JP5186210B2 - Flame retardant resin composition - Google Patents

Description

  The present invention relates to a resin composition excellent in flame retardancy and moldability and having 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, and can make a resin flame-retardant with a small amount.

  Such a thermoplastic resin (composition) is required to have high electrical characteristics in accordance with the use in addition to flame retardancy. In order to improve the electrical characteristics of such a resin, Japanese Patent Application Laid-Open No. 10-251528 (Patent Document 1) describes (b) ammonium polyphosphate 0.5 to 100 parts by weight of (a) thermoplastic resin. 50 parts by weight, (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, (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 2) describes (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 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, even with the resin compositions described in these documents, the effect of improving tracking resistance under severe conditions is insufficient.

  On the other hand, JP-A No. 2004-339510 (Patent Document 3) shows that the flame retardancy of a thermoplastic resin can be improved by using a specific (di) phosphinate and a halogen-based flame retardant together. ing. However, the composition described in this document is insufficient in improving electrical characteristics such as tracking resistance.

Japanese Patent Application Laid-Open No. 10-114854 (Patent Document 4) and Japanese Patent Application Laid-Open No. 10-273589 (Patent Document 5) disclose a polyester resin or polyamide resin, a halogenated flame retardant, an inorganic filler, and Na _3. (Acidic) such as HP ₂ O ₇ , K ₂ H ₂ P ₂ O ₇ , Na ₃ H ₂ P ₃ O ₁₀ , KNaH ₂ P ₂ O ₇ , Na ₂ H ₂ P ₂ O ₇ , Na ₈ P ₆ O ₁₉ A flame retardant resin molding composition containing pyro or metal metal phosphate and having improved electrical properties is disclosed. This document describes that an olefin polymer such as an ethylene-alkyl (meth) acrylate copolymer may be further contained in order to improve the comparative tracking index (CTI). However, even the compositions of these documents cannot sufficiently improve the tracking resistance. Further, in these documents, the improvement effect of CTI greatly varies depending on the type and amount of components used. For example, in the compositions of Patent Documents 4 and 5, the tracking resistance improvement effect is different from that of an olefin polymer. The combined use of pyro or alkali metal polyphosphate is not sufficient, and it is expressed by the combined use of a large amount of an inorganic substance (inorganic filler) having a synergistic effect such as alkaline earth metal sulfate or talc. For this reason, although the compositions of these documents can improve the tracking resistance at a certain level (for example, about 425 to 600 volts), the physical properties are significantly lowered. Moreover, even in the methods described in these documents, since thermally unstable pyro or alkali metal polyphosphate is used, the thermal stability of the resin is lowered, and the manufacturability and moldability of the resin composition are unsuitable. is there.
JP-A-10-251528 (Claim 1) JP 11-343389 A (Claim 1) JP 2004-339510 A (Claim 1) Japanese Patent Laid-Open No. 10-114854 (Claim 1, paragraph number [0013], Example) JP-A-10-273589 (Claims 1, 20 and Examples)

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

  Another object of the present invention is to provide a flame retardant resin composition capable of reliably improving electrical characteristics such as tracking resistance at a high level and a molded product thereof.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that at least one selected from a halogen flame retardant, a specific organic / inorganic acid salt, an olefin resin, a fluorine resin, and a Group 4 metal compound. It was found that the flame retardancy and electrical properties of the base resin can be reliably improved or improved at a high level without impairing moldability when combined with various electrical property improvers, and the present invention has been completed.

  That is, the flame retardant resin composition of the present invention comprises a base resin (A), a halogen flame retardant (B), an organic phosphinate (C1) and an oxo acid salt (C2) of a basic nitrogen-containing compound. A flame-retardant resin composition comprising at least one selected organic / inorganic acid salt (C) and an electrical property improver (D) and having improved electrical properties, the electrical property improver (D) is comprised by at least 1 sort (s) selected from the olefin resin, the fluorine resin, and the periodic table group 4 metal compound.

The base resin (A) is at least one thermoplastic resin selected from polyester resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, polyphenylene sulfide resin, styrene resin, and vinyl resin. It may be configured. 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, polybutylene terephthalate, copolyester mainly composed of butylene terephthalate unit, polypropylene terephthalate, copolyester mainly composed of propylene terephthalate unit, polyethylene terephthalate, and ethylene terephthalate unit as the main component. It may be composed of at least one selected from copolyesters.

  The halogen flame retardant (B) includes a bromine-containing acrylic resin (for example, brominated polybenzyl (meth) acrylate resin), a bromine-containing styrene resin (for example, brominated product of styrene resin, brominated styrene 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 organic phosphinate (C1) may be, for example, an aliphatic phosphinate that may have a substituent and / or an alicyclic phosphinate that may have a substituent. .

  In the flame retardant resin composition, the organic phosphinate (C1) may have a dialkylphosphinic acid which may have a substituent, a dicycloalkylphosphinic acid which may have a substituent, a substituent. Alkylene phosphinic acid which may have, alkenylene phosphinic acid which may have a substituent, (bi) cycloalkylene phosphinic acid which may have a substituent, and may have a substituent An organic phosphinic acid selected from alkanebis (alkylphosphinic acid), a periodic table group 1 metal, a periodic table group 2 metal, a periodic table group 4 metal, a periodic table group 7 metal, a periodic table group 8 metal, Periodic Table Group 10 Metal, Periodic Table Group 11 Metal, Periodic Table Group 12 Metal, Periodic Table Group 13 Metal, Periodic Table Group 14 Metal, Periodic Table Group 15 Metal, and Amino Triazine Compound (e.g. The oxo acid salt (C2) may be at least one oxo selected from condensed phosphoric acid, sulfuric acid, and pyrosulfuric acid, and may be a salt with at least one selected from melamine, melam, melem, and melon). It may be a salt of an acid and at least one basic nitrogen-containing compound selected from ammonia, a urea compound, a guanidine compound and an aminotriazine compound.

  Typically, the organic phosphinic acid salt (C1) has a dialkylphosphinic acid which may have a substituent, a dicycloalkylphosphinic acid which may have a substituent, and a substituent. An organic phosphinic acid selected from an alkylene phosphinic acid, an alkenylene phosphinic acid optionally having substituent (s), and an alkanebis (alkyl phosphinic acid) optionally having substituent (s); A salt with at least one selected from Group 13 metals of the periodic table, melamine, melam, melem, and melon, and the oxoacid salt (C2) is a salt of polyphosphoric acid and an aminotriazine compound, At least one selected from a salt of sulfuric acid and an aminotriazine compound, a salt of pyrosulfuric acid and an aminotriazine compound, and a condensed phosphoric acid amide. It may be.

  The organic / inorganic acid salt (C) may be composed of an organic phosphinate (C1) and an oxo acid salt (C2).

The electrical property improver (D) may be composed of at least an olefin resin and / or a periodic table Group 4 metal compound. The electrical property improver (D) is an α-C _2-3 olefin homo- or copolymer, α-C _2-3 olefin- (meth) acrylic acid 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) A copolymer, etc.), an acid-modified olefin resin, a fluorinated α- _C2-3 olefin homo- or copolymer, and at least one selected from titanium oxide.

  In the resin composition, the proportion of the halogen-based flame retardant (B) may be about 2 to 20 parts by weight with respect to 100 parts by weight of the base resin (A), and the proportion of the organic / inorganic acid salt (C) is About 3-30 weight part may be sufficient with respect to 100 weight part of base resin (A). Further, in the resin composition, the proportion of the organic / inorganic acid salt (C) is about 20 to 500 parts by weight with respect to 100 parts by weight of the halogen flame retardant (B), and the electrical property improver (D) The ratio may be about 10 to 150 parts by weight.

  The resin composition further includes a salt of an aminotriazine compound (for example, melamine cyanurate), a (hydrous) metal silicate salt (for example, talc, kaolin, etc.), a (hydrous) metal borate (for example, (hydrous) ) Zinc borate, (hydrous) calcium borate, etc.) (hydrous) metal stannate (eg, (hydrous) zinc stannate), metal oxides (eg, zinc oxide), metal sulfides (eg, Zinc sulfide and the like) and an alkaline earth metal compound (for example, calcium carbonate, calcium hydrogen phosphate and the like) may be included.

  The resin composition may contain at least one flame retardant aid (F) selected from aromatic compounds, phosphorus-containing compounds and antimony-containing compounds. The aromatic compound (or flame retardant aid (F)) is phenolic resin, polyphenylene oxide resin, aromatic epoxy resin, phenoxy resin, polyphenylene sulfide resin, polycarbonate resin, polyarylate resin, aromatic polyamide. At least one selected from a series resin, an aromatic polyester resin (an aromatic polyester resin that may be liquid crystalline) and an aromatic polyester amide resin (an aromatic polyester amide resin that may be liquid crystalline) It may be a seed. The phosphorus-containing compound (or flame retardant aid (F)) is composed of (condensed) phosphoric acid ester, (condensed) phosphoric acid ester amide, (crosslinked) aryloxyphosphazene, (sub-) phosphorous acid metal salt, hypoxia. It may be at least one selected from a metal phosphate, an organic (phosphorous) phosphonate, an organic (phosphorous) phosphonic acid metal salt, and an organic (phosphorous) phosphonic acid aminotriazine salt. In particular, the phosphorus-containing compound (or flame retardant aid (F)) is at least one selected from alkyl (phosphite) phosphonate metal salts, (phosphite) metal phosphate salts and hypophosphite metal salts. Also good.

  Furthermore, the resin composition may contain at least one additive selected from a filler, a heat stabilizer, a processing stabilizer, and a reactive stabilizer.

  The resin composition of the present invention is excellent in flame retardancy and electrical properties. 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 500 V or more (preferably 650 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.

  The flame retardant resin composition of the present invention combines a base resin, a halogen-based flame retardant, a specific organic / inorganic acid salt, and an electrical property improver with characteristics for improving electrical properties, so that flame retardant In addition to excellent properties, electrical characteristics can be improved. Further, according to the present invention, electrical characteristics such as tracking resistance can be reliably improved at a high level by the combination.

Detailed Description of the Invention

  The flame retardant resin composition of the present invention comprises at least a base resin, a halogen flame retardant, a specific organic / inorganic acid salt, and a specific electrical property improver. Such a resin composition is improved not only in flame retardancy but also in electrical characteristics (such as tracking resistance represented by a comparative tracking index).

[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 (C _4-40 dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, hexadecanedicarboxylic acid, and dimer acid, preferably C _4-14 dicarboxylic acid), and alicyclic rings. wherein the dicarboxylic acid (hexahydrophthalic acid, hexahydroterephthalic acid, such as _{C 8-12} dicarboxylic acid such as himic acid), an aromatic dicarboxylic acid _{[C 8-16} array Nji carboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, 2 , 6-naphthalenedicarboxylic acid), bisphenyl dicarboxylic acid (4,4'-biphenyl dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylalkane dicarboxylic acid (4,4'-diphenylmethane dicarboxylic acid, etc.), 4 , 4'-diphenylketone dicarboxylic acid) ], Derivatives thereof (such as lower alkyl esters, derivatives capable of forming esters such as acid anhydrides) 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.)], fat 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)], oxybenzoic acid (such as 3- or 4-hydroxybenzoic acid), oxy Naphthoic 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. Furthermore, the polyester resin includes 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 alicyclic diamines such as C _3-10 aliphatic diamines such as tetramethylene diamine and hexamethylene diamine, bis (4-aminocyclohexyl) methane, and bis (4-amino-3-methylcyclohexyl) methane. (Bis (amino C _5-8 cycloalkyl) C _1-4 alkane etc. which may have a substituent such as an alkyl group). If necessary, aromatic diamines such as phenylenediamine and metaxylylenediamine 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 naphthalenecarboxylic 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 alkylphenols such as cresol with benzeneformaldehyde resins (such as phenolic resins) and alkylbenzeneformaldehyde resins, and the main components 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 (PBSS), and the like can be used.

(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 epoxy resins such as brominated bisphenol type polycarbonate resins), bromine-containing epoxy compounds (for example, brominated bisphenol type epoxy resins (brominated bisphenol A type epoxy resins, etc.); Bisphenol type phenoxy resins (eg brominated phenoxy resins such as brominated bisphenol A type phenoxy resins), brominated polyaryl ether compounds (eg 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-based flame retardant is, for example, 1 to 30 parts by weight, preferably 2 to 25 parts by weight (for example, 2 to 20 parts by weight), more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the base resin. (For example, about 5 to 18 parts by weight).

[Organic / inorganic acid salts (C)]
The organic / inorganic acid salt (C) is at least one selected from an organic phosphinic acid salt (C1) and an oxo acid salt (C2) of a basic nitrogen-containing compound (a salt of an oxo acid and a basic nitrogen-containing compound). It consists of

(Organic phosphinate (C1))
Examples of the organic phosphinic acid salt (C1) include organic group-substituted phosphinic acid and polyvalent phosphinic acid (polyvalent organic group) obtained by substituting phosphinic acid with an organic group (such as an optionally substituted hydrocarbon group). A salt of an organic phosphinic acid such as a polyphosphinic acid in which a plurality of phosphinic acids are linked with each other [a salt with at least one salt-forming component selected from a metal, boron, ammonium and a basic nitrogen-containing compound (metal salt) , Boron salts (boryl compounds, etc.), ammonium salts, salts with amino group-containing nitrogen-containing compounds, etc.). The organic phosphinate can improve the electrical characteristics of the resin even when a halogen-based flame retardant is used. Therefore, the organic phosphinate seems to function as an electrical property improver. In the organic phosphinic acid salt, the organic phosphinic acid has a substituent {eg, a hydroxyl group, an unsaturated group [eg, a carbon-oxygen unsaturated bond-containing group such as a carboxyl group, an acyl group, an alkoxycarbonyl group (such as a methoxycarbonyl group), etc. Etc.], a hydrocarbon group (such as an alkyl group such as a methyl group), an alkoxy group (such as a methoxy group), etc.}. The organic phosphinic acid may have these substituents alone or in combination of two or more.

In the organic phosphinic acid salt (C1), as typical organic phosphinic acid, for example, a mono- or dialkylphosphinic acid [dialkylphosphinic acids (such as diC _1-10 alkylphosphinic acid)] which may have a substituent, For example, dimethylphosphinic acid, methylethylphosphinic acid, diethylphosphinic acid, ethylbutylphosphinic acid (ethyl n-butylphosphinic acid, ethylisobutylphosphinic acid, ethyl t-butylphosphinic acid, etc.), dipropylphosphinic acid (din-propyl) (Hydroxyphosphinic acid, diisopropylphosphinic acid, etc.), dibutylphosphinic acid (di-n-butylphosphinic acid, diisobutylphosphinic acid, di-t-butylphosphinic acid, etc.), dialkylphosphinic acids such as dioctylphosphinic acid; Hydroxyl group-containing dialkylphosphinic acids such as tilphosphinic acid, (hydroxyethyl) methylphosphinic acid, bis (hydroxymethyl) phosphinic acid, bis (hydroxyethyl) phosphinic acid; carboxyl groups such as (2-carboxyethyl) methylphosphinic acid Dialkylphosphinic acid; alkoxy group-containing dialkylphosphinic acid such as (methoxymethyl) methylphosphinic acid and bis (methoxymethyl) phosphinic acid; (2-carboxyethyl) methylphosphinic acid, (2-carboxypropyl) methylphosphinic acid, bis ( Carboxy group-containing dialkylphosphinic acids such as 2-carboxyethyl) phosphinic acid and bis (2-carboxypropyl) phosphinic acid; (2-methoxycarbonylethyl) methylphosphinic acid, [2- [beta] -hydroxyethylcarbonyl) ethyl] methylphosphinic acid, (2-methoxycarbonylpropyl) methylphosphinic acid, bis (2-methoxycarbonylethyl) phosphinic acid, bis (2-methoxycarbonylpropyl) phosphinic acid and other alkoxycarbonyl groups Dialkylphosphinic acid and the like], mono- or dicycloalkylphosphinic acid which may have a substituent [for example, monocycloalkylphosphinic acid (for example, cycloalkylalkylphosphinic acid such as cyclohexylmethylphosphinic acid), dicycloalkylphosphine acid (e.g., such as dicyclohexyl phosphinic acid), such as mono- or di-cycloalkyl phosphinic acids, such as (such as mono- or di-C _5-10 cycloalkyl phosphinic acid)], which may have a substituent model Or diaryl phosphinic acid [e.g., _{C 6-10} aryl phosphinic acids such as phenyl phosphinic acid, _{C 1-4} alkyl, such as alkyl aryl phosphinic acid (methylphenyl phosphinic acid; di _{C 6-10} aryl phosphinic acid such as diphenyl phosphinic acid Mono- or diarylphosphinic acids such as —C _6-10 aryl-phosphinic acid, etc.], optionally substituted alkylenephosphinic acids (eg 1-hydroxyphosphorane 1-oxide, 1-hydroxy-3- Methyl phosphophosphorane 1-oxide, C _3-8 alkylene phosphinic acid such as 2-carboxy-1-hydroxy-1H-phosphorane 1-oxide, etc.), and alkenylene phosphinic acid (eg 1- Hydroxy-2,3-dihydro-1H Phosphole 1-oxide, 1-hydroxy-2,5-dihydro -1H- phosphole 1-oxide, 1-hydroxy-3-cyclo _{C 3-8} alkenylene, such as methyl-2,5-dihydro -1H- phosphole 1-oxide Phosphinic acid, etc.), (bi) cycloalkylenephosphinic acid (for example, 1,3-cyclobutylenephosphinic acid, 1,3-cyclopentylenephosphinic acid, 1,4-cyclooctylene) which may have a substituent (Bi) C _4-10 cycloalkylene phosphinic acid such as phosphinic acid, 1,5-cyclooctylene phosphinic acid), bicycloalkenylene phosphinic acid optionally having a substituent, plural phosphinic acids (or organic phosphines) Acid) linked by a polyvalent organic group {for example, an optionally substituted phosphinic acid Lucanbisphosphinic acid [C _1-10 alkanebis (phosphinic acid) such as ethane-1,2-bis (phosphinic acid)], alkanebis (alkylphosphinic acid) optionally having a substituent [ethane-1, C _1-10 alkanebis (C _1-6 alkylphosphinic acid) such as 2-bis (methylphosphinic acid)] and the like}.

  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 7 metal, Group 8 metal, Group 10 metal, Group 11 metal of the periodic table , Group 12 metals, Group 13 metals, Group 14 metals, Group 15 metals and aminotriazine compounds (melamine, melamine condensates, 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).

  Preferred organic phosphinates include aliphatic phosphinates that may have a substituent and / or alicyclic phosphinates that may have a substituent, such as those having a substituent. Dialkylphosphinic acid which may have a substituent, dicycloalkylphosphinic acid which may have a substituent, alkylenephosphinic acid which may have a substituent, alkenylenephosphinic acid which may have a substituent, An organic phosphinic acid selected from (bi) cycloalkylenephosphinic acid which may have and an alkanebis (alkylphosphinic acid) which may have a substituent, a metal of Group 1 and a metal of Group 2 of the periodic table , Group 4 metal, Group 7 metal, Group 8 metal, Group 10 metal, Group 11 metal, Group 12 metal, Group 13 metal, Group 14 metal, Group 15 metal and Aminotria A salt with at least one selected from an organic compound {for example, a dialkylphosphinic acid salt which may have a substituent [dimethylphosphinic acid Ca salt, methylethylphosphinic acid Ca salt, diethylphosphinic acid Ca salt, ethylbutylphosphine Acid Ca salt, Dibutylphosphinic acid Ca salt, (2-carboxyethyl) methylphosphinic acid Ca salt, (2-carboxypropyl) methylphosphinic acid Ca salt, bis (2-carboxyethyl) phosphinic acid Ca salt, bis (2- Carboxypropyl) phosphinic acid and alkaline earth metal salts such as Mg salt corresponding to these calcium salts; dimethylphosphinic acid Al salt, methylethylphosphinic acid Al salt, diethylphosphinic acid Al salt, ethylbutylphosphinic acid Al salt, dibutyl Phosphinic acid Al salt, (2-Ca Aluminum salts such as Boxyethyl) methylphosphinic acid Al salt, (2-carboxypropyl) methylphosphinic acid Al salt, bis (2-carboxyethyl) phosphinic acid Al salt, bis (2-carboxypropyl) phosphinic acid Al salt; Phosphinic acid Ti salt, diethylphosphinic acid Ti salt, ethylbutylphosphinic acid Ti salt, dibutylphosphinic acid Ti salt and titanium salts such as titanyl salt corresponding to these salts; diethylphosphinic acid Zn salt, ethylbutylphosphinic acid Zn salt, Zn salt such as dibutylphosphinic acid Zn salt, methylethylphosphinic acid Zn salt, (2-carboxyethyl) methylphosphinic acid Zn salt, etc.], salt of aminotriazine compound (dimethylphosphinic acid melamine salt, methylethylphosphinic acid melamine salt, Jie ) Alkylenephosphinic acid salts [for example, alkaline earth metal salts of 1-hydroxyphosphorane 1-oxide (Ca salts, Mg salts, etc.), Al salts, Ti salts, titanyl salts, Zn salts, etc. Melamine salts, aminotriazine salts such as melamine, melam, melem double salts, etc.].

  Particularly preferred organic phosphinic acid salts include dialkylphosphinic acid which may have a substituent, dicycloalkylphosphinic acid which may have a substituent, alkylenephosphinic acid which may have a substituent, An organic phosphinic acid selected from alkenylene phosphinic acid optionally having substituent (s), and alkanebis (alkylphosphinic acid) optionally having substituent (s); A salt with at least one selected from Table 13 group metals (such as aluminum) and aminotriazine compounds (such as melamine, melam, melem, melon) is included. The organic phosphinic acid salts may be used alone or in combination of two or more.

  Specific examples of the organic phosphinic acid salt include, for example, JP-A-55-5979, JP-A-8-73720, JP-A-9-278784, JP-A-11-236392, JP-A-2001-2686. JP, JP 2004-238378, JP 2004-269526, JP 2004-269848, JP 2004-346325, JP 2001-513784, JP 2001-525327. 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. Compound described in Japanese Patent No. 6303694 And the like.

(Oxo acid salt of basic nitrogen-containing compound (C2))
Examples of the oxo acid (oxo acid other than the organic phosphinic acid) constituting the oxo acid salt (C2) include nitric acid, chloric acid (perchloric acid, chloric acid, chlorous acid, hypochlorous acid, etc.), phosphorus Acid [non-condensed phosphoric acid such as orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid; condensed phosphorous such as pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polymetaphosphoric acid, phosphoric anhydride (diphosphorus pentoxide) Acid (polyphosphoric acid, etc.), organic phosphoric acid (phosphoric acid (phosphoric acid other than hypophosphorous acid) and partial esters of alcohols such as alkanol and alkylene glycol (for example, monophosphoric acid such as dimethyl phosphate) Or dialkyl), sulfuric acid (non-condensed sulfuric acid such as peroxomonosulfuric acid, sulfuric acid and sulfurous acid; condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid (non-condensed such as orthoboric acid and metaboric acid) Oxalic acid, tetraboric acid, condensed boric acid such as boric anhydride), chromic acid, antimonic acid, molybdic acid, tungstic acid, etc. These oxo acids can be used alone or in combination of two or more. Of these oxo acids, condensed phosphoric acid (such as pyrophosphoric acid, polyphosphoric acid, polymetaphosphoric acid), sulfuric acid, condensed sulfuric acid (such as pyrosulfuric acid), and the like are preferable.

Examples of the basic nitrogen-containing compound (nitrogen-containing compound) constituting the oxoacid salt (C2) include a hydrogen atom bonded to a nitrogen atom (amino group (—NH ₂ ) or imino group (—NH—)). That is, nitrogen-containing compounds (chain or cyclic compounds) having active hydrogen atoms, such as ammonia, urea compounds (urea, etc.), guanidine compounds (dicyandiamide, guanidine, guanylurea, etc.), aminotriazine compounds [melamine, guanamine Benzoguanamine and / or condensates thereof (melamine condensates such as melam, melem, melon, etc.). These nitrogen-containing compounds can be used alone or in combination of two or more. Of the nitrogen-containing compounds, ammonia, urea, guanidine, dicyandiamide, melamine, and melamine condensates (melam, melem, melon, etc.) are preferable.

The oxo acid salt (C2) may be a polycondensate as long as it is a reaction (and calcination) product of an oxo acid and a basic nitrogen-containing compound. Examples of the polycondensation product of an oxo acid and the nitrogen-containing compound include the oxo acid and / or a salt of the oxo acid and the nitrogen-containing compound, and a cyanamide derivative (—N═C═N— or —N═C ( A compound having a unit represented by —N <) ₂ , for example, a polycondensate with a triazine compound such as melamine, a guanidine compound or the like). Such a polycondensate can be obtained, for example, by calcining and condensing the oxo acid and the cyanamide derivative in the presence of a binder (such as urea and / or oxo acid urea) as necessary. In many cases, it is a polymer compound having a bond. As such a polycondensate, the phosphoric acid salt of the nitrogen-containing compound (such as ammonium polyphosphate and urea phosphate) in addition to the phosphoric acid and organic phosphoric acid exemplified above as the oxo acid (particularly organic A condensed phosphoric acid amide (or polyphosphoric acid amide) using phosphoric acid and / or condensed phosphoric acid) can be used. In polyphosphoric acid amide, urea and / or urea phosphate are often used as the binder. The polycondensates can be used alone or in combination of two or more. Regarding polyphosphoric acid amide, for example, JP-A-7-138463 can be referred to. Such polyphosphoric acid amide can be produced by the method described in JP-B-51-39271 and JP-B-53-2170. Polyphosphoric amides are commercially available, for example, as “Sumisafe PM” [Sumitomo Chemical Co., Ltd.], “Tyen S” [Taihei Chemical Sangyo Co., Ltd.], and the like.

  Preferred oxo acid salts include, for example, salts of polyphosphoric acid and aminotriazine compounds [for example, polyphosphoric acid such as melamine polyphosphate, melam polyphosphate, melem polyphosphate, and melamine and / or melamine condensates (particularly melamine or melamine condensation). Salt of sulfuric acid and aminotriazine compound [for example, sulfuric acid and melamine such as sulfuric acid (di) melamine, sulfuric acid (di) melam, sulfuric acid (di) melem, melamine sulfate, melam, melem double salt) / Or salts with melamine condensate, etc.], salts of pyrosulfuric acid and aminotriazine compounds [for example, pyrosulfuric acid (di) melamine, pyrosulfuric acid (di) melam, pyrosulfuric acid (di) melem, melamine pyrosulfate, melam, Salt of pyrosulfuric acid such as melem double salt and melamine and / or melamine condensate], condensed phosphoric acid amide (or polyphosphoric acid) Bromide), and the like.

  In the oxoacid salt, the ratio (molar ratio) between the oxoacid and the nitrogen-containing compound is, for example, oxoacid / nitrogen-containing compound = 1 / 0.5 to 1/5, preferably 1 / 0.7 to 1 / 4, More preferably, it may be about 1 / 0.8 to 1/3.

  Such an oxoacid salt can improve the electrical characteristics of the resin even when a halogen-based flame retardant is used. Therefore, the oxo acid salt seems to function as an electrical property improver.

  The organic / inorganic acid salt (C) may be used alone or in combination of two or more. In particular, the organic / inorganic acid salt (C) may be composed of an organic phosphinic acid salt (C1) and an oxo acid salt (C2) in order to further improve electrical characteristics. When combining the organic phosphinate (C1) and the oxoacid salt (C2), the former / the latter (weight ratio) = 99/1 to 1/99, preferably 95/5 to 5/95, more preferably 90 / It may be about 10 to 10/90.

  The ratio of the organic / inorganic acid salt (C) is, for example, 1 to 60 parts by weight (eg 2 to 50 parts by weight), preferably 3 to 40 parts by weight (eg 4 to 4 parts by weight) with respect to 100 parts by weight of the base resin. 35 parts by weight), more preferably about 3 to 30 parts by weight (for example, 8 to 25 parts by weight). The proportion of the organic / inorganic acid salt (C) is, for example, 5 to 500 parts by weight, preferably 10 to 350 parts by weight, and more preferably 20 to 300 parts by weight with respect to 100 parts by weight of the halogen-based flame retardant (B). Part by weight (for example, 30 to 280 parts by weight), particularly about 40 to 270 parts by weight may be used, and usually about 20 to 500 parts by weight may be used.

[Electrical property improver (D)]
The electrical property improver (D) is a component for improving the electrical properties of the base resin at a high level in combination with a halogen-based flame retardant (and organic / inorganic acid salt). And at least one selected from Group 4 metal compounds. The resinous electrical property improver (olefin resin, fluorine resin) is a resin different from the base resin (A).

(Olefin resin)
Examples of the olefin resin include olefin monomers [alpha-olefins such as ethylene, propylene, 1-butene, 3-methyl-1-pentene, 4-methyl-1-butene, 1-hexene and 1-octene. (in particular, _{alpha-C 2-10} olefin); cyclic olefin {e.g., cyclobutene, cyclopentene, _(such as _{C 3-10} cycloalkene) cycloalkenes such as cyclohexene; Shikuropenchin, _{C 3-10} cycloalkyne, such as cyclohexanol Shin; crosslinking Cyclic olefins (polycycloalkenes such as norbornene and tetradicyclododecene, dicycloalkadienes such as dicyclopentadiene); or derivatives thereof (alkyl-substituted, alkylidene-substituted, alkoxy-substituted, acyl-substituted, Carboxy substitution etc.) etc.] Germany or copolymer, olefin monomer or polymer, copolymerizable monomer [vinyl monomer, for example, (meth) acrylic acid or salt thereof (metal salt, etc.), (meth) acrylic Acrylic monomers such as acid esters ((meth) acrylic acid alkyl esters, (meth) acrylic acid glycidyl esters, etc.); organic acid vinyl ester monomers such as vinyl acetate; fumaric acid, (anhydrous) maleic acid, (Anhydrous) itaconic acid, (anhydrous) citraconic acid, (anhydrous) α, β-unsaturated dicarboxylic acid monomers such as nadic acid; vinyl cyanide monomers such as (meth) acrylonitrile, etc.] And polymers (random copolymers, block copolymers, graft copolymers, etc.).

As typical olefin resin, for example, α-olefin resin [for example, homo- or copolymer of α-C _2-3 olefin such as polyethylene, polypropylene, propylene-ethylene copolymer; ethylene- (meth) Α- _C2-3 olefin- (meth) acrylic acid copolymer such as acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, metal salt (such as ionomer) of ethylene- (meth) acrylic acid copolymer Polymer, α-C _2-3 olefin- (meth) acrylic acid ester copolymer (α-C _2-3 olefin- (meth) acrylic acid alkyl ester copolymer such as ethylene-ethyl acrylate copolymer, ethylene - (meth) ne copolymers of alpha-C _2-3 olefin and a copolymerizable monomer such as acrylic acid glycidyl ester copolymer) ], Modified olefin resin [for example, olefin resin (olefin homo- or copolymer) is converted into acid component (for example, α, β-unsaturated carboxylic acid ((meth) acrylic acid, maleic acid, fumaric acid, itacon) Acid-modified olefin resin modified with acid, citraconic acid, nadic acid, etc. and / or acid anhydride thereof, etc.], cyclic olefin resin (eg, homopolymer of cyclic olefin, 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-based resins, α-C _2-3 olefin homo- or copolymer (polyethylene, polypropylene, ethylene / propylene copolymer, etc., particularly polypropylene, ethylene / propylene copolymer), α-C _{2− 3-} olefin- (meth) acrylic acid 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 (especially ethylene-ethyl acrylate copolymer), α-C _2-3 olefin- (meth) acrylic acid glycidyl ester copolymer (especially ethylene- (meth) acrylic acid glycidyl ester copolymer) ), Etc.], acid-modified olefin resins [for example, olefins obtained by modifying an α-C _2-3 olefin homo- or copolymer with an acid component. Preferred are vinyl resins (particularly acid-modified polypropylene such as maleic anhydride-modified polypropylene).

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 .

(Fluorine resin)
Fluorine-based resins (fluorine-containing resins) include fluorine-containing monomers alone or copolymers, such as fluorine-containing monomers (tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoro Alkyl vinyl ether, etc.) or a copolymer, the fluorine-containing monomer and other copolymerizable monomers (olefin monomers such as ethylene and propylene, and acrylic monomers such as (meth) acrylate) And the like) and the like. Specific examples of such a fluororesin include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene- Examples of the copolymer include a perfluoroalkyl vinyl ether copolymer, an ethylene-tetrafluoroethylene copolymer, and an ethylene-chlorotrifluoroethylene copolymer. Preferred fluorine-based resins include fluorinated α-C _2-3 olefins (particularly tetrafluoroethylene) homopolymers or copolymers. Fluorocarbon resins can be used alone or in combination of two or more.

  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.

(Group 4 metal compounds of the periodic table)
The periodic table Group 4 metal compound includes, for example, metal compounds such as titanium, zirconium, and hafnium, and is usually titanium or zirconium (particularly titanium) compound in many cases. Typical periodic table Group 4 metal compounds include titanium compounds [e.g., titanium oxide or hydroxide (e.g., titanium oxide such as titanium dioxide), titanium halide (e.g., titanium fluoride), titanium oxo acid. Salt (such as titanium sulfate), hydrates thereof (such as titanium oxide mono- or dihydrate)], and zirconium compounds (such as zirconium oxide) corresponding to these titanium compounds. Preferred Group 4 metal compounds of the periodic table include titanium oxide. These periodic table Group 4 metal compounds may be used alone or in combination of two or more.

  The periodic table group 4 metal compound may be used in the form of particles (or powder), and the average particle size of the powdered periodic table group 4 metal compound is, for example, 0.01 to 20 μm, preferably 0. 0.02 to 10 μm, more preferably about 0.05 to 5 μm.

  The electrical property improver (D) may be used alone or in combination of two or more. In a preferred embodiment, the electrical property improver (D) may be at least composed of an olefin resin and / or a periodic table Group 4 metal compound (particularly an olefin resin). In particular, when the organic / inorganic acid salt (C) is an organic phosphinate, the electrical property improver (D) is often composed of at least an olefin resin and / or a Group 4 metal compound of the periodic table.

  The proportion of the electrical property improving agent (D) is, for example, 0.5 to 30 parts by weight (for example, 1 to 25 parts by weight), preferably 2 to 20 parts by weight (for example, 3 parts) with respect to 100 parts by weight of the base resin. ˜18 parts by weight), more preferably about 3 to 15 parts by weight. The proportion of the electrical property improver (D) is, for example, 3 to 300 parts by weight, preferably 5 to 200 parts by weight, and more preferably 10 to 150 parts by weight (for example, 100 parts by weight of the halogen flame retardant). 15 to 130 parts by weight) or about 30 to 180 parts by weight (for example, 40 to 160 parts by weight, preferably 50 to 140 parts by weight).

[Electrical property improvement aid (E)]
The resin composition of the present invention may further contain an electrical property improving aid. The electrical property improving aid (E) is a compound that is not any of the components (B) to (D) and acts as an aid for improving electrical properties, such as nitrogen-containing compounds [aminotriazines. Compound (melamine; guanamine; melamine condensate such as melam, melem, etc.), salt of aminotriazine compound (organic acid or inorganic acid salt of said aminotriazine compound, for example, cyanurate such as melamine cyanurate, etc.)], Inorganic acid metal compounds {e.g., inorganic acid metal salts [e.g. (hydrous) silicate metal salts (talc, kaolin, silica, diatomaceous earth, clay, wollastonite, etc.), (hydrous) metal borate (e.g., ( (Hydrated) zinc borate, (hydrated) calcium borate, (hydrated) aluminum borate), (hydrated) metal stannate (for example, ( Water) zinc stannate), metal sulfate (calcium sulfate, magnesium sulfate, barium sulfate, etc.)], metal oxide (magnesium oxide, iron oxide, zinc oxide, alumina, etc.), metal hydroxide (aluminum hydroxide) , Magnesium hydroxide, zirconium hydroxide, alumina hydrate (boehmite)), metal sulfide (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.), alkaline earth metal compound (eg, alkaline earth metal salt (eg, And alkaline earth metal carbonates such as calcium carbonate and calcium hydrogen phosphate)) and the like. Among these, preferred electrical property improving aids include organic acid salts (particularly cyanuric acid salts) of aminotriazine compounds, metal silicates, metal borates, alkaline earth metal compounds, and the like. These electrical property improving aids can be used alone or in combination of two or more.

  The proportion of the electrical property improving aid (E) is, for example, 0 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight (for example, based on 100 parts by weight of the base resin). 1.5 to 10 parts by weight).

[Flame Retardant (F)]
The resin composition of the present invention may further contain a flame retardant aid (F). Flame retardant aids (F) include aromatic compounds (phenolic resins, aniline resins, polyphenylene oxide resins, aromatic epoxy resins (bisphenol type epoxy resins, novolac type epoxy resins, etc.), phenoxy resins, polyphenylene sulfide types. Resin, polycarbonate resin, polyarylate resin, aromatic polyamide resin, aromatic polyester resin (for example, aromatic polyester resin that may be liquid crystalline), aromatic polyester amide resin (for example, liquid crystalline) Aromatic resins such as aromatic polyesteramide resins), phosphorus-containing compounds (phosphorus-containing compounds that do not belong to the category of organic / inorganic acid salts (C) such as organic phosphinic acids), antimony-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 compounds (such as copper oxide), silicon-containing compounds [(poly ) Organosiloxane (silicone resin such as polydimethylsiloxane and polymethylphenylsiloxane, silicone oil, polysilsesquioxane, etc.), layered silicate (smectite layered silicate such as montmorillonite, Li-type fluorine teniolite, Na-type Swellable synthetic fluorine mica, vermiculite, halloysite, etc.), sulfur-containing compounds (organic sulfonic acid compounds, metals of perfluoroalkanesulfonic acid, etc.) Salt, sulfamine oxidation Such things or a salt thereof), and others. These flame retardant aids 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 Amide (phosphoramide etc.)], phosphonitrile compounds [eg aryloxyphosphazenes (phenoxyphosphazenes, tolyloxyphosphazenes, xylyloxyphosphazenes, phenoxytolyloxyphosphazenes, phenoxyxysilylphosphazenes, etc.) Cyclic and / or chain phosphazene compounds, their crosslinked phosphazene compounds (for example, phenoxyphosphazenes crosslinked with bisphenol residues), and WO99 / 19383, WO00 / 9518, WO02 / 98886 And phosphazene compounds described in WO04 / 24844], organic (phosphorous) phosphonic acid compounds [for example, organic phosphonic acid esters, organic (phosphorous) phosphonic acid metal salts (Li, Na, K, Mg, Ca, Al, Metal salts such as Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, and Mn), basic nitrogen compound salts (melamine salt, guanamine salt, benzoguanamine salt) and / or organic (sulfur) phosphonic acid Or condensate salts thereof (such as melamine condensates such as melam, melem, melon), And inorganic phosphorus compounds [for example, red phosphorus, (phosphite) metal phosphate (calcium phosphite, calcium hypophosphite, aluminum phosphite, phosphoric acid / aluminum phosphite double salt, boron phosphate, etc.), hypophosphorous acid Acid metal salts (calcium hypophosphite, aluminum hypophosphite, etc.)] and the like. Particularly preferred organic (phosphorous) phosphonic acid compounds are phosphorus-containing compounds.

Specific examples of the organic (sub) phosphonic acid compound include, for example, methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, isobutylphosphonic acid, octylphosphonic acid, hydroxyalkylphosphonic acid (Hydroxymethylphosphonic acid, hydroxyethylphosphonic acid, hydroxypropylphosphonic acid, etc.), alkoxyalkylphosphonic acid (methoxymethylphosphonic acid, ethoxyethylphosphonic acid, etc.), carboxyalkylphosphonic acid (carboxymethylphosphonic acid, 2-carboxyethylphosphonic acid, etc.) Methylphosphonous acid, ethylphosphonous acid, n-propylphosphonous acid, isopropylphosphonous acid, n-butylphosphonous acid, isobutylphosphonous acid, octylphosphonous acid Which have a substituent may be alkyl (sub) phosphonate (C _1-16 alkyl (sub) such as phosphonic acid); ethane-1,2-diphosphonic acid, have a substituent such as hydroxy ethane diphosphonic acid Alkylenediphosphonic acid (C _2-6 alkylenediphosphonic acid etc.) which may be substituted; alkylidene diphosphonic acid (C ₁ ) which may have a substituent such as 1-hydroxyethylidene-1,1-diphosphonic acid _-4 alkylidene diphosphonic acid); nitrilotris (alkylphosphonic acid) optionally having a substituent (such as hydroxyl group) such as nitrilotris (methylphosphonic acid) [nitrilotris ( _C1-4 alkylphosphonic acid) Etc.]; Oxydi (alkylphosphine) which may have a substituent (hydroxyl group etc.) such as oxydimethylphosphonic acid Phosphate) [such as oxydiphthalic (C _1-4 alkyl phosphonic acid)]; polyvinylphosphonic acid, polymer type phosphonic acids such as polyallyl acid; ester [methylphosphonic acid monomethyl ester of the organic (nitrite) phosphonic acid, 2 -Mono- or polyalkyl esters of alkyl (sub) phosphonic acid ( _C1-16 alkyl (sub) phosphon) which may have a substituent such as ethyl carboxyethyl phosphonate, triethyl carboxymethyl phosphonate, triethyl carboxyethyl phosphonate such as mono- or _{di-C 1-16} alkyl esters of the acids); pentaerythritol ester of methylphosphonic acid, 2-ethyl-2-hydroxymethyl-1,3-propanediol ester of methylphosphonic acid, hydroxyethyl poly (oxyethyl) phosphonic acid ester Such as an ester of an alkyl (sub) phosphonic acid with a polyhydric alcohol, which may have a substituent such as; a salt of these organic (sub) phosphonic acids [methyl (sub) phosphonic acid Ca salt, ethyl (suboxide) ) Phosphonic acid Ca salt, n-propyl (sub-) phosphonic acid Ca salt, isopropyl (sub-) phosphonic acid Ca salt, n-butyl (sub-) phosphonic acid Ca salt, isobutyl (sub-) phosphonic acid Ca salt, octyl (sub-) Phosphonic acid Ca salt, methyl (sub-) phosphonic acid Mg salt, ethyl (sub-) phosphonic acid Mg salt, n-propyl (sub-) phosphonic acid Mg salt, isopropyl (sub-) phosphonic acid Mg salt, n-butyl (sub-) phosphon Mg salt of acid, Mg salt of isobutyl (phosphorous acid), Mg salt of octyl (phosphorous acid), Ca salt of 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotris (methylphosphoric acid) Sulphonic acid) Ca salts, alkaline earth metal salts such as nitrilotris (methylphosphonic acid) Mg salts; methyl (phosphorous) phosphonic acid Ti salt, ethyl (phosphorous) phosphonic acid Ti salt, n-propyl (phosphorous) phosphonic acid Ti salt Isopropyl (phosphorous) Ti salt, n-butyl (phosphorous) phosphonic acid Ti salt, isobutyl (phosphorous) phosphonic acid Ti salt, octyl (phosphorous) phosphonic acid Ti salt, 1-hydroxyethylidene-1,1-diphosphonic acid Ti salts, nitrilotris (methylphosphonic acid) Ti salts and titanium salts such as titanyl salts corresponding to these Ti salts (including titanyl salts); methyl (sub) phosphonic acid Al salt, ethyl (sub) phosphonic acid Al salt, n-Propyl (phosphorous) phosphonic acid Al salt, Isopropyl (phosphorous) phosphonic acid Al salt, n-Butyl (phosphorous) phosphonic acid Al salt, Isobutyl (sub-) Succinic acid Al salt, octyl (phosphorous) phosphonic acid Al salt, ethane-1,2-diphosphonic acid Al salt, carboxymethylphosphonic acid Al salt, 2-carboxyethylphosphonic acid Al salt, Al salt of methylphosphonic acid monomethyl ester, 1- Aluminum salts such as hydroxyethylidene-1,1-diphosphonic acid Al salt, nitrilotris (methylphosphonic acid) Al salt; methyl (sub-) phosphonic acid Zn salt, ethyl (sub-) phosphonic acid Zn salt, n-propyl (sub-) phosphon Zn salt of acid, Zn salt of isopropyl (phosphorous acid), Zn salt of n-butyl (phosphorous acid), Zn salt of isobutyl (phosphorous acid), Zn salt of octyl (phosphorous acid), 1-hydroxyethylidene-1,1 -Organics such as zinc salts such as Zn diphosphonate and nitrilotris (methylphosphonic acid) Zn Sub-) phosphonic acid metal salt; methyl (sub-) phosphonic acid melamine salt, ethyl (sub-) phosphonic acid melamine salt, n-propyl (sub-) phosphonic acid melamine salt, isopropyl (sub-) phosphonic acid melamine salt, n-butyl (sub-acid) ) Melamine salt of phosphonate, melamine salt of isobutyl (sub-) phosphonate, melamine salt of octyl (sub-) phosphonate, melam salt corresponding to these melamine salts, melem salt, melon salt, melamine melam melem mela salt, melamine Aminotriazine compounds (melamine or condensates thereof) such as melam, melem, melon double salt, 1-hydroxyethylidene-1,1-diphosphonic acid mono to tetramelamine salt, nitrilotris (methylphosphonic acid) mono to hexane melamine salt Salt (organic (sub) phosphonic acid aminotriazine salt etc.) etc. The Of these, organic (sub) phosphonates are particularly preferable.

  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 / 7134 JP, US Patent 3,789,091, JP-U.S. Patent 3,849,368 and JP also include compounds described in U.S. Patent No. 4,390,477.

  These organic (phosphite) phosphoric acid compounds or salts thereof can be used alone or in combination of two or more.

  Preferred flame retardant aids (F) include (condensed) phosphate esters, (condensed) phosphate ester amides, (crosslinked) aryloxyphosphazenes, (phosphite) metal salts, hypophosphite metal salts, organic ( Sub-) phosphonic acid esters, organic (sub-) phosphonic acid metal salts, and organic (sub-) phosphonic acid aminotriazine salts, and particularly preferred flame retardant aids (F) include alkyl (sub-). At least one selected from metal phosphonates, metal (phosphite) phosphates and metal hypophosphites is included.

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.

  Among these flame retardant aids, it is particularly preferable to use at least one selected from aromatic compounds, phosphorus-containing compounds and antimony-containing compounds. In particular, when an oxo acid salt (C2) of a basic nitrogen-containing compound is used as the organic / inorganic acid salt (C), flame retardancy can be further improved by using an antimony-containing compound. In addition, the resin composition of this invention was excellent in the flame retardance reliably by the high level by combining the said component (B)-(D), even if it does not contain such a flame retardant adjuvant. Both electrical characteristics can be achieved.

  The ratio of the flame retardant aid (F) is, for example, 0 to 30 parts by weight (for example, 0.05 to 20 parts by weight), preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the base resin (A). Part (for example, 0.3 to 10 parts by weight), more preferably about 0.5 to 5 parts by weight.

(Other additives)
The flame retardant resin composition of the present invention further includes other additives such as other flame retardants (nitrogen-based, phosphorus-based flame retardants, etc.), fillers, stabilizers (ultraviolet absorbers, weather resistance (light) stabilizers). , Heat stabilizer, processing stabilizer, phosphorus stabilizer, reactive stabilizer, etc.), antistatic agent, lubricant, mold release agent, crystallization nucleator, plasticizer, colorant (dye, pigment, etc.), lubricant Further, an anti-dripping agent 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 a filler, a heat stabilizer, a processing stabilizer, and the like.

(filler)
Examples of the filler include conventional fibrous, plate-like, and granular fillers. Examples of the fibrous filler include inorganic fibers (glass fiber, carbon fiber, boron fiber, potassium titanate fiber (whisker), etc.), organic fiber (amide fiber, etc.) and the like. Examples of the plate-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). Examples thereof include sulfides (such as molybdenum disulfide and tungsten disulfide), carbides (such as fluorinated graphite and silicon carbide), activated carbon, and boron nitride. Preferred fillers include inorganic fibers (especially glass fibers). 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)
Examples of the heat resistance stabilizer include hindered phenol compounds (hindered phenol antioxidants) [for example, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6- t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-m-cresol), triethylene glycol-bis- (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate), pentaerythritol - tetrakis (3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate) branched such as _{C 3- 6} alkylphenols, etc.], phosphorus compounds (phosphorus antioxidants) [phosphites (bis (2,4-di-t-butylphenyl) pentae Bis (C _1-9 alkyl-aryl) pentaerythritol diphosphite such as lithitol 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, phenylnaphthylamine, 1,4 -Hindered amines such as phenylenediamine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate], hydroquinone Compounds (hydroquinone antioxidants) [for example, 2,5-di-t-butylhydro Quinones, etc.], quinoline compounds (quinoline antioxidants) [for example, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, etc.], etc .; alkali or alkaline earth metal compounds [e.g., hydrogen phosphate alkali or alkaline earth metal salts (e.g., magnesium dihydrogen phosphate, calcium dihydrogen phosphate, calcium hydrogen phosphate (dibasic calcium 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, or 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 ratio of the heat stabilizer is, for example, 0 to 15 parts by weight (for example, 0.001 to 10 parts by weight), preferably 0.01 to 5 parts by weight, and more preferably (particularly) with respect to 100 parts by weight of the base resin. 0.05 to 2 parts by weight). 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)
Examples of the processing stabilizer 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. _C10-34 saturated or unsaturated fatty acids such as arachidonic acid, erucic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid), long chain fatty acid amides (eg capric acid amide, lauric acid amide, myristic acid amide, palmitic acid) 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 (ethylenebisstearylamide), hexamethylenediamine-distearic acid amide, ethylene Diamine-dioleic acid amide, ethylenediamine-dierucic acid amide, ethylenediamine- (stearic acid amide) oleic acid amide, etc.), long chain fatty acid esters (eg, ethylene glycol distearic acid ester, glycerin monostearic acid ester, trimethylolpropane monostearic acid) Esters, pentaerythritol stearates, sorbitan monostearate, monostearate of polyalkylene glycol (polyethylene glycol, etc.), corresponding palmitate, laurate, behenate, montanate, oleic acid Long chain fatty acid esters exemplified above such as esters), polyalkylene glycols (polyethylene glycol, polypropylene glycol) , Polytetramethylene glycol, polyoxyethylene-polyoxypropylene copolymer, etc.), silicone compounds, waxes [for example, natural paraffin, synthetic paraffin, micro wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.) Etc.]. A processing stabilizer can be used individually or in combination of 2 or more types.

  The ratio of the processing stabilizer may be, for example, 0 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)
Examples of the reactive stabilizer 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 polymer, etc.], oxetane-based reactive stabilizer [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, etc. Carbodiimide, poly [ Like Rukirenbisu polycarbosilane imides such as (alkyl or cycloalkyl aryl) carbodiimide]. 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 halogen flame retardant (B), an organic / inorganic acid salt (C), It can be prepared by mixing the electrical property improver (D) and, if necessary, other components (electrical property enhancement aid, flame retardant 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.

  The flame retardant resin composition (and the molded product) of the present invention reliably ensures flame retardancy and electrical properties at a high level without impairing moldability and despite containing a halogen-based flame retardant. Can be compatible. For example, the resin composition (and the molded product) of the present invention has a flame retardancy based on the UL94 flammability test of V-2 or higher, preferably V-1 or higher, when measured with a thickness of 1.6 mm of the test piece. More preferably, it is V-0 or more. In the resin composition (and molded product) of the present invention, the comparative tracking index (CTI) based on IEC112 (UL746A) is 400 V or more (for example, about 400 to 1000 V), preferably 450 V or more (for example, 450 to About 900 V), more preferably 500 V or more (for example, about 500 to 850 V). In particular, in the resin composition of the present invention, a combination of a halogen-based flame retardant, a specific organic / inorganic acid salt, and a specific electrical property improver can reliably improve electrical properties at a remarkably high level. The tracking index (CTI) can be 600 V or higher (for example, about 600 to 850 V), preferably 650 V or higher (for example, about 650 to 750 V).

  The resin composition (and molded product) of the present invention has a flame retardancy 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.

  Further, the base resin (A), halogen-based flame retardant (B), organic / inorganic acid salt (C), electrical property improver (D), electrical property improvement aid (E) used in Examples and Comparative Examples, The flame retardant aid (F), filler (G), heat stabilizer (H), processing stabilizer (I), and reactive stabilizer (J) are as follows.

1. Base resin (A)
(A-1): Polybutylene terephthalate [inherent viscosity = 0.85]
(A-2): Polypropylene terephthalate [Intrinsic viscosity = 0.85]
(A-3): Polyethylene terephthalate [Intrinsic viscosity = 0.75]
(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, Inc.]
(B-2): Brominated polystyrene [Pyrocheck 68PB, manufactured by Ferrochemicals]
(B-3): Brominated polystyrene [SYTEX HP-7010P, manufactured by Albemarle]
(B-4): Ethylene bistetrabromophthalimide [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. Organic and inorganic acid salts (C)
Organic phosphinate (C1)
(C1-1): Aluminum methylethylphosphinate (C1-2): Calcium methylethylphosphinate (C1-3): Aluminum dimethylphosphinate (C1-4): 1-hydroxyphosphorane 1-oxide Aluminum salt of (C1-5): Melamine salt of dimethylphosphinic acid (C1-6): Aluminum salt of (2-carboxyethyl) methylphosphinic acid (C1-7): Aluminum salt of diethylphosphinic acid Oxo acid salt (C2)
(C2-1): Melamine polyphosphate [Melapur 200, manufactured by DSM]
(C2-2): Condensed phosphoric acid amide [Theien S, manufactured by Taihei Chemical Industry Co., Ltd.]
(C2-3): Dimelamine sulfate [Apinon-901, manufactured by Sanwa Chemical Co., Ltd.]
Acid pyrophosphate metal salt (C3: used in comparative examples)
(C3-1): Sodium acid pyrophosphate.

4). Electrical property improver (D)
Olefin resin (D1)
(D1-1): Ethylene / ethyl acrylate copolymer [NUC-6570, manufactured by Nippon Unicar Co., Ltd.]
(D1-2): Ethylene / glycidyl methacrylate copolymer [Bond First E, manufactured by Sumitomo Chemical Co., Ltd.]
(D1-3): Maleic anhydride modified polyolefin [Toughmer MP, manufactured by Mitsui Chemicals, Inc.]
(D1-4): Polypropylene [Noblen J, manufactured by Sumitomo Chemical Co., Ltd.]
(D1-5): Ethylene / propylene copolymer [J707ZB, manufactured by Mitsui Chemicals, Inc.]
Fluorine resin (D2)
(D2-1): Polytetrafluoroethylene [Teflon 6J, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.]
Periodic table Group 4 metal-containing compound (D3)
(D3-1): Titanium oxide [TITONE SR-1, manufactured by Sakai Chemical Industry Co., Ltd.].

5. Electric property improvement aid (E)
(E-1): Talc (E-2): Hydrous zinc borate [Firebrake ZB, manufactured by Borax Japan Co., Ltd.]
(E-3): Melamine cyanurate (E-4): Calcium carbonate.

6). Flame retardant aid (F)
Aromatic compounds (F1)
(F1-1): Bisphenol A type epoxy resin [Epicoat 1004K, manufactured by Yuka Shell Epoxy Co., Ltd.]
(F1-2): Novolac type epoxy resin [EPPN-201, manufactured by Nippon Kayaku Co., Ltd.]
(F1-3): Polycarbonate resin [Panlite L1225, manufactured by Teijin Chemicals Ltd.]
Phosphorus-containing compound (F2)
(F2-1): Resorcinol bis (di-2,6-xylyl phosphate) [PX200, manufactured by Daihachi Chemical Industry Co., Ltd.]
(F2-2): Phenoxytolyloxyphosphazene [KEMIDANT302S, manufactured by Chemipro Kasei Co., Ltd.]
(F2-3): Cyclic phenoxyphosphazene (3-tetramer mixture)
(F2-4): 1,4-piperazinediyltetraphenyl phosphate (F2-5): ethylphosphonic acid aluminum salt (F2-6): ethylphosphonic acid aluminum salt (F2-7): aluminum phosphite salt ( F2-8): calcium hypophosphite antimony-containing compound (F3)
(F3-1): Antimony trioxide (F3-2): Sodium antimonate.

7). Filler (G)
(G-1): Glass fiber (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)
Hindered phenol heat resistance stabilizer (H1)
(H1-1): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
Heat stabilizer (H2)
(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): calcium dihydrogen phosphate (H2-4): hydrotalcite [DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.].

9. Processing stabilizer (I)
(I-1): Polyethylene wax [Sunwax, Sanyo Chemical Industries, Ltd.]
(I-2): Montanate 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): Polycardiimide [Carbodilite HMV-8CA, manufactured by Nisshinbo Industries, Inc.].

(Examples 1-32 and Comparative Examples 1-12)
Filling base resin (A) with halogen flame retardant (B), organic / inorganic acid salt (C), electrical property improver (D), electrical property improver (E), flame retardant aid (F), filling After mixing the agent (G), the heat resistance stabilizer (H), and the processing stabilizer (I) in the ratios shown in Tables 1 to 4, a resin composition was prepared by melt mixing with a 30 mm diameter twin screw extruder. A predetermined test piece was molded by an injection molding machine using this resin composition, and flame retardancy (1.6 mm) and electrical characteristics were measured. In Comparative Example 10, foaming of the resin occurred during the extrusion preparation and molding of the resin composition due to the acidic sodium pyrophosphate. The results are shown in Tables 1-4.

（実施例３３〜４８）
ベース樹脂（Ａ）に、ハロゲン系難燃剤（Ｂ）、有機・無機酸塩（Ｃ）、電気特性向上剤（Ｄ）、電気特性向上助剤（Ｅ）、難燃助剤（Ｆ）、充填剤（Ｇ）、耐熱安定剤（Ｈ）、加工安定剤（Ｉ）、反応性安定剤（Ｊ）を表５に示す割合（重量部）で混合し、押出機により混練押出してペレット状の樹脂組成物を調製した。得られたペレットを用いて、射出成形により試験用成形品を作製し、燃焼性（１．６ｍｍ）及び耐トラッキング性（比較トラッキング指数）を評価した。結果を表５に示す。

(Examples 33 to 48)
Filling base resin (A) with halogen flame retardant (B), organic / inorganic acid salt (C), electrical property improver (D), electrical property improver (E), flame retardant aid (F), filling The resin (G), the heat stabilizer (H), the processing stabilizer (I), and the reactive stabilizer (J) are mixed in the proportions (parts by weight) shown in Table 5 and kneaded and extruded by an extruder to form a pellet-shaped resin. A 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 5.

（実施例４９〜５８、比較例１３〜１４）
ベース樹脂（Ａ）に、ハロゲン系難燃剤（Ｂ）、有機・無機酸塩（Ｃ）、電気特性向上剤（Ｄ）、電気特性向上助剤（Ｅ）、難燃助剤（Ｆ）、充填剤（Ｇ）、耐熱安定剤（Ｈ）、加工安定剤（Ｉ）を表６に示す割合（重量部）で混合し、押出機により混練押出してペレット状の樹脂組成物を調製した。得られたペレットを用いて、射出成形により試験用成形品を作製し、燃焼性（０．８ｍｍ）及び耐トラッキング性（比較トラッキング指数）を評価した。結果を表６に示す。

(Examples 49-58, Comparative Examples 13-14)
Filling base resin (A) with halogen flame retardant (B), organic / inorganic acid salt (C), electrical property improver (D), electrical property improver (E), flame retardant aid (F), filling The agent (G), the heat stabilizer (H), and the processing stabilizer (I) were mixed in the proportions (parts by weight) shown in Table 6 and kneaded and extruded with an extruder to prepare a pellet-shaped resin composition. Using the obtained pellets, test molded articles were produced by injection molding, and the flammability (0.8 mm) and the tracking resistance (comparative tracking index) were evaluated. The results are shown in Table 6.

Claims (26)

At least one organic / inorganic acid salt selected from a base resin (A), a halogen flame retardant (B), an organic phosphinic acid salt (C1) and an oxo acid salt (C2) of a basic nitrogen-containing compound ( and C), is composed out with electrical characteristics improver (D), and a flame-retardant resin composition having improved electrical characteristics, oxo acid salt of the oxo acid salt (C2) is, amino triazine compounds A flame retardant resin composition in which the electrical property improver (D) is composed of at least one selected from an olefin resin, a fluorine resin and a Group 4 metal compound of the periodic table.   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. The resin composition according to claim 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 according to claim 1, comprising at least one selected from the group consisting of:   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 The resin composition according to claim 1, which is 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 resin according to claim 1, wherein the organic phosphinate (C1) is an aliphatic phosphinate that may have a substituent and / or an alicyclic phosphinate that may have a substituent. Composition. The organic phosphinic acid salt (C1) may have a dialkylphosphinic acid which may have a substituent, a dicycloalkylphosphinic acid which may have a substituent, an alkylenephosphinic acid which may have a substituent, Selected from optionally substituted alkenylene phosphinic acid, optionally substituted (bi) cycloalkylenephosphinic acid, and optionally substituted alkanebis (alkylphosphinic acid) Organophosphinic acid, Periodic Table Group 1 metal, Periodic Table Group 2 metal, Periodic Table Group 4 metal, Periodic Table Group 7 metal, Periodic Table Group 8 metal, Periodic Table Group 10 metal, Periodic Table Group A salt with at least one selected from Group 11 metal, Group 12 metal, Periodic group 13 metal, Periodic group 14 metal, Periodic group 15 metal and aminotriazine compound; Seo salt (C2) is condensed phosphoric acid, and at least one oxoacid chosen from sulfuric acid and pyrosulfate, amino triazine compound resin composition according to claim 1, wherein the salt.   The organic phosphinic acid salt (C1) may have a dialkylphosphinic acid which may have a substituent, a dicycloalkylphosphinic acid which may have a substituent, an alkylenephosphinic acid which may have a substituent, An organic phosphinic acid selected from alkenylene phosphinic acid optionally having substituent (s) and alkanebis (alkylphosphinic acid) optionally having substituent (s), Group 2 metal of Periodic Table, Group 13 of Periodic Table A salt of at least one selected from metal, melamine, melam, melem, and melon, wherein the oxo acid salt (C2) is a salt of polyphosphoric acid and an aminotriazine compound, a salt of sulfuric acid and an aminotriazine compound, pyro The resin composition according to claim 1, wherein the resin composition is at least one selected from a salt of sulfuric acid and an aminotriazine compound, and a condensed phosphoric acid amide.   The resin composition according to claim 1, wherein the organic / inorganic acid salt (C) comprises an organic phosphinic acid salt (C1) and an oxo acid salt (C2). The resin composition according to claim 1, wherein the electrical property improver (D) comprises at least an olefin resin and / or a Group 4 metal compound of the periodic table. The electrical property improver (D) is an α-C _2-3 olefin homo- or copolymer, α-C _2-3 olefin- (meth) acrylic acid copolymer, α-C _2-3 olefin- (meta ) Acrylic acid C _1-4 alkyl ester copolymer, α-C _2-3 olefin- (meth) acrylic acid glycidyl ester copolymer, acid-modified olefin resin, fluorinated α-C _2-3 olefin alone or The resin composition according to claim 1, wherein the resin composition is at least one selected from a copolymer and titanium oxide.   The proportion of the halogen-based flame retardant (B) is 2 to 20 parts by weight and the proportion of the organic / inorganic acid salt (C) is 3 to 30 parts by weight with respect to 100 parts by weight of the base resin (A). 1. The resin composition according to 1.   The proportion of the organic / inorganic acid salt (C) is 20 to 500 parts by weight and the proportion of the electrical property improver (D) is 10 to 150 parts by weight with respect to 100 parts by weight of the halogen flame retardant (B). The resin composition according to 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 (E).   And at least selected from melamine cyanurate, talc, kaolin, (hydrous) zinc borate, (hydrous) calcium borate, (hydrous) zinc stannate, zinc oxide, zinc sulfide, calcium carbonate, and calcium hydrogen phosphate The resin composition of Claim 1 containing a kind of electrical property improvement adjuvant (E).   The resin composition according to claim 1, further comprising at least one flame retardant aid (F) selected from aromatic compounds, phosphorus-containing compounds and antimony-containing compounds.   Flame retardant aid (F) is phenol resin, polyphenylene oxide resin, aromatic epoxy resin, phenoxy resin, polyphenylene sulfide resin, polycarbonate resin, polyarylate resin, aromatic polyamide resin, aromatic polyester resin The resin composition according to claim 17, wherein the resin composition is at least one selected from a resin and an aromatic polyesteramide resin.   Flame retardant aid (F) is (condensed) phosphoric acid ester, (condensed) phosphoric acid ester amide, (crosslinked) aryloxyphosphazene, (sub) phosphorous acid metal salt, hypophosphorous acid metal salt, organic (sub) The resin composition according to claim 17, wherein the resin composition is at least one selected from phosphonic acid esters, organic (phosphorous) phosphonic acid metal salts, and organic (phosphorous) phosphonic acid aminotriazine salts.   The resin composition according to claim 17, wherein the flame retardant aid (F) is at least one selected from an alkyl (phosphite) metal salt, a (phosphite) metal salt, and a hypophosphite metal salt.   The resin composition according to claim 1, further comprising at least one additive selected from a filler, a heat stabilizer, a processing stabilizer, and a reactive stabilizer.   (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 at a test piece thickness of 1.6 mm, the flame retardancy according to the UL94 flammability test is V-2 or higher, and (ii) the comparative tracking index according to IEC112 is 500 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 650 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 25, which is an electrical / electronic part, an office automation equipment part, a household electrical equipment part, an automobile part, or a mechanical mechanism part.