicyclic polyamides obtained from aliphatic dicarboxylic acids such as C _8-14 alkanedicarboxylic acids; aromatic dicarboxylic acids (eg terephthalic acid and / or isophthalic acid) and aliphatic diamines (eg hexamethylenediamine, nonamethylene) And polyamides obtained from aromatic and aliphatic dicarboxylic acids (for example, terephthalic acid and adipic acid) and aliphatic diamines (for example, hexamethylenediamine). Polyamide resins can be used alone or in combination of two or more.

  Among these polyamide resins, non-aromatic or aliphatic polyamides (polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12 etc.), semi-aromatic polyamides (polyamide MXD6, polyamide 9T etc.) ), Semi-aromatic copolymer polyamide (polyamide 6T / 6, polyamide 6T / 66, polyamide 6T / 11, polyamide 6T / 12, polyamide 6I / 6, polyamide 6I / 66, polyamide 6T / 6I, polyamide 6T / 6I / 6 Polyamide 6T / 6I / 66, polyamide 6T / M5T, etc.).

(Polycarbonate resin)
Polycarbonate resins include polymers obtained by reaction of dihydroxy compounds (such as alicyclic diols and bisphenol compounds) with carbonates such as phosgene or diphenyl carbonate. Examples of bisphenol compounds include bis (hydroxyaryl) C _1-10 alkanes such as bis (4-hydroxyphenyl) methane and 2,2-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) Bis (hydroxyaryl) C _4-10 cycloalkane such as cyclohexane; 4,4′-dihydroxydiphenyl ether; 4,4′-dihydroxydiphenyl sulfone; 4,4′-dihydroxydiphenyl sulfide; 4,4′-dihydroxydiphenyl ketone Is mentioned.

  Preferred polycarbonate-based resins include bisphenol A type polycarbonate.

(Polyphenylene oxide resin)
The polyphenylene oxide resin (polyphenylene ether resin) includes a homopolymer and a copolymer. Homopolymers include poly (2,6-dimethyl-1,4-phenylene) oxide, poly (2,5-dimethyl-1,4-phenylene) oxide, poly (2,5-diethyl-1,4-phenylene). Poly (mono, di or tri C _1-6 alkyl-phenylene) oxide such as phenylene) oxide, poly (mono or di C _6-20 aryl-phenylene) oxide, poly (mono C _1-6 alkyl-mono C _{6- 20} aryl-phenylene) oxide and the like.

  As the copolymer of polyphenylene oxide, a copolymer having two or more kinds of monomer units of the homopolymer (for example, 2,6-dimethyl-1,4-phenylene oxide unit and 2,3,6-trimethyl- Random copolymers having 1,4-phenylene oxide units, etc.), alkylphenol-modified benzeneformaldehyde resin blocks obtained by reacting benzeneformaldehyde resin (such as phenolic resin) or alkylbenzeneformaldehyde resin with alkylphenol such as cresol, and the like A modified polyphenylene oxide copolymer composed of a polyphenylene oxide block as a structure, a polyphenylene oxide or a copolymer thereof, a styrenic polymer and / or an unsaturated carboxylic acid or anhydride ((meth) acrylic acid, Such as water-maleic acid) and modified graft copolymers are grafted.

(Polyphenylene sulfide resin)
The polyphenylene sulfide resin (polyphenylene thioether resin) includes homopolymers and copolymers having a phenylene sulfide skeleton — (Ar—S) — [wherein Ar represents a phenylene group]. Examples of the phenylene group (—Ar—) include a substituted phenylene group (for example, an alkylphenylene group having a substituent such as a C _1-6 alkyl group, a phenyl group, in addition to a p-, m-, or o-phenylene group. An arylphenylene group having a substituent such as: -Ar-A ¹ -Ar- [wherein Ar represents a phenylene group, A ¹ represents a direct bond, O, CO, or SO ₂ ]. . The polyphenylene sulfide-based resin may be a homopolymer using the same repeating unit among phenylene sulfide units composed of such phenylene groups, or may be a copolymer containing different types of 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 phenylene sulfide groups. As the copolymer, a combination containing a p-phenylene sulfide group as a main repeating unit and an m-phenylene sulfide group is preferred, and a substantially linear copolymer containing 60 mol% (preferably 70 mol%) or more of p-phenylene sulfide groups. It may be.

  The polyphenylene sulfide-based resin may be a polymer obtained by oxidizing or thermally crosslinking a low molecular weight linear polymer, and is a polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional monomer. There may be. The polyphenylene sulfide resin also includes a branched or crosslinked polyphenylene sulfide resin obtained by polymerizing a monomer having three or more functional groups, and a resin composition obtained by blending this resin with the linear polymer.

  As the polyphenylene sulfide-based resin, polyphenylene sulfide, polybiphenylene sulfide (PBPS), polyphenylene sulfide ketone (PPSK), polybiphenylene sulfide sulfone (PPSS), and the like can be used. Polyphenylene sulfide resins can be used alone or in combination of two or more.

(Styrene resin)
Styrenic resins include styrene monomers (styrene, vinyltoluene, 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 etc. such as maleic anhydride] A graft copolymer, a styrene block copolymer, etc. are mentioned.

  Preferred styrenic resins include polystyrene (GPPS), styrene-methyl methacrylate copolymer, styrene- (meth) acrylic acid copolymer, styrene-acrylonitrile copolymer (AS resin), rubber component (polybutadiene, acrylic rubber). , Styrene-butadiene copolymer rubber, EPDM, EVA, etc.) and a graft copolymer obtained by polymerizing a styrene monomer and, if necessary, a copolymerizable monomer (acrylonitrile, methyl methacrylate, etc.) [impact polystyrene ( HIPS), ABS resin, MBS resin, etc.], copolymers composed of polystyrene blocks and diene or olefin blocks [e.g., styrene-butadiene-styrene (SBS) block copolymers, styrene-isoprene block copolymers, Styrene-isoprene-styrene ( IS) block copolymer, hydrogenated styrene-butadiene-styrene (SEBS) block copolymer, hydrogenated styrene-isoprene-styrene (SEPS) block copolymer, epoxidized SBS, epoxidized SIS and the like. .

(Vinyl resin)
Examples of vinyl resins include vinyl monomers (eg, vinyl esters such as vinyl acetate; chlorine-containing vinyl monomers (eg, vinyl chloride); vinyl ketones; vinyl ethers; vinyl amines such as N-vinyl carbazole, etc.) ) Or a copolymer thereof, or a copolymer with another copolymerizable monomer. Derivatives of the vinyl resins (for example, polyvinyl acetals such as polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral, and ethylene-vinyl acetate copolymers) can also be used.

  These resins or polymer compounds may be used alone or in combination of two or more.

  Preferred base resins include thermoplastic resins such as polyester resins, which may be liquid crystal polyesters, styrene resins, polyamide resins and polyphenylene oxide resins (particularly at least one selected from polyamide resins and polyester resins). Thermoplastic resins), and more preferably polyester resins (PBT resins, PPT resins, PET resins, etc.).

The number average molecular weight of the base resin is not particularly limited and is appropriately selected depending on the type and use of the resin, for example, 5 × 10 ³ to 200 × 10 ⁴ , preferably 1 × 10 ^{4 to} 150 × 10 ⁴ , Preferably, it can be selected from the range of about 1 × 10 ^{4 to} 100 × 10 ⁴ . When the base resin is a polyester resin, the number average molecular weight is, for example, 5 × 10 ^{3 to} 100 × 10 ⁴ , preferably 1 × 10 ⁴ to 70 × 10 ⁴ , and more preferably 1.2 × 10 ⁴ to. It may be about 30 × 10 ⁴ .

(Halogen flame retardant (B))
Organic halides can be used as the halogen-based flame retardant (B). The organic halide usually contains at least one selected from chlorine, bromine and iodine atoms.

Examples of halogen flame retardants include halogen-containing acrylic resins [halogenated polybenzyl (meth) acrylate resins such as polybrominated polybenzyl (meth) acrylates such as poly (pentabromobenzyl (meth) acrylate), poly (penta) Halogenated benzyl (meth) acrylates such as chlorobenzyl (meth) acrylate) or halogen-containing styrene resins [for example, styrene resins (styrene homo- or copolymers) are halogenated ( For example, halogenated styrenic resins (brominated polystyrene, chlorinated polystyrene, etc.) obtained by treatment with chlorine, bromine, bromine chloride, etc., homo- or copolymers of halogenated styrene monomers, etc.], halogen-containing Polycarbonate resin (brominated polycarbonate Halogenated polycarbonate such as chlorinated polycarbonate), halogen-containing epoxy compounds (halogenated epoxy resins such as brominated epoxy resins and chlorinated epoxy resins; halogenated phenoxy resins such as brominated phenoxy resins), halogenated polyaryl ether compounds [For example, bis (halogenated aryl) ethers such as octa to decabromodiphenyl ether and octa to decachlorodiphenyl ether (for example, bis (halogenated phenyl) ether); halogen-containing polyphenylene oxide resins such as brominated polyphenylene ether, etc.] , halogenated aromatic imide compounds [e.g., alkylene bis-brominated phthalimides (e.g., C _2-6 alkylene bis bromination Futarui such as ethylene bis-brominated phthalimide Donado) brominated aromatic imide compounds, such as (e.g., bisimide like compounds), etc.], halogenated bis-aryl compound [e.g., bis such brominated diphenyl (halogenated C _6-10 aryl); bis such brominated diphenyl methane (Halogenated C _6-10 aryl) C _1-4 alkane; halogenated bisphenols such as brominated bisphenol A or derivatives thereof (brominated polyesters obtained by polymerizing ethylene oxide adducts of halogenated bisphenols, etc.), halogenated Alicyclic hydrocarbons (bridged saturated or unsaturated halogenated alicyclic hydrocarbons such as halogenated polycycloalkadienes such as dodecachloropentacyclooctadeca-7,15-diene), trihalides ( Aryloxy) triazine compounds [eg bromine Brominated tri (aryloxy) triazine compounds, such as tri-phenoxy-triazine], and others. Halogen flame retardants can be used alone or in combination of two or more.

As the halogen-based flame retardant, a compound containing a chlorine atom and / or a bromine atom is preferable. In particular, an organic bromide containing a bromine atom [bromine-containing acrylic resin, bromine-containing styrene resin, bromine-containing polycarbonate resin (for example, Brominated bisphenol type polycarbonate resins such as brominated bisphenol A type polycarbonate resins), bromine-containing epoxy compounds [for example, brominated epoxy resins such as brominated bisphenol type epoxy resins (brominated bisphenol A type epoxy resins, etc.); Brominated phenoxy resins such as bisphenol type phenoxy resins (such as brominated bisphenol A type phenoxy resin)], brominated polyaryl ether compounds (such as bis (brominated aryl) ether compounds such as octabromodiphenyl ether), Iodination aromatic imide compounds, brominated bis-aryl compound, brominated tri etc. (aryloxy) triazine compounds] a bromine atom-containing flame retardants, etc.] is preferable. Among these bromine atom-containing flame retardants, brominated polybenzyl (meth) acrylate resins, brominated styrene resins [for example, brominated styrene resins such as brominated polystyrene (or brominated styrene resins) Brominated styrene monomer or copolymer (for example, polybrominated styrene, etc.), brominated bisphenol type polycarbonate resin, brominated bisphenol type epoxy resin, brominated bisphenol type phenoxy resin And at least one selected from alkylene bis brominated phthalimide (for example, C _2-6 alkylene bis brominated phthalimide such as ethylene bis brominated phthalimide) is preferable.

  The proportion of the halogen flame retardant is, for example, 3 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably about 7 to 20 parts by weight with respect to 100 parts by weight of the base resin.

(Phosphate (C))
The phosphate (C) is a polyphosphate (C1) of an aminotriazine condensate, an aminotriazine and / or a polymetaphosphate (C2) of an aminotriazine condensate, an aminotriazine having a number average condensation degree of 20 or more and / or Alternatively, it is composed of at least one selected from polyphosphate (C3) of aminotriazine condensate and (poly) phosphate (C4) of (poly) alkylenepolyamines.

(Polyphosphate (C1))
The polyphosphate (C1) is a salt of polyphosphoric acid (or polyphosphoric acid skeleton) and an amine composed at least of an aminotriazine condensate. In the polyphosphate (C1), the polyphosphoric acid (or polyphosphoric acid skeleton) is not particularly limited, and may be pyrophosphoric acid (diphosphoric acid), triphosphoric acid, tetraphosphoric acid, and the like, as will be described later. It may be formed or introduced by reaction of a phosphoric acid component (such as phosphoric acid) with aminotriazine.

  In the aminotriazine condensate, examples of the aminotriazine (triazine compound having an amino group) include 1,3,5-triazine having an amino group such as melamine and guanamine. As the aminotriazine, usually at least melamine (particularly melamine alone) is often used. Representative aminotriazine condensates include melamine condensates (eg, melam, melem, melon) and the like.

  Bases (amines) that form salts with polyphosphoric acid can be composed of at least an aminotriazine condensate and may contain other bases. For example, the base may be composed of an aminotriazine condensate and an aminotriazine (for example, melamine). In particular, the base may be composed of melamine, melam and melem.

  The polyphosphate (C1) is a commercially available product [for example, “PMP-100”, “PMP-200”, “PMP-300” of melamine, melam, and melem polyphosphate of Nissan Chemical Industries, Ltd., Polyphosphoric acid aminotriazine salts such as “PHOSMEL-100” and “PHOSMEL-200”] may be used, or prepared ones may be used. The polyphosphate (C1) may be prepared by reacting polyphosphoric acid with an aminotriazine condensate, and reacting (and firing) a phosphoric acid component (usually orthophosphoric acid) as an acid component with an aminotriazine. May be prepared. Usually, the polyphosphate (C1) is often a reaction (and calcination) product of a phosphoric acid component (particularly orthophosphoric acid) and an aminotriazine (particularly melamine). In the preparation of the reaction (and calcination) product, the ratio of each component (phosphoric acid, aminotriazine, etc.), reaction temperature (and calcination temperature), reaction time (and calcination time), etc. can be selected as appropriate. In addition, the polyphosphate (C1) obtained by the reaction of the phosphoric acid component does not necessarily have a polyphosphate skeleton. For example, a melamine / melem / melam polyphosphate containing a sulfur component described later may not have a polyphosphate skeleton depending on the amount of the sulfur component used as a raw material. In the present invention, as long as a phosphoric acid component is used as a raw material, a compound not having (or possibly having) a polyphosphoric acid skeleton is also included in the polyphosphate (C1).

  In the polyphosphate (C1), the ratio of the base (or amines) is, for example, 0.3 to 3 mol, preferably 0.4 to 2.5 mol, more preferably 0 with respect to 1 mol of the phosphorus atom. About 5 to 2 mol may be sufficient.

  Especially, in the salt of melamine, melam and melem (amines) and polyphosphoric acid (melamine, melam, melem double salt of polyphosphate), the ratio of each base (amines) constitutes polyphosphate Melamine may be about 0.05 to 1 mol, melam about 0.3 to 0.6 mol, and melem about 0.05 to 0.8 mol with respect to 1 mol of phosphorus atoms. In addition, a polyphosphate having a relatively low melamine content can also be suitably used. In such a polyphosphate, about 0.05 to 0.4 mol of melamine with respect to 1 mol of phosphorus atoms constituting the polyphosphate, The melam may be about 0.3 to 0.6 mol or melem about 0.3 to 0.8 mol. JP-A-10-306081 can be referred to for details of such polyphosphate (melamine, melam, melem double salt) containing melamine, melam and melem and a method for producing the same. For example, the melamine / melam / melem double salt of polyphosphate has a ratio of melamine of 2.0 to 4.0 mol per mol of (a) melamine and phosphoric acid (as an orthophosphoric acid equivalent). The step of obtaining the reaction product by mixing at a temperature of 0 to 330 ° C, and the reaction product obtained in the step (b) and (a) are performed at a temperature of 340 to 450 ° C for 0.1 to 30 hours. It can manufacture by going through the process of baking.

  Moreover, the polyphosphate (C1) may contain a sulfur component (or sulfur atom). For example, in the preparation of the polyphosphate described below, such a sulfur component is converted into a polyphosphate (C1) by using a phosphoric acid component (particularly phosphoric acid) and a sulfur component (particularly sulfuric acid) in combination as an acid component. It can be included. The polyphosphate (C1) containing such a sulfur component is, for example, phosphoric acid, about 0.05 to 20 mol of sulfuric acid with respect to 1 mol of this phosphoric acid, and 1 mol of phosphoric acid and sulfuric acid in total. It may be a fired product obtained by firing a reaction product with about 1 to 4 moles of melamine. Such a polyphosphate containing a sulfur component (melamine, melem, melam double salt of polyphosphoric acid containing a sulfur atom) is disclosed in Japanese Patent Application Laid-Open No. 10-306082, and a mixture containing each component in the above proportion is disclosed. The reaction product is obtained by reacting at a temperature of 0 to 330 ° C., and the reaction product obtained in this step is baked at a temperature of 340 to 400 ° C. for 0.1 to 30 hours.

  In addition, the solubility with respect to the water of polyphosphate (C1) in 25 degreeC may be about 0.01-0.1 g / 100mL, for example. Further, the pH of the aqueous slurry containing 10 wt% of the polyphosphate (C1) may be, for example, about 2 to 7 (for example, 2.5 to 7) at 25 ° C. In particular, the pH of an aqueous slurry containing 10 wt% of the melamine polyphosphate, melam, melem double salt may be about 4 to 7 at 25 ° C., for example.

  Preferable polyphosphate (C1) includes a melamine / melam / melem double salt polyphosphate which may contain a sulfur component [particularly (i) about 0.05 to 1 mol of melamine per mol of phosphorus atom, Melamine / melum / melem double salt containing about 0.3 to 0.6 mol of melam and about 0.05 to 0.8 mol of melem, and / or (ii) phosphoric acid and 1 mol of this phosphoric acid In contrast, a fired product obtained by firing a reaction product of about 0.05 to 20 mol of sulfuric acid and about 1 to 4 mol of melamine with respect to 1 mol of phosphoric acid and sulfuric acid in total.

(Polymetaphosphate (C2))
The polymetaphosphate (C2) is a salt of polymetaphosphate (or polymetaphosphate skeleton) and aminotriazine and / or aminotriazine condensate. In the polymetaphosphate (C2), the polymetaphosphoric acid (or polymetaphosphoric acid skeleton) is not particularly limited, and may be trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, etc. Acid or the like) and aminotriazine may be formed or introduced.

  Examples of aminotriazines and aminotriazine condensates include the compounds exemplified above (for example, melamine condensates such as melamine, melam, melem) and the like. Usually, polymetaphosphate (C2) is often a salt of melamine and / or melamine condensate.

  In addition, a polymetaphosphate (C2) may use a commercial item, and may use what was prepared. The polymetaphosphate (C2) may be prepared by reacting polymetaphosphoric acid with aminotriazine and / or aminotriazine condensate, and requires a phosphoric acid component (usually orthophosphoric acid) and an aminotriazine as an acid component. Depending on the case, it may be prepared by reacting (and baking) in the presence of a crosslinking agent or a binder (such as urea). Usually, polymetaphosphate (C2) is a reaction product obtained by reacting (and firing) a metaphosphoric acid component (especially orthophosphoric acid) and aminotriazine (especially melamine) in the presence of a crosslinking agent (such as urea). It may be a thing. In the preparation of the reaction (and calcination) product, the ratio of each component (phosphoric acid component, aminotriazine, etc.), reaction temperature (and calcination temperature), reaction time (and calcination time), etc. can be selected as appropriate.

  In the polymetaphosphate (C2), the proportion of aminotriazine and / or aminotriazine condensate is, for example, 0.3 to 2.5 mol, preferably 0.5 to 2 mol, relative to 1 mol of phosphorus atom. Preferably about 0.7-1.5 mol may be sufficient. In particular, polymetaphosphate (C2) is a melamine polymetaphosphate containing 0.8 to 1.2 mol (for example, 1.0 to 1.1 mol) of melamine (or melamine equivalent) with respect to 1 mol of phosphorus atom. It may be. Details of such a melamine polymetaphosphate and a method for producing the same can be referred to, for example, JP-A-10-81691. For example, the melamine polymetaphosphate comprises (a) melamine, a crosslinking agent (particularly urea), and an orthophosphoric acid aqueous solution containing 40% by weight or more of orthophosphoric acid. The urea is formed at a ratio of ˜1.5 moles and to a mole ratio of 0.1 to 1.5 moles of orthophosphoric acid at a temperature of 0 to 140 ° C. to form a reaction mixture, and A step of obtaining a powdery product comprising a double salt of orthophosphoric acid, melamine and urea by stirring the reaction mixture at a temperature of 0 to 140 ° C. while removing moisture; and (b) (a) step You may manufacture by performing the process baked for 0.1 to 30 hours at the temperature of 240-340 degreeC, preventing the solidification of the powdery product obtained by this.

  The solubility of polymetaphosphate (C2) in water may be, for example, about 0.01 to 0.1 g / 100 mL at 25 ° C. Further, the pH of the aqueous slurry containing 10% by weight of polymetaphosphate (C2) may be, for example, about 2.5 to 4.5 at 25 ° C.

  Preferred polymetaphosphate (C2) includes melamine polymetaphosphate (particularly, melamine polymetaphosphate containing 1.0 to 1.1 mol of melamine with respect to 1 mol of phosphorus atom).

(Polyphosphate (C3))
The polyphosphate (C3) is a salt of polyphosphoric acid having a number average condensation degree of 20 or more, preferably 40 or more, and aminotriazine and / or aminotriazine condensate. In particular, in the polyphosphate (C3), the value of the number average condensation degree is 20 to 200, preferably 40 to 150, as polyphosphoric acid. This number average degree of condensation is the average of the degree of condensation and is determined using ³¹ P solid state NMR.

  In the polyphosphate (C3), examples of the aminotriazine (triazine compound having an amino group) include 1,3,5-triazine having an amino group such as melamine and guanamine. As the aminotriazine, usually at least melamine (particularly melamine alone) is often used. In the polyphosphate (C3), examples of the aminotriazine condensate include melamine condensates (for example, melam, melem, melon) and the like. Preferable polyphosphate (C3) includes, for example, a polyphosphate (for example, melamine polyphosphate) containing at least melamine as a salt.

  In the polyphosphate (C3), the ratio of aminotriazine and / or aminotriazine condensate is, for example, 0.5 to 3 mol, preferably 0.8 to 2.5 mol (for example, with respect to 1 mol of phosphorus atom). 1 to 2.2 mol), more preferably about 1.1 to 2 mol (for example, 1.2 to 1.8 mol). In particular, in polyphosphate (C3) (particularly melamine polyphosphate), the proportion of melamine is 1.1 mol or more (for example, 1.1 to 2.0 mol), preferably 1 mol per mol of phosphorus atom. It may be 1.2 mol or more (for example, 1.2 to 1.8 mol).

  Further, the pH of the aqueous slurry containing 10% by weight of polyphosphate (C3) is, for example, 4.5 or more (for example, about 4.6 to 7), preferably 5.0 or more (for example, at 25 ° C.) About 5.0 to 6.5). The pH measurement method is not particularly limited. For example, 25 g of salt and 255 g of 25 ° C. pure water are placed in a container (for example, a 300 ml beaker), and the resulting slurry is stirred. You may measure pH.

  Further, in the polyphosphate (C3), the content of the water-soluble substance is less than 1% by weight of the whole polyphosphate (C3) (for example, about 0 to 0.5% by weight), preferably 0.1% by weight. (For example, about 0.001 to 0.09% by weight).

  The polyphosphate (C3) is not particularly limited, but usually an aminotriazine and / or aminotriazine condensate [for example, 1,3,5-aminotriazine compound such as melamine] and orthophosphoric acid, aminotriazine and / or Alternatively, a step of converting the aminotriazine condensate [for example, 1,3,5-aminotriazine such as melamine] to an orthophosphate, and further, the obtained orthophosphate is dehydrated by heat treatment to produce aminotriazine and / or amino It is obtained through a step of converting the triazine condensate into a polyphosphate. The heat treatment (heat treatment) may be performed at a temperature of 300 ° C. or higher (eg, about 305 to 400 ° C.), preferably 310 ° C. or higher (eg, about 310 to 330 ° C.). In addition to orthophosphates of aminotriazines and / or aminotriazine condensates, other phosphates of aminotriazines and / or aminotriazine condensates may be used, for example mixtures of orthophosphates and pyrophosphates. .

  The orthophosphate of aminotriazine and / or aminotriazine condensate can be prepared in various ways. In a preferred method, aminotriazine and / or aminotriazine condensate may be added to an aqueous solution of orthophosphoric acid. Further, orthophosphoric acid may be added to an aqueous slurry of aminotriazine and / or aminotriazine condensate.

  In addition, in the manufacturing method of polyphosphate (C3), the usage-amount of a melamine is 1 mol or more (for example, about 1.05-2.0 mol) with respect to 1 mol of phosphoric acid (orthophosphoric acid), It may be preferably 1.1 mol or more (for example, about 1.15 to 1.8 mol), more preferably 1.2 mol or more (for example, about 1.25 to 1.6 mol).

  The reaction time required to prepare the polyphosphate (C3) is generally 2 minutes or more, preferably 5 minutes or more and generally less than 24 hours.

  The details of such polyphosphate (C3) and its production method can also be referred to, for example, WO00 / 02869.

(Phosphate (C4))
Phosphate (C4) is a salt of (poly) phosphoric acid and (poly) alkylene polyamines as a base. In the phosphate (C4), (poly) phosphoric acid includes phosphoric acid (orthophosphoric acid), pyrophosphoric acid (diphosphoric acid), triphosphoric acid, tetraphosphoric acid, metaphosphoric acid (trimetaphosphoric acid, tetrametaphosphoric acid, Hexametaphosphoric acid, etc.). The phosphate (C4) may contain (poly) phosphoric acid as an acid alone or in combination of two or more.

  The (poly) alkylene polyamines may be a chain (linear or branched) compound or a cyclic compound. Note that the cyclic (poly) alkylene polyamine may form a ring in which adjacent nitrogen atoms are bonded to each other. Phosphate (C4) may contain (poly) alkylenepolyamines alone or in combination of two or more.

Typical (poly) alkylene polyamines include, for example, alkylene polyamines [for example, alkylene diamines (for example, diaminomethane, ethylene diamine, 1,2-propane diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, C _1-20 alkylene diamines such as 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, preferably C _2-10 alkylene diamines; pyrazolidine, etc.) ], Polyalkylene polyamines {for example, dialkylene polyamines [for example, diC _2-10 alkylene polyamines such as diethylenetriamine and piperazine, preferably diC _2-6 alkylene polyamines], Polyamines (eg, tri-C _2-10 alkylene polyamines such as triethylenetetramine), di- to _octaalkylene polyamines such as tetraalkylene polyamines (eg, tetra-C _2-10 alkylene polyamines such as tetraethylenepentamine)} Etc. In these (poly) alkylene polyamines, the hydrogen atom of the amino group or imino group may be substituted with a substituent (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group).

Preferred (poly) alkylene polyamines include dialkylene polyamines, especially dialkylene diamines (eg diC _2-4 alkylene such as piperazine, 2,5-dimethylpiperidine, 1,4-bis (aminoethyl) piperazine). Diamines).

  In the phosphate (C4), the ratio of (poly) alkylene polyamines is, for example, 0.1 to 3 mol, preferably 0.2 to 2.5 mol, and more preferably 1 to 3 mol, relative to 1 mol of (poly) phosphoric acid. Preferably it is about 0.3-2 mol, especially about 0.5-1.5 mol (for example, 0.8-1.2 mol).

  The phosphate (C4) only needs to contain at least (poly) alkylenepolyamines as a base, and other bases [for example, aminotriazines such as ammonia and melamine or condensates thereof (such as the compounds exemplified above), amino It may be a salt (double salt) containing a triazine derivative (such as an amino group-containing compound such as a compound described in JP-A No. 2003-26935).

  In addition, as (poly) alkylene polyamines (poly) phosphate (C4), commercially available products [Asahi Denka Kogyo Co., Ltd., "ADK STAB FP-2000", "ADK STAB FP-2100", "ADK STAB FP-2200" "Adekastab T-1063F" etc.], and compounds described in JP-A Nos. 2003-26935 and 2004-238568 may be used.

Preferred phosphates (C4) include dialkylenediamine polyphosphates (particularly di-C _2-4 such as polyphosphate piperazine salts, polyphosphate piperazine / aminotriazine double salts (polyphosphate piperazine / melamine double salts, etc.)). Polyphosphate of alkylenediamine] and the like.

  The proportion of the phosphate (C) is, for example, 1 to 50 parts by weight, preferably 3 to 40 parts by weight, and more preferably about 5 to 35 parts by weight with respect to 100 parts by weight of the base resin. The proportion of the phosphate (C) is, for example, 5 to 500 parts by weight, preferably 10 to 300 parts by weight, and more preferably 20 to 280 parts by weight with respect to 100 parts by weight of the halogen flame retardant (B). (For example, 30 to 250 parts by weight), particularly about 50 to 200 parts by weight may be used.

(Flame retardant aid (D))
The resin composition of the present invention may further contain a flame retardant aid (D). Flame retardant aids (D) include aromatic resins (phenolic resins, aniline resins, polyphenylene oxide resins, aromatic epoxy resins, polyphenylene sulfide resins, polycarbonate resins, polyarylate resins, aromatic polyamide resins. , Aromatic polyester resins (for example, aromatic polyester resins that may be liquid crystalline), aromatic polyester amide resins (for example, aromatic polyester amide resins that may be liquid crystalline), antimony, etc. -Containing compounds, molybdenum-containing compounds (such as molybdenum oxide), tungsten-containing compounds (such as tungsten oxide), bismuth-containing compounds (such as bismuth oxide), tin-containing compounds (such as tin oxide), iron-containing compounds (such as iron oxide), copper-containing Other than compounds (copper oxide, etc.) and phosphate (C) Phosphorus-containing compounds (phosphorus-containing compounds not belonging to the category of the phosphate (C)), silicon-containing compounds [(poly) organosiloxane, polysilsesquioxane, layered silicates, etc.], sulfur-containing compounds (organic sulfones) Acid compounds, metal salts of perfluoroalkanesulfonic acid, sulfamic acid compounds or salts thereof, and fluorine-containing resins. These flame retardant aids can be used alone or in combination of two or more.

  Among these flame retardant aids, in particular, aromatic resins (phenolic resins, polyphenylene oxide resins, aromatic epoxy resins, phenoxy resins, polyphenylene sulfide resins, polycarbonate resins, polyarylate resins, aromatic polyamide resins) Resin, aromatic polyester-based resin and aromatic polyesteramide-based resin), an antimony-containing compound, a fluorine-containing resin, a silicon-containing compound and a phosphorus-containing compound are preferably used. When an antimony-containing compound and / or a phosphorus-containing compound is used, flame retardancy can be further improved, and when a fluorine-containing resin and / or a silicon-containing compound is used, dripping can be effectively prevented.

  In addition, when using aromatic resin as a flame retardant adjuvant, resin different from base resin can be used. For example, when the base resin is a polyester resin (aromatic saturated polyester resin), as the aromatic resin, a non-polyester aromatic resin (for example, phenol resin, polyphenylene oxide resin, aromatic epoxy resin, phenoxy) Resin, polyphenylene sulfide resin, polycarbonate resin, polyarylate resin, aromatic polyamide resin, aromatic polyesteramide resin, and the like.

Examples of the antimony-containing compound include antimony oxide [antimony trioxide (Sb ₂ O ₃ etc.), antimony pentoxide (xNa ₂ O · Sb ₂ O ₅ · yH ₂ O (x = 0 to 1, y = 0 to 4). Etc.)], antimonates [metal antimonates (for example, alkali metal salts such as sodium antimonate, alkaline earth metal salts such as magnesium antimonate, etc.), ammonium antimonate, etc.]. These antimony-containing compounds can be used alone or in combination of two or more. Of the antimony-containing compounds, antimony oxide and alkali metal salts of antimonic acid are preferred.

  In addition, the antimony-containing compound may be used after surface treatment with a surface treatment agent such as an epoxy compound, a silane compound, an isocyanate compound and / or a titanate compound, if necessary.

  In addition, the average particle diameter of an antimony containing compound may be 0.02-5 micrometers, for example, Preferably about 0.1-3 micrometers may be sufficient.

  The fluorine-containing resin includes a fluorine-containing monomer alone or a copolymer, for example, a fluorine-containing monomer (tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether, etc.) Or a copolymer of fluorine-containing monomers and other copolymerizable monomers (olefin monomers such as ethylene and propylene, and acrylic monomers such as (meth) acrylate). Polymers and the like are included.

  Specific examples of the fluorine-containing resin include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene- Examples thereof include perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, and ethylene-chlorotrifluoroethylene copolymers. A fluorine-containing resin can be used individually or in combination of 2 or more types.

  The fluorine-containing resin may be used in the form of particles, and the average particle size may be, for example, about 10 to 5000 μm, preferably about 100 to 1000 μm, and more preferably about 100 to 700 μm.

Examples of silicon-containing compounds include smectite layered silicates such as montmorillonite, saponite, beidellite, hectorite, and fluorine hectorite, Li-type fluorine teniolite, Na-type fluorine teniolite, Li-type tetrasilicon fluorine mica, and Na-type tetrasilicon fluorine mica. And swellable synthetic fluorine mica, vermulite, halloysite and the like. The layered silicate is a modified layered silicate intercalated with an organic onium cation such as quaternary ammonium or quaternary phosphonium between layers, epoxy group, amino group, carboxyl group, acid anhydride group, oxazoline group. Modified layered silicates to which reactive functional groups such as the above are added (layered silicates treated with a silane coupling agent having reactive functional groups) and the like are also included. Furthermore, as other silicon-containing compounds, (poly) organosiloxanes, for example, polyorganosiloxanes such as polydimethylsiloxane and polymethylphenylsiloxane (organosiloxane homopolymers or copolymers) and the like can be mentioned. Among these (poly) organosiloxanes, organosiloxanes having a viscosity of about 1 × 10 ^{−3 to} 5 × 10 ⁻² m ² s ⁻¹ (25 ° C.) are preferable. These silicon-containing compounds can be used alone or in combination of two or more.

  Phosphorus-containing compounds include (condensed) phosphate esters [eg, resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), biphenyl bis (diphenyl phosphate), bisphenol-A (diphenyl phosphate), resorcinol bis (di- 2,6-xylyl phosphate), hydroquinone bis (di-2,6-xylyl phosphate), biphenyl bis (di-2,6-xylyl phosphate), bisphenol-A bis (di-2,6-xyl) Silyl phosphate), pentaerythritol diphenyl phosphate, pentaerythritol di-2,6-xylyl phosphate, 2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane-4-methanol-1-oxide And US Patent 4 No. 54775 and US Pat. No. 4,801,625, etc.], (condensed) phosphoric ester amides [for example, 1,4-piperazinediyltetraphenylphosphate, 1,4-piperazinediyltetra-2,6- Xylyl phosphate, N, N′-bis (neopentylenedioxyphosphinyl) piperazine, and phosphate esters described in JP-A-10-175985, JP-A-2001-139823, and JP-A-2001-35489 Amides, etc.], phosphonitrile compounds [eg, cyclic and / or chain phosphines such as aryloxyphosphazenes (phenoxyphosphazenes, tolyloxyphosphazenes, xylyloxyphosphazenes, phenoxytolyloxyphosphazenes, phenoxyxylylphosphazenes). Fazen compounds, their cross-linked phosphazene compounds (for example, phenoxyphosphazenes cross-linked with bisphenol residues) and the like described in WO99 / 19383, WO00 / 9518, WO02 / 98886 and WO04 / 24844 Phosphazene compounds, etc.], organic (sub) phosphonic acid compounds [for example, pentaerythritol dimethylphosphonate, pentaerythritol diethylphosphonate, pentaerythritol diphenylphosphonate, methylphosphonic acid esters (for example, trimethylolpropane ester of methylphosphonic acid, bis [2 -Methyl-2-oxo-5-ethyl-1,3-dioxa-2-phospha (V) cyclohexane-5-ylmethyl]), U.S. Pat. No. 3,789. No. 91, U.S. Pat. No. 3,849,368, U.S. Pat. No. 4,390,477, etc. Organic (sub) phosphonic acid esters, organic (sub) phosphonic acid metal salts, basic nitrogen compound salts of organic (sub) phosphonic acid (Melamine salts, guanamine salts, benzoguanamine salts and / or their condensate salts (organic (sub) phosphonic acid aminotriazine salts such as melamine condensates such as melam, melem, melon)), organic phosphinic acid compounds, and inorganic Phosphorus compounds (for example, red phosphorus, (phosphite) metal phosphates (calcium phosphite, aluminum phosphite, phosphoric acid / aluminum phosphite double salt, boron phosphate, etc.), metal hypophosphites (hypophosphite) Calcium phosphate, aluminum hypophosphite, etc.)).

  As the organic phosphinic acid compound, for example, an organic group-substituted phosphinic acid in which an organic group (such as an optionally substituted hydrocarbon group) is substituted for phosphinic acid, a polyvalent phosphinic acid (a plurality of polyvalent organic groups) Organic phosphinic acids such as polyphosphinic acids linked with phosphinic acid, and esters thereof (for example, 10-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-benzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and other phosphaphenanthrene oxides) or a salt thereof [at least one selected from metals, boron, ammonium and basic nitrogen-containing compounds With metal salt-forming components (including metal salts, boron salts (boryl compounds, etc.), ammonium salts, amino groups And salts with iodine-containing compound)] can be employed. In addition, the organic phosphinic acid compound (particularly, organic phosphinic acid or a salt thereof) seems to function as an electrical property improver in addition to the function as a flame retardant aid.

  Examples of metals that form organic phosphinates include Group 1 metals (alkali metals) (lithium, potassium, sodium, etc.), Group 2 metals (alkaline earth metals) (magnesium, calcium, barium, etc.) , Periodic table group 4 metals (titanium, zirconium etc.), transition metals (periodic table group 7 metals such as manganese; periodic table group 8 metals such as iron; periodic table group 9 metals such as cobalt; nickel etc. Periodic Table Group 10 Metals; 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 Group 14 Metals such as Tin, Antimony And periodic table group 15 metals. These metals can be used alone or in combination of two or more. The metal salt may be a hydrate salt such as a hydrate magnesium salt, a hydrate calcium salt, a hydrate aluminum salt, or a hydrate zinc salt. Metal salts also include salts in which the metal is partially oxidized (eg, titanyl salts, zirconyl salts, etc.). Examples of basic nitrogen-containing compounds that form salts include nitrogen-containing compounds having amino groups [aminotriazine compounds (melamine, guanamine, benzoguanamine and / or condensates thereof (melamine condensates such as melam, melem, melon, etc.) Etc.), guanidine compounds (eg guanidine etc.)], urea compounds (eg urea) 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. 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, and a melamine, melam, melem, and melon double salt.

  Of the metals and nitrogen-containing compounds that form these salts, Group 1 metal, Group 2 metal, Group 4 metal, Group 8 metal, Group 12 metal, Group 13 metal and aminotriazine compound of the periodic table ( Melamine, melamine condensate, etc.) are preferred.

  In the organic phosphinic acid salt, some or all of the acid groups of the organic phosphinic acid having an acid group (such as a carboxy group) as a substituent are salts (such as the salts exemplified above, for example, the same metal or nitrogen as phosphinic acid) Salt of the containing compound) may be formed (for example, may be carboxylated).

  The organic phosphinic acid can be substituted with a substituent {for example, a hydroxyl group, an unsaturated group [for example, a carbon-oxygen unsaturated bond-containing group such as a carboxyl group, an acyl group, an alkoxycarbonyl group (such as a methoxycarbonyl group)], an alkoxy group. Group (for example, methoxy group and the like) may be included. The organic phosphinic acid may have these substituents alone or in combination of two or more.

As typical organic phosphinic acid, for example, mono- or dialkylphosphinic acid having a substituent [for example, dialkylphosphinic acid such as diethylphosphinic acid; (hydroxymethyl) methylphosphinic acid, (hydroxyethyl) methylphosphinic acid, (hydroxy Hydroxyl group-containing dialkylphosphinic acids such as propyl) methylphosphinic acid, bis (hydroxymethyl) phosphinic acid, bis (hydroxyethyl) phosphinic acid, bis (hydroxypropyl) methylphosphinic acid; (methoxymethyl) methylphosphinic acid, bis (methoxy Alkoxy group-containing dialkylphosphinic acids such as methyl) phosphinic acid; (2-carboxyethyl) methylphosphinic acid, (2-carboxypropyl) methylphosphinic acid, bis (2-carboxyethyl) Carboxy group-containing dialkylphosphinic acids such as phosphinic acid and bis (2-carboxypropyl) phosphinic acid; (2-methoxycarbonylethyl) methylphosphinic acid, [2- (β-hydroxyethylcarbonyl) ethyl] methylphosphinic acid, (2-methoxycarbonylpropyl) methylphosphinic acid, bis (2-methoxycarbonylethyl) phosphinic acid, alkoxycarbonyl group-containing dialkylphosphinic acid such as bis (2-methoxycarbonylpropyl) phosphinic acid, etc.], having a substituent which may be alkylene phosphinic acid (e.g., 1-hydroxy-phospholane 1-oxide, 1-hydroxy-3-methyl-Hosuhosu Horan 1-oxide, such as 2-carboxy-1-hydroxy -1H- phospholane 1-oxide _{C 3- 8} Alkylene phosphinic acid (eg, 1-hydroxy-2,3-dihydro-1H-phosphole 1-oxide, 1-hydroxy-2,5-dihydro-1H) -Cyclo C _3-8 alkenylene phosphinic acid such as phosphole 1-oxide, 1-hydroxy-3-methyl-2,5-dihydro-1H-phosphole 1-oxide, etc.), optionally having a substituent (bi ) Cycloalkylenephosphinic acid (for example, 1,3-cyclobutylenephosphinic acid, 1,3-cyclopentylenephosphinic acid, 1,4-cyclooctylenephosphinic acid, 1,5-cyclooctylenephosphinic acid, etc. And C _4-10 cycloalkylenephosphinic acid).

  Moreover, as a typical organic phosphinic acid salt, a salt of the above organic phosphinic acid, for example, a salt of a mono- or dialkylphosphinic acid having a substituent [for example, (hydroxyethyl) methylphosphinic acid Ca salt, bis (2-hydroxy Ethyl) phosphinic acid Ca salt, (hydroxyethyl) methylphosphinic acid Ca salt, bis (2-hydroxyethyl) phosphinic acid Ca salt, [2- (β-hydroxyethylcarbonyl) ethyl] methylphosphinic acid Ca salt, (2- Carboxyethyl) methylphosphinic acid Ca salt, (2-methoxycarbonylethyl) methylphosphinic acid Ca salt and alkaline earth metal salts such as Mg salt corresponding to these calcium salts; diethylphosphinic acid Al salt, (hydroxyethyl) methyl Phosphinic acid Al salt, bis (2-hydroxyethyl) ) Aluminum such as phosphinic acid Al salt, bis (2-hydroxypropyl) phosphinic acid Al salt, [2- (β-hydroxyethylcarbonyl) ethyl] methylphosphinic acid Al salt, (2-carboxyethyl) methylphosphinic acid Al salt (Hydroxyethyl) methylphosphinic acid Ti salt, bis (2-hydroxyethyl) phosphinic acid Ti salt, bis (2-hydroxypropyl) phosphinic acid Ti salt, [2- (β-hydroxyethylcarbonyl) ethyl] methylphosphine Ti salts such as acid Ti salts and titanyl salts corresponding to these salts; Zn salts of (hydroxyethyl) methylphosphinic acid, Zn salts of bis (2-hydroxyethyl) phosphinic acid, Zn salts of bis (2-hydroxypropyl) phosphinic acid , [2- (β-hydroxyethylcarbonyl) Metal salt such as zinc salt such as til] methylphosphinic acid Zn salt, (2-carboxyethyl) methylphosphinic acid Zn salt; (hydroxyethyl) methylphosphinic acid melamine salt, bis (2-hydroxyethyl) phosphinic acid melamine salt, Bis (2-hydroxypropyl) phosphinic acid melamine salt, [2- (β-hydroxyethylcarbonyl) ethyl] methylphosphinic acid melamine salt, aminotriazine compounds such as melamine melam memel double salt corresponding to these melamine salts and And the like, an alkylene phosphinic acid salt optionally having a substituent [for example, alkaline earth metal salts (Ca salt, Mg salt etc.) of 1-hydroxyphosphorane 1-oxide, Al salt, Ti salt, Metal salts such as titanyl salt and Zn salt; melamine salt, melamine melam memel double salt Aminotriazine salts, etc.] and the like.

  Preferred organic phosphinic acid compounds include mono- or dialkylphosphinic acids having a substituent (hydroxyl group, carboxyl group, acyl group, alkoxycarbonyl group, alkoxy group, etc.) or salts thereof (particularly metal salts, aminotriazine salts), substituted Alkylenephosphinic acid or its salt which may have a group (especially metal salt, aminotriazine salt), alkenylenephosphinic acid which may have a substituent or a salt thereof (especially metal salt, aminotriazine salt) And (bi) cycloalkylenephosphinic acid or a salt thereof (particularly metal salt, aminotriazine salt) which may have a substituent.

  The organic phosphinic acid compounds are, for example, JP-A-55-5979, JP-A-8-73720, JP-A-9-278784, JP-A-11-236392, JP-A-2001-2686. JP 2004-238378 A, JP 2004-269526 A, JP 2004-269984 A, JP 2004-346325 A, JP 2001-513784 A, JP 2001-525327 A, JP No. 2001-525328, No. 2001-525329, No. 2001-540224, U.S. Pat. No. 4,180,495, U.S. Pat. No. 4,208,321, U.S. Pat. No. 4,208,322, U.S. Pat. No. 6,229,044, U.S. Pat. Compounds described in It may be use.

  Examples of organic (phosphorous) phosphonic acid compounds include, for example, JP-A-48-57988, JP-A-55-5979, JP-A-56-84750, JP-A-63-22866, Japanese Laid-Open Patent Application Nos. 1-226891, 2-180875, 4-234893, 7-224078, 7-247112, 8-59679, and 8 JP-A-245659, JP-A-9-272759, JP-A-2000-63843, JP-A-2001-2688, JP-A-2001-64438, JP-A-2001-64521, JP-A-2001-98161. No. 1, JP-A 2001-98273, JP-A 2001-106919, WO 00/11108, WO 01 / Compounds described in JP 7134 may also be mentioned.

  The flame retardant aid (D) may be composed of at least one selected from at least an aromatic resin, an antimony-containing compound, a silicon-containing compound, and a phosphorus-containing compound. The fluorine-containing resin is often combined with other flame retardant aids (for example, at least one selected from antimony-containing compounds, silicon-containing compounds, and phosphorus-containing compounds). When combining a fluorine-containing resin and another flame retardant aid, the proportion of the fluorine-containing resin is 3 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the other flame retardant aid. Preferably it may be about 10 to 20 parts by weight.

  In the present invention, the electrical characteristics of the base resin (A) can be improved without adding the flame retardant aid (D). In addition, the organic phosphinic acid compound as the flame retardant aid (D) includes an aminotriazine condensate polyphosphate (C1), an aminotriazine and / or an aminotriazine condensate polymetaphosphate (C2), and (poly). Often combined with at least one phosphate (C) selected from (poly) phosphates (C4) of alkylenepolyamines.

  The ratio of the flame retardant aid (D) is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, and more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the base resin (A). About a part. In particular, the ratio of the flame retardant aid (D) is, for example, 5 parts by weight or more (for example, 6 to 25 parts by weight), preferably 8 to 20 parts by weight, based on 100 parts by weight of the base resin (A). Preferably, it may be about 9 to 18 parts by weight (for example, 10 to 15 parts by weight).

  The proportion of the flame retardant aid (D) is, for example, 0.05 to 300 parts by weight (for example, 0.1 to 250 parts by weight), preferably 100 parts by weight of the halogen flame retardant (B), preferably 0.2 to 200 parts by weight (for example, 0.5 to 180 parts by weight), more preferably 1 to 150 parts by weight (for example, 5 to 140 parts by weight), particularly 10 to 130 parts by weight (for example, 20 to 120 parts by weight). Part), usually 30 to 110 parts by weight (for example, 50 to 100 parts by weight). The ratio (weight ratio) of the phosphate (C) and the flame retardant aid (D) is the former / the latter = 10/90 to 99.9 / 0.1, preferably 20/80 to 99/1. More preferably, it may be about 25/75 to 97/3.

(Olefin resin (E))
The resin composition of the present invention may further contain an olefin resin (E) as an electrical property improving resin. When an olefin resin is used, electrical characteristics (for example, tracking resistance) can be further improved.

Examples of the olefin resin include olefin monomers {ethylene-propylene, 1-butene, 3-methyl-1-pentene, 4-methyl-1-butene, 1-hexene, 1-octene and other α-olefins. (in particular, _{alpha-C 2-10} olefin); cyclic olefins [e.g., cyclobutene, cyclopentene, _(such as _{C 3-10} cycloalkene) cycloalkenes such as cyclohexene; crosslinked cyclic; _{C 3-10} cycloalkyne such cyclohexanol Shin Olefins (polycycloalkenes such as norbornene and tetradicyclododecene, dicycloalkadienes such as dicyclopentadiene); or derivatives thereof (alkyl-substituted, alkylidene-substituted, alkoxy-substituted, acyl-substituted, carboxy-substituted) Etc.) etc.] etc.} homopolymer or copolymer, The olefin monomer or polymer and a copolymerizable monomer [vinyl monomer such as (meth) acrylic acid or a salt thereof (metal salt, etc.), (meth) acrylic acid ester ((meth) Acrylic monomers such as alkyl acrylate, glycidyl (meth) acrylate, etc .; vinyl acid monomers such as vinyl acetate; fumaric acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, Copolymers (Random Copolymer) with α, β-unsaturated dicarboxylic acid monomers such as (anhydrous) citraconic acid and (anhydrous) nadic acid; vinyl cyanide monomers such as (meth) acrylonitrile And a copolymer, a block copolymer, a graft copolymer, and the like.

Specific examples of the olefin resin include α-olefin resins [for example, homo- or copolymers of α-C _2-3 olefins such as polyethylene, polypropylene, propylene-ethylene copolymers; ethylene- (meta ) Acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid metal salt copolymer, ethylene- (meth) acrylic acid ester copolymer (ethylene-ethyl acrylate copolymer) Copolymers of α-C _2-3 olefins and copolymerizable monomers such as ethylene- (meth) acrylic acid alkyl ester copolymers; ethylene- (meth) acrylic acid glycidyl ester copolymers, etc.] Etc.], acid-modified olefin resin [for example, olefin resin (olefin homo- or copolymer), acid component (for example, Acid-modified olefin resins modified with α, β-unsaturated carboxylic acid (such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, etc.) and / or acid anhydrides thereof] And cyclic olefin resins (for example, cyclic olefin homopolymer, α-C _2-10 olefin-cyclic olefin copolymer, etc.). Olefin resins can be used alone or in combination of two or more. Among these olefin resins, α-C _2-3 olefin- (meth) acrylic acid ester copolymer [for example, α-C _2-3 olefin- (meth) acrylic acid C _1-4 alkyl ester copolymer] (Especially ethylene-ethyl acrylate copolymer), α-C _2-3 olefin- (meth) acrylic acid glycidyl ester copolymer (especially ethylene- (meth) acrylic acid glycidyl ester copolymer) and the like], An acid-modified olefin resin [for example, an olefin resin obtained by modifying an α-C _2-3 olefin alone or a polymer with an acid component (particularly, acid-modified polypropylene) or the like is preferable.

The number average molecular weight of the olefin resin is not particularly limited, but is, for example, about 300 to 20 × 10 ⁵ , preferably about 500 to 10 × 10 ⁴ .

  The proportion of the olefinic resin can be selected from the range of 0 to 50 parts by weight with respect to 100 parts by weight of the base resin, for example, 0 to 30 parts by weight (for example, 0.5 to 25 parts by weight), preferably 1 to 20 parts by weight (for example, 1.5 to 18 parts by weight), more preferably 2 to 15 parts by weight (for example, 2 to 15 parts by weight), particularly about 3 to 15 parts by weight (for example, 5 to 15 parts by weight). There may be. The ratio of the olefin resin is, for example, 0 to 300 parts by weight (for example, 0.5 to 250 parts by weight), preferably 1 to 200 parts by weight (for example, 5 parts by weight) with respect to 100 parts by weight of the halogen flame retardant. -180 parts by weight), more preferably 10-160 parts by weight (for example, 20-150 parts by weight), and particularly about 30-120 parts by weight (for example, 50-100 parts by weight). Furthermore, the ratio of the olefin resin is, for example, 1 to 150 parts by weight, preferably 5 to 100 parts by weight, with respect to 100 parts by weight of the total amount of the halogen-based flame retardant (B) and the phosphate (C). The amount is preferably about 10 to 90 parts by weight.

(Other additives)
The flame retardant resin composition of the present invention further includes other additives, for example, electrical property improvement aids (additives for improving electrical properties), other flame retardants (nitrogen-based, phosphorus-based flame retardants, etc.). , Fillers, stabilizers (ultraviolet absorbers, weather resistance (light) stabilizers, heat stabilizers, processing stabilizers, phosphorus stabilizers, reactive stabilizers, etc.), antistatic agents, lubricants, mold release agents, crystallization Nucleating agents, plasticizers, colorants (dyes, pigments, etc.), lubricants, anti-dripping agents, etc. may be contained. These other additives can be used alone or in combination of two or more. Among these additives, the resin composition may contain an electrical property improving aid, a filler, a heat stabilizer, a processing stabilizer, and the like.

(Electrical property improvement aid (F))
Examples of the electrical property improving aid (F) include non-phosphorus nitrogen-containing compounds [aminotriazine compounds (melamine; guanamine; melamine condensates such as melam, melem, etc.), salts of aminotriazine compounds (the above aminotriazine compounds) Organic acid or inorganic acid salt of, for example, cyanuric acid salt of melamine cyanurate, etc.], inorganic acid metal compound {for example, inorganic acid metal salt [for example, (hydrous) silicate metal salt (talc, kaolin, silica , Diatomaceous earth, clay, wollastonite, etc.), (hydrated) metal borate (eg, (hydrated) zinc borate, (hydrated) calcium borate, (hydrated) aluminum borate), (hydrated) stannic acid Metal salts (for example, (hydrated) zinc stannate), sulfate metal salts (calcium sulfate, magnesium sulfate, barium sulfate, etc.), etc. }, Metal oxides (magnesium oxide, iron oxide, titanium oxide, zinc oxide, alumina, etc.), metal hydroxides (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate (boehmite), etc.), Metal sulfides (such as zinc sulfide, molybdenum sulfide, tungsten sulfide), alkaline earth metal compounds (for example, alkaline earth metal salts (for example, alkaline earth metal carbonates such as calcium carbonate and calcium hydrogen phosphate), etc.) Inorganic metal compounds are mentioned. These electrical property improving aids can be used alone or in combination of two or more.

  The proportion of the electrical property improving aid is, for example, 0 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 1.5 to 15 parts by weight (for example, 2 to 15 parts) with respect to 100 parts by weight of the base resin. Part by weight). The proportion of the electrical property improving aid is, for example, about 0 to 300 parts by weight, preferably about 0.5 to 200 parts by weight, and more preferably about 1 to 150 parts by weight with respect to 100 parts by weight of the halogen flame retardant. There may be.

(Filler (G))
Examples of the filler (G) include conventional fiber-like, plate-like, and powder-like 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-like filler include glass flakes, mica, graphite, and various metal foils. Powdered 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 (such as milled fiber, glass beads, and glass balloons). , Silicate (talc, kaolin, silica, diatomaceous earth, clay, wollastonite, etc.), sulfide (molybdenum disulfide, tungsten disulfide, etc.), carbide (fluorinated graphite, silicon carbide, etc.), activated carbon, boron nitride Etc. can be exemplified. A filler can be used individually or in combination of 2 or more types.

  The amount of the filler used is, for example, 0 to 100 parts by weight, preferably 1 to 80 parts by weight (for example, 5 to 75 parts by weight), and more preferably 10 to 70 parts by weight (100 parts by weight of the base resin). For example, it may be about 20 to 65 parts by weight.

(Heat resistance stabilizer (H))
Examples of the heat resistance stabilizer (H) include hindered phenol compounds (hindered phenol antioxidants) [for example, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-methyl). -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (6-tert-butyl-m-cresol), triethylene glycol bis- Branches such as (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate), pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) C _3-6 alkylphenols, etc.], phosphorus compounds (phosphorus antioxidants) [phosphites (bis (2,4-di-t-butylphenyl) pe Bis (C _1-9 alkyl-aryl) pentaerythritol diphosphite such as teraerythritol diphosphite), phosphonites (tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphos Phonite, etc.), sulfur compounds (sulfur antioxidants) [dilauryl thiodipropionate, etc.], amine antioxidants (amine antioxidants) [for example, naphthylamine, bis (2,2, 6,6-tetramethyl-4-piperidyl) sebacate, hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate], hydroquinone compounds (hydroquinone antioxidants) [ For example, 2,5-di-t-butylhydroquinone etc.], quinoline compounds (quinoline oxidation) Inhibitor) [for example, conventional antioxidants such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, etc.]; alkali or alkaline earth metal compounds [for example, alkali hydrogen phosphate or alkali Earth metal salt (for example, sodium dihydrogen phosphate, potassium dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate, calcium monohydrogen phosphate (dicalcium phosphate, CaHPO ₄ ), dihydrogen phosphate Barium, hydrogen phosphate (or monohydrogen or dihydrogen) alkaline earth metal salts such as barium monohydrogen phosphate]]; inorganic metals or mineral stabilizers (hydrotalcite, zeolite, etc.).

  These heat stabilizers can be used alone or in combination of two or more.

  In particular, at least a hindered phenol compound may be used as a heat resistance stabilizer. For example, the heat stabilizer may be composed of a hindered phenol compound alone, and a hindered phenol compound and another heat stabilizer (eg, phosphorus compound, alkali or alkaline earth metal compound, and hydrotalcite). Or at least one selected from the above.

  The proportion of the heat stabilizer is, for example, about 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably (particularly 0.05 to 2 parts by weight) with respect to 100 parts by weight of the base resin. You can choose from a range of Moreover, when combining a hindered phenol-type compound and another heat stabilizer, the ratio of a hindered phenol-type compound and another heat stabilizer is the former / the latter (weight ratio) = 99/1-1/99. , Preferably 98/2 to 10/90, more preferably about 95/5 to 20/80.

(Processing stabilizer (I))
Examples of the processing stabilizer (I) include long chain fatty acids (for example, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, montanic acid, oleic acid, linoleic acid. , Linolenic acid, arachidonic acid, erucic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and other C _10-34 saturated or unsaturated fatty acids), long chain fatty acid amides (eg capric amide, lauric acid amide, myristic acid Amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, oleic acid amide, stearyl stearic acid amide, stearyl oleic acid amide, ethylenediamine-distearic acid amide, hexamethylenediamine-distearic acid amide, ethylenediamine-dioleic acid Ami , Ethylenediamine-dierucamide, ethylenediamine- (stearic acid amide) oleic acid amide), long chain fatty acid esters (eg, ethylene glycol distearic acid ester, glycerin monostearic acid ester, trimethylolpropane monostearic acid ester, pentaerythritol) Stearic acid ester, sorbitan monostearic acid ester, monostearic acid ester of polyalkylene glycol (polyethylene glycol, etc.), and corresponding palmitic acid ester, lauric acid ester, behenic acid ester, montanic acid ester, oleic acid ester, etc. Exemplary esters of long chain fatty acids), polyoxyalkylene glycols (polyethylene glycol, polyoxyethylene-polyoxypropylene) Copolymer, etc.), silicone compounds, waxes [e.g., natural paraffin, synthetic paraffin, microcrystalline wax, polyolefin waxes (such as polyethylene wax), etc.] and the like. A processing stabilizer can be used individually or in combination of 2 or more types.

  The ratio of the processing stabilizer is, for example, 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of the base resin.

(Reactive stabilizer (J))
Examples of the reactive stabilizer (J) include epoxy-based reactive stabilizers [glycidyl ether compounds (bisphenol-A diglycidyl ether, phenyl glycidyl ether, etc.), glycidyl ester compounds (benzoic acid glycidyl ester, versatic acid glycidyl ester). Etc.), epoxy group-containing acrylic polymers, etc.], oxetane-based reactive stabilizers [1,4-bis {[3-ethyl-3-oxetanylmethoxy] methyl} benzene, di [1-ethyl (3-oxetanyl) Methyl] ether, etc.], oxazoline-based reactive stabilizers [1,3-phenylenebis (2-oxazoline), 1,4-phenylenebis (2-oxazoline), etc.], carbodiimide-based reactive stabilizers [polyarylcarbodiimide, Polyalkylaryl carbodiimide, Polycarboxylates imides such as Li [alkylenebis (alkyl- or cycloalkyl aryl) carbodiimide], Rhein Chemie Corporation "Stabaxol" series, "Carbodilite" series, etc.] of Nisshinbo Industries, Ltd., and the like. These reactive stabilizers may be used alone or in combination of two or more.

  The proportion of the reactive stabilizer is selected from the range of, 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. it can.

  The flame retardant resin composition of the present invention may be a powder mixture or a molten mixture, and a base resin (A), a halogenated flame retardant (B), a phosphate (C), and, if necessary. It can be prepared by mixing other components (flame retardant aid, olefin resin, electrical property improving aid, additive, etc.) by a conventional method. The present invention also includes a molded body formed of 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, and (2) once, A method of preparing pellets (master batches) having different compositions and mixing (diluting) the pellets with a predetermined amount for molding to obtain a molded body having a predetermined composition. (3) One or more of each component in a molding machine The method of directly charging and molding can be adopted. All or a part of the components other than the base resin may be mixed in advance and mixed with the base resin, or may be directly mixed with the base resin without previously mixing the components other than the base resin. Also, the order of addition of components other than the base resin is not particularly limited, and all the components other than the base resin may be added to the base resin all at once, and the components remaining after adding and mixing some components (May be divided into multiple times if necessary).

  In addition, a molded object can be manufactured by melt-kneading a flame-retardant resin composition by a conventional method, and shape | molding by conventional methods, such as extrusion molding, injection molding, and compression molding.

  Although the flame retardant resin composition (and molded product) of the present invention contains a halogen-based flame retardant, it can achieve both flame retardancy and electrical characteristics. When the resin composition (and molded product) of the present invention is measured with a test piece thickness of 1.6 mm, the flame retardancy based on the UL94 flammability test is V-2 or more, preferably V-1 or more, and more preferably. Is V-0 or higher. Further, in the resin composition (and molded product) of the present invention, the comparative tracking index (CTI) based on IEC112 (UL746A) is 350 V or more (for example, about 350 to 1000 V), preferably 400 V or more (for example, 400 to 400). 900V), more preferably 500V or more (for example, about 500 to 800V), or 600V or more (for example, about 600 to 750V).

  The resin composition (and molded product) of the present invention has a flame retardancy based on the UL94 flammability test of V-1 or higher, preferably V-0 or higher when measured with a test piece thickness of 0.8 mm. In addition, the comparative tracking index (CTI) based on IEC112 (UL746A) is 350 V or more (for example, about 350 to 1000 V), preferably 400 V or more (for example, about 400 to 900 V), more preferably 450 V or more (for example, 450 About 850V).

  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 / electronic parts, office automation (OA) equipment parts, home appliance parts, It can be suitably used for automobile parts, machine mechanism parts, and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the flame retardance and electrical property (comparison tracking index) of the resin composition were evaluated by the following test.

[Flammability test]
In accordance with UL94, the flammability was evaluated at a thickness of 1.6 mm or 0.8 mm of the test piece.

[Comparison tracking index (CTI)]
Based on IEC112 (UL746A), a comparative tracking index (CTI) [unit: V] was evaluated using a 0.1% ammonium chloride aqueous solution A (test piece thickness: 3 mm).

[Moldability (mold deposit)]
A 30 mm shot of a 70 mm × 50 mm × 3 mm molded piece was molded using an 80 t injection molding machine [manufactured by Toshiba Machine Co., Ltd.], and the mold deposit on the mold surface was evaluated by the following criteria by visual observation.

◯: No mold deposit is observed on the mold surface. Δ: Mold deposit is slightly observed on the mold surface. X: Remarkable mold deposit is observed on the mold surface.

  Base resins, halogenated flame retardants, phosphates, flame retardant aids, electrical property improving resins, electrical property improving aids, fillers, heat stabilizers, and processing stabilizers used in Examples and Comparative Examples are as follows. It is.

1. Base resin (A)
(A-1): Polybutylene terephthalate [Intrinsic viscosity = 0.85]
(A-2): Polyethylene terephthalate [Intrinsic viscosity = 0.75]
(A-3): Polypropylene terephthalate [Intrinsic viscosity = 0.85]
(A-4): Polyamide 66
(A-5): 12.5 mol% isophthalic acid-modified polybutylene terephthalate [inherent viscosity = 0.80].

2. Halogen flame retardant (B)
(B-1): Poly (pentabromobenzyl acrylate) [FR1025, manufactured by Bromchem Far East]
(B-2): Brominated polystyrene [Pyrocheck 68PB, manufactured by Ferrochemicals]
(B-3): Brominated polystyrene [SYTEX HP-7010P, manufactured by Albemarle]
(B-4): Ethylenebistetrabromophthalimide [SYTEX BT-93, manufactured by Albemarle Corporation]
(B-5): Brominated bisphenol A type epoxy resin [SRT5000, manufactured by Sakamoto Pharmaceutical Co., Ltd.]
(B-6): Brominated bisphenol A type polycarbonate resin [Fireguard FG-7500, manufactured by Teijin Chemicals Ltd.].

3. Phosphate (C)
(C1-1): Melamine polyphosphate, melam, melem double salt [manufactured by Nissan Chemical Industries, PMP200]
(C1-2): Melamine, melam, melem double salt of polyacid consisting of phosphorus, sulfur and oxygen [prepared according to JP-A-10-306082, Example 3]
(C1-3): Melamine, melam, melem double salt of polyphosphate [prepared according to JP-A-10-306081, Example 5]
(C2-1): Melamine salt of polymetaphosphate [prepared according to JP-A-10-81691, Example 1]
(C3-1): melamine polyphosphate [prepared according to WO 00/02869, Examples]
(C3-2): Melamine polyphosphate [manufactured by Nissan Chemical Industries, Ltd., PHOSMEL-200]
(C4-1): Polyphosphate piperazine salt [Asahi Denka Kogyo Co., Ltd., Adeka Stub T-1063F]
(C4-2): piperazine salt of polyphosphate [Asahi Denka Kogyo Co., Ltd., ADK STAB FP-2100]
[Phosphate C used in Comparative Example]
(CI): dimelamine pyrophosphate [Budit 311 manufactured by Budenheim]
(C-II): ammonium polyphosphate [manufactured by Chisso Corporation, Terrage C60].

4). Flame retardant aid (D)
[Antimony-containing compound (D1)]
(D1-1): Antimony trioxide (D1-2): Sodium antimonate [Fluorine-containing resin (D2)]
(D2-1): Polytetrafluoroethylene [Silicon-containing compound (D3)]
(D3-1): Swellable synthetic mica [ME100, manufactured by Coop Chemical Co., Ltd.]
[Phosphorus-containing compound (D4)]
(D4-1): Aluminum salt of (2-carboxyethyl) methylphosphinic acid (D4-2): Calcium salt of (2-carboxyethyl) methylphosphinic acid (D4-3): Resorcinol bis (di-2,6 -Xylyl phosphate)
(D4-4): Cyclic phenoxyphosphazene (3-tetramer mixture)
(D4-5): 1,4-piperazinediyltetraphenyl phosphate (D4-6): Bis [2-methyl-2-oxo-5-ethyl-1,3-dioxa-2-phospha (V) cyclohexane methylphosphonate -5-ylmethyl]
(D4-7): Aluminum salt of diethylphosphinic acid [Aromatic resin (D5)]
(D5-1): Polycarbonate resin [Panlite L1225, manufactured by Teijin Chemicals Ltd.].

5. Electrical property improving resin (E) (olefin resin (E))
(E-1): Ethylene / ethyl acrylate copolymer [NUC-6570, manufactured by Nippon Unicar Co., Ltd.]
(E-2): Ethylene / glycidyl methacrylate copolymer [Bondfast E, manufactured by Sumitomo Chemical Co., Ltd.]
(E-3): Maleic anhydride-modified polyolefin [Toughmer MP, manufactured by Mitsui Chemicals, Inc.].

6). Electric property improvement aid (F)
(F-1): Titanium oxide [TITONE SR-1, manufactured by Sakai Chemical Industry Co., Ltd.]
(F-2): Talc (F-3): Melamine cyanurate.

7). Filler (G)
(G-1): Glass fiber [a chopped strand having a diameter of 13 μm and a length of 3 mm]
(G-2): Glass fiber [chopped strand having a diameter of 10 μm and a length of 3 mm].

8). Heat stabilizer (H)
(H1-1): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
(H2-1): Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (H2-2): Tetrakis (2,4-di-t-butylphenyl) -4, 4'-biphenylenephosphonite (H2-3): hydrotalcite [DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.]
(H2-4): calcium dihydrogen phosphate.

9. Processing stabilizer (I)
(I-1): Polyethylene wax [Sunwax, Sanyo Chemical Industries, Ltd.]
(I-2): Montanic acid ester [LUZA WAX, manufactured by Toyo Petrolite Co., Ltd.].

10. Reactive stabilizer (J)
(J-1): Bisphenol-A diglycidyl ether [Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.]
(J-2): Polycarbodiimide [Carbodilite HMV-8CA, manufactured by Nisshinbo Industries, Inc.].

Examples 1-26 and Comparative Examples 1-13
Base resin (A), halogen flame retardant (B), phosphate (C), flame retardant aid (D), electrical property improving resin (E), electrical property improving aid (F), filler ( G), heat stabilizer (H), processing stabilizer (I), and reactive stabilizer (J) are mixed in the proportions (parts by weight) shown in Tables 1 to 3 and kneaded with a 30 mm diameter twin screw extruder. Extruded to prepare a pellet-shaped resin composition. Using the obtained pellets, a test molded product was produced by injection molding, and flammability, tracking resistance (comparative tracking index) and moldability (mold deposit) were evaluated. The results are shown in Tables 1-3. In Comparative Example 10, foaming decomposition of the resin occurred during extrusion.

Examples 27-35
Base resin (A), halogen flame retardant (B), phosphate (C), flame retardant aid (D), electrical property improving resin (E), electrical property improving aid (F), filler ( G), heat stabilizer (H), processing stabilizer (I), and reactive stabilizer (J) are mixed in the proportions (parts by weight) shown in Table 4 and kneaded and extruded by an extruder to form a pellet-shaped resin composition. Was prepared. Using the obtained pellets, a test molded product was produced by injection molding, and flammability (1.6 mm) and tracking resistance (comparative tracking index) were evaluated. The results are shown in Table 4.

Examples 36-40, Comparative Examples 14-15
Base resin (A), halogen flame retardant (B), phosphate (C), flame retardant aid (D), electrical property improving resin (E), electrical property improving aid (F), filler ( G), the heat resistance stabilizer (H) and the processing stabilizer (I) were mixed in the proportions (parts by weight) shown in Table 4 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 the flammability (0.8 mm) and the tracking resistance (comparative tracking index) were evaluated. The results are shown in Table 4.

Claims (23)

  A flame retardant resin composition comprising a base resin (A), a halogen-based flame retardant (B), and a phosphate (C) and having improved electrical characteristics, the phosphate (C) A polyphosphate (C1) of an aminotriazine condensate, a polymetaphosphate (C2) of an aminotriazine and / or an aminotriazine condensate, a polyphosphoric acid having a number average condensation degree of 20 or more, an aminotriazine and / or an aminotriazine A flame retardant resin composition comprising at least one selected from a salt (C3) with a condensate and a (poly) phosphate (C4) of a (poly) alkylenepolyamine.   The base resin (A) is composed of at least one thermoplastic resin selected from polyester resins, polyamide resins, polycarbonate resins, polyphenylene oxide resins, polyphenylene sulfide resins, styrene resins, and vinyl resins. The resin composition according to claim 1. The base resin (A) is composed of a homo- or copolyester having at least one unit selected from 1,4-cyclohexanedimethylene terephthalate, C _2-4 alkylene terephthalate and C _2-4 alkylene naphthalate. Item 2. The resin composition according to Item 1.   The base resin (A) is a polybutylene terephthalate, a copolyester whose main component is a butylene terephthalate unit, a polypropylene terephthalate, a copolyester whose main component is a propylene terephthalate unit, a polyethylene terephthalate, and a copolyester whose main component is an ethylene terephthalate unit. The resin composition of Claim 1 comprised by at least 1 type selected from these.   Halogen flame retardant (B) is bromine-containing acrylic resin, bromine-containing styrene resin, bromine-containing polycarbonate resin, bromine-containing epoxy compound, brominated polyarylether compound, brominated aromatic imide compound, brominated bisaryl compound And at least one bromine atom-containing flame retardant selected from a brominated tri (aryloxy) triazine compound.   Halogen flame retardant (B) is brominated polybenzyl (meth) acrylate resin, brominated styrene resin, brominated bisphenol type polycarbonate resin, brominated bisphenol type epoxy resin, brominated bisphenol type phenoxy resin and alkylene bis brominated The resin composition according to claim 1, wherein the resin composition is at least one selected from phthalimide.   The phosphate (C) may contain a sulfur component, melamine polyphosphate, melam, melem double salt (C1), melamine polymetaphosphate (C2), melamine polyphosphate (C3) having a number average condensation degree of 40 or more ) And (poly) phosphates (C4) of dialkylenediamines, the resin composition according to claim 1. Melamine polyphosphate containing phosphate (C) containing 0.05 to 1 mol of melamine, 0.3 to 0.6 mol of melam, and 0.05 to 0.8 mol of melem with respect to 1 mol of phosphorus atom Melam melem double salt (C1a), phosphoric acid, 0.05 to 20 mol of sulfuric acid with respect to 1 mol of this phosphoric acid, and 1 to 4 mol of melamine with respect to 1 mol of phosphoric acid and sulfuric acid in total Baked product (C1b) obtained by calcining the reaction product, melamine polymetaphosphate (C2) containing 1.0 to 1.1 mol of melamine per mol of phosphorus atom, a number average condensation degree of 40 or more, and phosphorus Consists of at least one selected from melamine polyphosphate (C3) containing 1.1 to 2.0 moles of melamine per mole of atoms and (poly) phosphate (C4) of di-C _2-4 alkylenediamines The resin composition according to claim 1. .   The proportion of the halogen-based flame retardant (B) is 3 to 30 parts by weight and the proportion of the phosphate (C) is 1 to 30 parts by weight with respect to 100 parts by weight of the base resin (A). Resin composition.   The resin composition according to claim 1, wherein the proportion of the phosphate (C) is 30 to 250 parts by weight with respect to 100 parts by weight of the halogen flame retardant (B).   The resin composition according to claim 1, further comprising at least one flame retardant aid (D) selected from an aromatic resin, an antimony-containing compound, a fluorine-containing resin, a silicon-containing compound, and a phosphorus-containing compound.   Flame retardant aid (D) is phenol resin, polyphenylene oxide resin, aromatic epoxy resin, phenoxy resin, polyphenylene sulfide resin, polycarbonate resin, polyarylate resin, aromatic polyamide resin, aromatic polyester resin Resin and aromatic polyesteramide resin, antimony oxide, antimonate, (poly) organosiloxane, layered silicate, fluorine-containing monomer alone or copolymer, (condensed) phosphate ester, (condensed) phosphorus Acid ester amide, (bridged) aryloxyphosphazene, (phosphorous) metal salt, hypophosphite metal salt, organic (phosphorous) phosphonic acid metal salt, organic (phosphorous) phosphonic acid aminotriazine salt, organic (sub) phosphon From acid esters, organic phosphinic acid metal salts, and organic phosphinic acid aminotriazine salts At least one type of claim 11 resin composition according were-option.   The resin composition according to claim 11, wherein the ratio of the flame retardant aid (D) is 1 to 150 parts by weight with respect to 100 parts by weight of the halogen flame retardant (B).   Furthermore, the resin composition of Claim 1 containing an olefin resin (E). The resin composition according to claim 14, wherein the olefin resin (E) is at least one selected from an α- _C2-3 olefin- (meth) acrylic acid ester copolymer and an acid-modified olefin resin.   Further, it contains at least one additive selected from an electrical property improving aid (F), a filler (G), a heat stabilizer (H), a processing stabilizer (I), and a reactive stabilizer (J). The composition of claim 1.   Further, selected from salts of aminotriazine compounds, (hydrous) metal silicate, (hydrous) metal borate, (hydrous) metal stannate, metal oxides, metal sulfides, and alkaline earth metal compounds The resin composition according to claim 1, comprising at least one electrical property improving aid (F).   Furthermore, at least one kind of electricity selected from melamine cyanurate, talc, kaolin, (hydrous) zinc borate, (hydrous) calcium borate, (hydrous) zinc stannate, zinc oxide, zinc sulfide, and calcium hydrogen phosphate The resin composition of Claim 1 containing a characteristic improvement adjuvant (F).   (I) When measured at a test piece thickness of 0.8 mm, the flame retardancy according to UL94 combustion test is V-1 or higher, and (ii) the comparative tracking index according to IEC112 is 350 V or higher. 1. The resin composition according to 1.   (I) When measured with a test piece thickness of 1.6 mm, the flame retardancy according to UL94 flammability test is V-2 or higher, and (ii) the comparative tracking index according to IEC112 is 400 V or higher. Item 2. The resin composition according to Item 1.   (I) When measured with a test piece thickness of 1.6 mm, the flame retardancy according to the UL94 flammability test is V-0 or higher, and (ii) the comparative tracking index according to IEC112 is 600 V or higher. Item 2. The resin composition according to Item 1.   The molded object formed with the resin composition of Claim 1. The molded body according to claim 22, which is an electrical / electronic part, an office automation equipment part, a household electrical equipment part, an automobile part, or a mechanical mechanism part.