JP5405738B2 - Flame retardant resin composition - Google Patents

Description

  The present invention relates to a resin composition having excellent flame retardancy and a molded article formed from the flame retardant resin composition.

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

On the other hand, in Japanese Patent Application Laid-Open No. 10-114854 (Patent Document 1) and Japanese Patent Application Laid-Open No. 10-273589 (Patent Document 2), a composition containing a polyester resin, a polyamide resin, a halogenated flame retardant, or the like is used. A flame retardant resin molding composition with improved electrical properties comprising an effective amount of pyro / polyphosphate metal salt to improve (such as comparative tracking index) is disclosed. However, even when a halogen-based flame retardant and pyro / polyphosphate are used in combination, the effect of improving the comparative tracking index is insufficient, and it is difficult to achieve both flame retardancy and electrical characteristics.
JP-A-10-11854 (Claim 1 and Example) JP-A-10-273589 (Claim 1 and Example)

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

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

  As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that when a halogen-based flame retardant, an organic phosphinic acid or a salt thereof, and a flame retardant aid are combined, the flame resistance and electrical characteristics of the base resin can be obtained even in a small amount. The present invention has been completed.

  That is, the flame retardant resin composition of the present invention is composed of a base resin, a halogen flame retardant, an organic phosphinic acid or a salt thereof, and a flame retardant aid, and has improved electrical characteristics. The halogen-based flame retardant includes bromine-containing acrylic resin, bromine-containing styrene resin, bromine-containing polycarbonate resin, bromine-containing epoxy compound (including bromine-containing phenoxy resin), bromine-containing phosphate ester, bromine-containing triazine compound, bromine It may be a bromine atom-containing flame retardant such as a containing isocyanuric acid compound, a brominated polyarylether compound, a brominated aromatic imide compound, or a brominated bisaryl compound. The organic phosphinic acid may be a compound represented by the following formula (1).

（式中、Ｒ^１及びＲ^２は同一又は異なって、置換基を有していてもよい炭化水素基を示す。Ｒ^１及びＲ^２は互いに結合して隣接するリン原子とともに環を形成してもよい）
有機ホスフィン酸の塩は、有機ホスフィン酸と、金属及びアミノ基を有する窒素含有化合物から選択された少なくとも一種との塩であってもよい。前記難燃助剤は、例えば、アンチモン含有化合物、フッ素含有樹脂、ケイ素含有化合物、芳香族樹脂、（縮合）リン酸アミノトリアジン塩を除くリン含有化合物などであってもよい。なお、難燃助剤が樹脂状難燃剤である場合、前記ベース樹脂とは種類の異なる成分が使用できる。

(In the formula, R ¹ and R ² are the same or different and each represents a hydrocarbon group which may have a substituent. R ¹ and R ² are bonded to each other to form a ring with an adjacent phosphorus atom. Also good)
The salt of organic phosphinic acid may be a salt of organic phosphinic acid and at least one selected from a nitrogen-containing compound having a metal and an amino group. The flame retardant aid may be, for example, an antimony-containing compound, a fluorine-containing resin, a silicon-containing compound, an aromatic resin, a phosphorus-containing compound other than a (condensed) phosphate aminotriazine salt. In addition, when a flame retardant adjuvant is a resin-like flame retardant, a different component from the said base resin can be used.

  The proportion of each component with respect to 100 parts by weight of the base resin is such that the halogen-based flame retardant is about 3 to 30 parts by weight, the proportion of the organic phosphinic acid or its salt is about 1 to 30 parts by weight, and the flame retardant aid is 0.1 to 30 parts. It may be about parts by weight. You may contain organic phosphinic acid or its salt 5-500 weight part and flame retardant adjuvant 0.1-200 weight part with respect to 100 weight part of halogenated flame retardants.

The resin composition may further contain an olefin resin (such as an α-C _2-3 olefin- (meth) acrylic ester copolymer). Further, the resin composition may further contain an electrical property improving aid and the like. The electrical property improving aid is a metal oxide, metal sulfide, (hydrous) metal silicate, (hydrous) metal borate, (hydrous) metal stannate, hydrogen phosphate metal salt, aminotriazine compound, It may be at least one selected from pyrophosphate, polyphosphate, polymetaphosphate and polyphosphate amide.

  The proportion of the organic phosphinic acid or a salt thereof may be 10 to 300 parts by weight with respect to 100 parts by weight of the halogen-based flame retardant, and the proportion of the olefin resin may be a halogen-based flame retardant and an organic phosphinic acid or a salt thereof. The total amount may be 1 to 150 parts by weight with respect to 100 parts by weight.

  The resin composition may further contain at least one selected from an antioxidant, a stabilizer, a lubricant and a filler.

  The resin composition may have a comparative tracking index based on IEC112 of 300 V or higher (particularly 350 V or higher). In addition, the resin composition has (a) (i) flame retardancy based on UL94 flammability test of V-1 or more when measured at a test piece thickness of 1.6 mm, and (ii) IEC112 Resin composition having a compliant comparative tracking index of 500 V or more, (b) (i) When measured at a test piece thickness of 1.6 mm, flame retardancy in accordance with UL94 flammability test is V-0 or more, And (ii) a resin composition having a comparative tracking index conforming to IEC112 of 350 V or more, (c) (i) when measured at a test piece thickness of 0.8 mm, flame retardancy conforming to UL94 flammability test is V Also included is a resin composition having a value of −0 or more and (ii) a comparative tracking index according to IEC112 of 300 V or more.

  The molded product formed with the said resin composition is also contained in this invention. The molded article may be at least one selected from electrical and / or electronic parts, home appliance parts, office automation (OA) equipment parts, mechanical mechanism parts, and automobile parts.

  In the present invention, since a halogen-based flame retardant, an organic phosphinic acid or a salt thereof, and a flame retardant aid are combined, even if the amount of these components used is small, not only the flame retardancy of the resin, Improve characteristics (such as comparative tracking index). Moreover, in the flame-retardant resin composition further containing an olefin resin, electrical characteristics such as tracking resistance can be further improved.

Detailed Description of the Invention

  The flame retardant resin composition of the present invention comprises a base resin, a halogen flame retardant, an organic phosphinic acid or a salt thereof, and a flame retardant aid. 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)
The base resin is not particularly limited and includes various thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin constituting the base resin include polyester resins, polyamide resins, polycarbonate resins, polyphenylene oxide resins, polyphenylene sulfide resins, acrylic resins, styrene resins, and vinyl resins.

(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 (for example, C _4-40 dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, hexadecanedicarboxylic acid, and dimer acid, preferably C _4-14 dicarboxylic acids), fats cyclic dicarboxylic acids (e.g., hexahydrophthalic acid, hexahydroterephthalic acid, _{C 8-12} dicarboxylic acids such as himic acid), an aromatic dicarboxylic acid _{[C 8-16} dicarboxylic acids, for example, an array Nji carboxylic acid (phthalic acid, Isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc.), bisphenyl-dicarboxylic acid (4,4'-biphenyldicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylalkanedicarboxylic acid (4,4 ' -Diphenylmethane dicarboxylic acid), 4,4'-di Phenyl ketone dicarboxylic acid etc.)], or derivatives thereof (for example, derivatives capable of forming an ester such as lower alkyl esters, aryl esters, acid anhydrides, etc.). These dicarboxylic acid components may be used alone or in combination of two or more. Furthermore, you may use together polyvalent carboxylic acids, such as trimellitic acid and a pyromellitic acid, as needed.

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

Examples of the diol component include aliphatic diols [for example, alkylene glycol (for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, etc. C _2-12 alkylene glycol, 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) , Tripropylene glycol, polytetramethylene glycol, etc.)], alicyclic diols [for example, 1,4-cyclohexanediol, cycloalkane dialkanol (1,4- Cyclohexane di _{C 5-6} cycloalkane _{C 1-2} alkanols such as methanol, 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. These 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 (p-hydroxybenzoic acid, m-hydroxybenzoic acid, etc.), oxynaphthoic acid (2-hydroxy-6-naphthoic acid, etc.), 4-carboxy-4'-hydroxybiphenyl. , Hydroxyphenylacetic acid, glycolic acid, D-, L- or D / L-lactic acid, oxycarboxylic acids such as oxycaproic acid, or derivatives thereof.

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 arylates (such as 1,4-cyclohexanedimethylene terephthalate units) and alkylene arylates (alkylene terephthalate and / or alkylene naphthalate units such as C _2-4 alkylene terephthalate units, C _2. A homopolyester or copolyester having at least one unit selected from _-4 alkylene naphthalate units) as a main component (for example, about 50 to 100% by weight, preferably about 75 to 100% by weight) [for example, poly 1, 4-cyclohexanedimethylene terephthalate (PCT), polyalkylene terephthalate (for example, polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (P T) 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; cycloalk Copolyester containing at least one unit selected from candialkylene 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 a butylene terephthalate unit as a main component (for example, polybutylene terephthalate, polybutylene terephthalate copolyester), polypropylene terephthalate resins containing a propylene terephthalate unit as a main component ( For example, polypropylene terephthalate, polypropylene terephthalate copolyester) and polyethylene terephthalate resin (for example, polyethylene terephthalate, polyethylene terephthalate copolyester) containing ethylene terephthalate units as main components are included. In addition, these polyester-type resin can be used individually or in combination of 2 or more types.

In the copolyester, the copolymerizable monomer includes C _2-6 alkylene glycol (such as linear alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol), and a repeating number of 2 to 2. Polyalkylene glycols having about 4 oxyalkylene units (eg, glycols containing poly (oxy-C _2-4 alkylene) units such as diethylene glycol and polytetramethylene glycol), C _4-12 aliphatic dicarboxylic acids (succinic acid, glutar Acid, adipic acid, sebacic acid, etc.), alicyclic diol (1,4-cyclohexanedimethanol, etc.), aromatic diol [C _2-3 alkylene oxide adduct of bisphenols such as 2,2-bis (4 -(2-hydroxyethoxy) phenyl) propane Etc.], aromatic dicarboxylic acids [asymmetric aromatic dicarboxylic acids (phthalic acid, isophthalic acid, 5-sulfoisophthalic acid monosodium salt, etc.), diphenyldicarboxylic acid, etc.], oxycarboxylic acids (oxybenzoic acid, oxynaphthoic acid, 4 -Carboxy-4'-hydroxybiphenyl and the like). 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 66 / 6I / 6, polyamide 66 / 6I / 11, polyamide 66 / 6I / 12, polyamide 66 / 6I / 610, polyamide 66 / 6I / 612, polyamide 6T / M5T, etc.) Is preferred.

(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 (4-hydroxyphenyl) methane and bis (hydroxyaryl) C _1-10 alkanes such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A); 1,1-bis (4 Bis (hydroxyaryl) C _4-10 cycloalkanes such as -hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl sulfone; 4,4'-dihydroxydiphenyl sulfide; 4,4'- Examples thereof include dihydroxy diphenyl ketone.

  Preferred polycarbonate-based resins include bisphenol A type polycarbonate. Polycarbonate resins can be used alone or in combination of two or more.

(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.), benzene formaldehyde resins (formaldehyde condensates such as phenol resins) and alkylbenzene formaldehyde resins, alkylphenol modified benzene formaldehyde resins obtained by reacting alkylphenols such as cresol A modified polyphenylene oxide copolymer composed of a block and a polyphenylene oxide block as a main structure, a polyphenylene oxide or a copolymer thereof, a styrenic polymer and / or an unsaturated carboxylic acid or anhydrous ((Meth) acrylic acid, maleic anhydride) and the like modified graft copolymers are grafted. Polyphenylene oxide resins can be used alone or in combination of two or more.

(Polyphenylene sulfide resin)
The polyphenylene sulfide resin (polyphenylene thioether resin) includes a homopolymer and a copolymer having a polyphenylene 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 (or a single bond), O, CO, or SO ₂ ], etc. It may be. The polyphenylene sulfide resin may be a homopolymer using the same repeating unit among the phenylene sulfide groups composed of such phenylene groups, or may be a copolymer containing different repeating units.

  The homopolymer is preferably a substantially linear polymer having a p-phenylene sulfide group as a repeating unit. Copolymers can be used in combination of two or more different 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 relatively low molecular weight linear polymer, and may have a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional monomer. It may be a polymer. The polyphenylene sulfide resin also includes a branched or crosslinked polyphenylene sulfide resin obtained by polymerizing a monomer having three or more functional groups, and a resin composition obtained by blending this resin with the linear polymer.

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

The number average molecular weight of the polyphenylene sulfide resin is, for example, about 300 to 30 × 10 ⁴ , preferably about 400 to 10 × 10 ⁴ .

(Acrylic resin)
Examples of the acrylic resin include (meth) acrylic acid, (meth) acrylic acid C _1-10 alkyl ester such as methyl (meth) acrylate, and (meth) acrylic acid hydroxy C ₁ such as hydroxyethyl (meth) acrylate. _-10 Alkyl esters, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, (meth) acrylic monomers such as (meth) acrylamide and (meth) acrylonitrile, or copolymers or (meth) Copolymers of acrylic monomers and other copolymerizable monomers are included. Preferable acrylic resins include poly (meth) methyl acrylate, (meth) acrylic acid-styrene copolymer, methyl (meth) acrylate-styrene copolymer, and the like. These acrylic resins can be used alone or in combination of two or more.

(Styrene resin)
Examples of the styrenic resin include a styrene monomer (eg, styrene, vinyltoluene, etc.) or a copolymer; a styrene monomer and a vinyl monomer [eg, (meth) acrylic monomer (For example, (meth) acrylonitrile, (meth) acrylic acid ester, (meth) acrylic acid, etc.), α, β-monoolefinic unsaturated carboxylic acid such as maleic anhydride or acid anhydride or ester thereof) and the like A styrene graft copolymer, a styrene block copolymer, and the like.

  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. . These styrenic resins can be used alone or in combination of two or more.

(Vinyl resin)
Examples of vinyl resins include vinyl monomers (eg, vinyl esters such as vinyl acetate; chlorine-containing vinyl monomers (eg, vinyl chloride); fluorine-containing vinyl monomers; vinyl ketones; vinyl ethers; N- For example, vinylamines such as vinylcarbazole, etc.) or copolymers with other copolymerizable monomers. 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 vinyl resins can be used alone or in combination of two or more.

(Other resins)
Other resins include polyacetal resins (polyacetal homo- or copolymers); ketone resins; polysulfone resins (for example, polysulfone, poly (ether sulfone), poly (4,4′-bisphenol ether sulfone, etc.); polyethers Examples include ketone resins (polyether ketone, poly (ether ether ketone), etc.), polyether imides, thermoplastic polyurethane resins, thermoplastic polyimides, polyoxybenzylenes, thermoplastic elastomers, etc. Thermosetting resins Examples thereof include phenol resins, amino resins, thermosetting polyester resins, epoxy resins, silicone resins, vinyl ester resins, polyurethane resins, and the like.

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

  Preferable base resins include thermoplastic resins such as polyester resins, which may be liquid crystal polyesters, polyacetal resins, styrene resins, polyamide resins, polyphenylene oxide resins, and more preferably polyester resins (PBT). Resin, PPT resin, PET resin, etc.), polyamide resin and the like.

  The base resin may be an alloy composed of a plurality of resins. Among the base resins, for example, a polycarbonate resin, a polyphenylene oxide resin, a polyphenylene sulfide resin, and the like may be used as an alloy in combination with other resins (for example, a polyester resin and / or a polyamide resin).

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)
Organic halides can be used as the halogen-based flame retardant. The organic halide usually contains at least one halogen atom 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 copolymers], halogen-containing styrene resins [halogenated polystyrene (brominated polystyrene, chlorinated polystyrene and other styrene resins) Treated halides, halogenated styrene monomers alone or copolymers, etc.), halogen-containing polycarbonate resins (brominated polycarbonates, halogenated polycarbonates such as chlorinated polycarbonate, etc.), halogen-containing Poxy compounds (halogenated epoxy resins such as brominated epoxy resins and chlorinated epoxy resins; halogenated phenoxy resins such as brominated phenoxy resins), halogen-containing phosphate esters [for example, tris (bromoethyl) phosphate, tris (mono or Bromine-containing phosphoric acid such as dibromopropyl) phosphate, tris (mono or dibromobutyl) phosphate, tris (mono to tribromoneopentyl) phosphate, bis (tribromoneopentyl) phenyl phosphate, tris (mono to tribromophenyl) phosphate Esters, etc.], halogen-containing triazine compounds (eg, bromine-containing triazine compounds such as tris (tribromophenoxy) triazine), halogen-containing isocyanuric acid compounds [eg, tris (2 Bromine-containing isocyanuric acid compounds such as 3-dibromopropyl) isocyanurate, tris (2,3,4-tribromobutyl) isocyanurate, tris (pentabromobenzyl) isocyanurate], 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], halogenated Aromatic imide compounds [eg brominated aromatic imide compounds such as ethylene bis brominated phthalimide (eg bisimide compounds etc.)], halogenated bisaryl compounds [eg dibrominated Bis (halogenated C _6-10 aryl) such as phenyl; Bis (halogenated C _6-10 aryl) C _1-4 alkane such as brominated diphenylmethane; Halogenated bisphenols such as brominated bisphenol A or derivatives thereof (halogen) Brominated polyesters obtained by polymerizing ethylene oxide adducts of bisphenols)), halogenated alicyclic hydrocarbons (crosslinked cyclic saturated or unsaturated halogenated alicyclic hydrocarbons such as dodecachloropentacyclooctadeca And halogenated polycycloalkadiene such as 7,15-diene). Halogen flame retardants can be used alone or in combination of two or more.

  The halogen-based flame retardant is preferably a compound containing a chlorine atom and / or a bromine atom, and particularly an organic bromide containing a bromine atom [bromine-containing acrylic resin, bromine-containing styrene resin, bromine-containing polycarbonate resin, bromine -Containing epoxy compounds (brominated epoxy resins such as brominated epoxy resins, brominated phenoxy resins such as brominated phenoxy resins), brominated phosphates, brominated triazine compounds, brominated isocyanuric compounds, brominated polyaryl ethers Bromine atom-containing flame retardants such as compounds (such as bis (brominated aryl) ether compounds such as octabromodiphenyl ether), brominated aromatic imide compounds and brominated bisaryl compounds) are preferred.

  Among these bromine atom-containing flame retardants, in particular, brominated polybenzyl (meth) acrylate resins, alkylene brominated phthalimides, brominated products of styrene resins, and homo- or copolymers of brominated styrene monomers (brominated) At least one selected from polystyrene and the like is preferable. Further, at least one selected from brominated bisphenol A type epoxy resin, brominated bisphenol A type phenoxy resin and brominated bisphenol A type polycarbonate resin is also preferable.

(Organic phosphinic acid or its salt)
An organic phosphinic acid or a salt thereof (hereinafter sometimes simply referred to as an organic phosphinic acid compound) includes an organic group (hydrocarbon having a substituent) on a bisphosphinic acid condensed with phosphinic acid or phosphinic acid. Group substituted organic group-substituted phosphinic acid, polyvalent phosphinic acid (polyvalent phosphinic acid in which a plurality of phosphinic acids are linked by a polyvalent organic group), or a salt thereof [metal, boron, ammonium and basic nitrogen And salts with at least one salt-forming component selected from the containing compounds (metal salts, boron salts (boryl compounds, etc.), ammonium salts, salts with amino group-containing nitrogen-containing compounds, etc.) and the like can be used. The organic phosphinic acid compound can improve the electrical characteristics of the resin even when a halogen-based flame retardant is used. Therefore, the organic phosphinic acid compound seems to function as an electrical property improver.

  Of the organic phosphinic acids, compounds represented by the above formula (1), polyvalent phosphinic acids (such as bisphosphinic acid) and the like are preferable.

In the formula (1), examples of the hydrocarbon group represented by R ¹ and R ² include an aliphatic hydrocarbon group [an alkyl group (linear or branched chain such as methyl, ethyl, t-butyl group, etc.). _{-Like C1-20} alkyl group), alkenyl group (such as linear or branched _C2-20 alkenyl group such as vinyl, allyl, isopropenyl group, etc.), alicyclic hydrocarbon group [cycloalkyl group, etc. (Such as C _5-10 cycloalkyl group such as cyclohexyl group), etc.], aromatic hydrocarbon group [aryl group (such as C _6-10 aryl group such as phenyl group)], aralkyl group (C _6-10 such as benzyl group). Aryl-C _1-4 alkyl group etc.)] and the like.

The ring formed by combining R ¹ and R ² together with the adjacent phosphorus atom is a heterocycle (phosphorus atom-containing heterocycle) having the phosphorus atom as a heteroatom constituting the ring, and is usually a 4- to 20-membered heterocycle. A ring, preferably a 5- to 16-membered heterocycle is mentioned. The phosphorus atom-containing heterocycle may be a bicyclo ring. The phosphorus atom-containing heterocycle may have an unsaturated group (alkenylene group, alkynylene group, etc.) and / or a substituent in the ring.

Examples of the substituent of the hydrocarbon group and the phosphorus atom-containing heterocycle include a halogen atom (fluorine, chlorine, bromine, iodine atom, etc.) and an alkyl group (methyl, ethyl, t-butyl group, etc.) -Like C _1-6 alkyl group, etc.), alkenyl groups (such as linear or branched C _2-6 alkenyl groups such as vinyl groups), the above-exemplified cycloalkyl groups, the above-exemplified aryl groups, and the above-exemplified aralkyls. Group, hydroxyl group, alkoxy group (such as linear or branched C _1-4 alkoxy group such as methoxy and ethoxy group), carboxyl group, acyl group (such as C _2-6 acyl group such as acetyl group), alkoxy carbonyl group (C _1-4 alkoxy such as methoxy carbonyl group - carbonyl group), an amino group, N- substituted amino group (methylamino group, dimethyl An alkyl amino group such as amino group), a nitro group, a cyano group, and a oxo group (= O). The hydrocarbon and phosphorus atom-containing heterocycle may have one of the above-described substituents and may have a plurality of the same or different substituents.

  Examples of the organic phosphinic acid (1) include compounds such as the following formulas (1a) and (1b).

（式中、環Ｚ^１及びＺ^２は同一又は異なって、リン原子を環の構成原子として含む４〜１０員環を示し、前記置換基を有してもよい。Ｒ^１及びＲ^２は前記に同じ）
なお、前記環Ｚ^１、及び環Ｚ^１と環Ｚ^２とで構成されるビシクロ環は、前記式(1)において、Ｒ^１及びＲ^２が隣接するリン原子と共に形成する環（リン原子含有ヘテロ環）に対応する。

(In the formula, rings Z ¹ and Z ² are the same or different and each represents a 4- to 10-membered ring containing a phosphorus atom as a constituent atom of the ring, and may have the substituent. R ¹ and R ² are Same as)
Incidentally, the bicyclo ring formed by ring Z ^1, and the ring Z ¹ and the ring Z ^2, in the formula (1), the ring (phosphorus atom-containing hetero forming together with the phosphorus atom to which R ¹ and R ² are adjacent Corresponding to the ring).

The number of members of rings Z ¹ and Z ² may be preferably 4 to 8 members, more preferably about 5 to 6 members. In the heterocycles Z ¹ and Z ² , the heterocycle may have 1 to 2 carbon-carbon unsaturated bonds.

In the formula (1a), R ¹ and R ² are preferably an alkyl group (C _1-16 alkyl group etc.) optionally having a substituent (hydroxyl group, carboxyl group, alkoxy group etc.). .

  Examples of metals that form organic phosphinates include Group 1 metals (alkali metals) (potassium, sodium, etc.), Group 2 metals (alkaline earth metals) (magnesium, calcium, barium, etc.), periodicity, 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; periodic tables such as nickel Group 10 metals; periodic table Group 11 metals such as copper), periodic table Group 12 metals such as zinc, and periodic table Group 13 metals such as aluminum. These metals can be used alone or in combination of two or more. Among these metals, at least one selected from Group 1 metal, Group 2 metal, Group 4 metal, Group 8 metal, Group 12 metal and Group 13 metal of the periodic table, in particular, Periodic Table 2 Group metals and / or Group 13 metals of the periodic table are preferred. The metal salt may be a hydrate salt such as a hydrate magnesium salt, a hydrate calcium salt, a hydrate aluminum salt, a hydrate zinc salt, and the like. 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. Of these nitrogen-containing compounds, aminotriazine compounds (such as melamine and melamine condensates) are particularly preferable.

  These salt-forming components can be used alone or in combination of two or more. The organic phosphinic acid salt includes a double salt of an organic phosphinic acid and a plurality of salt-forming components, for example, a melamine, melam, melem, double salt, melamine, melam, melem, melon.

Specific examples of the organic phosphinic acid compound include the organic phosphinic acid represented by the above formula (1a) or a salt thereof, for example, an alkylphosphinic acid [dialkylphosphinic acid (diC _1-10 which may have a substituent). Alkylphosphinic acid, etc.), for example, dimethylphosphinic acid, methylethylphosphinic acid, diethylphosphinic acid, ethyl (n-, iso- or t-) butylphosphinic acid, di-n-propylphosphinic acid, diisopropylphosphinic acid, di-n- Dialkylphosphinic acids such as butylphosphinic acid, diisobutylphosphinic acid, di-t-butylphosphinic acid, dipentylphosphinic acid, dioctylphosphinic acid; (hydroxymethyl) methylphosphinic acid, (hydroxyethyl) methylphosphinic acid, bis (hydroxymethyl) phosphine Acid, bi Hydroxyl group-containing dialkylphosphinic acid such as (hydroxyethyl) phosphinic acid; Carboxyl group-containing dialkylphosphinic acid such as (2-carboxyethyl) methylphosphinic acid; Alkoxy group-containing dialkylphosphinic acid such as (methoxymethyl) methylphosphinic acid] , aryl phosphinic acid _{[C 6-10} aryl phosphinic acids such as phenyl phosphinic acid, and _{di-C 6-10} aryl phosphinic acid such as diphenyl phosphinic acid], _{C 1-4} alkyl, such as alkyl aryl phosphinic acid (methylphenyl phosphinic acid -C _6-10 aryl - phosphinic acid and the like), and salts of these organic phosphinic acid (dimethyl phosphinic acid Ca salt, methyl ethyl phosphinic acid Ca salt, diethyl phosphinic acid Ca salt, di (n- or i -) Propylphosphinic acid Ca salt, di (n-, iso- or t-) butylphosphinic acid Ca salt, ethyl (n- or iso-) propylphosphinic acid Ca salt, ethyl (n-, iso- or t-) butyl Phosphinic acid Ca salt, di (n-, iso- or t-) butylphosphinic acid Ca salt, dipentylphosphinic acid Ca salt, dioctylphosphinic acid Ca salt, (2-carboxyethyl) methylphosphinic acid Ca salt and calcium salts thereof Alkaline earth metal salts such as Mg salts corresponding to: dimethylphosphinic acid Al salt, methylethylphosphinic acid Al salt, diethylphosphinic acid Al salt, di (n- or iso-) propylphosphinic acid Al salt, di (n- , Iso- or t-) butyl phosphinic acid Al salt, ethyl (n- or iso-) propyl phosphinic acid Al salt, ethyl ( n-, iso- or t-) butylphosphinic acid Al salt, dipentylphosphinic acid Al salt, dioctylphosphinic acid Al salt, aluminum salt such as (2-carboxyethyl) methylphosphinic acid Al salt; dimethylphosphinic acid Ti salt, methyl Ethylphosphinic acid Ti salt, diethylphosphinic acid Ti salt, di (n- or iso-) propylphosphinic acid Ti salt, di (n-, iso- or t-) butylphosphinic acid Ti salt, ethyl (n- or iso-) Propylphosphinic acid Ti salt, ethyl (n-, iso- or t-) butylphosphinic acid Ti salt, dipentylphosphinic acid Ti salt, dioctylphosphinic acid Ti salt, (2-carboxyethyl) methylphosphinic acid Ti salt and salts thereof Titanium salts such as titanyl salts, Zn dimethylphosphinic acid salts, and diethyl Phosphinic acid Zn salt, methylethylphosphinic acid Zn salt, di (n- or iso-) propylphosphinic acid Zn salt, di (n-, iso- or t-) butylphosphinic acid Zn salt, ethyl (n- or iso-) Zinc salts such as Zn salt of propylphosphinic acid, Zn salt of ethyl (n-, iso- or t-) butylphosphinic acid, Zn salt of dipentylphosphinic acid, Zn salt of dioctylphosphinic acid, Zn salt of (2-carboxyethyl) methylphosphinic acid Dimethylphosphinic acid melamine salt, methylethylphosphinic acid melamine salt, diethylphosphinic acid melamine salt, di (n- or iso-) propylphosphinic acid melamine salt, di (n-, iso- or t-) butylphosphinic acid melamine salt; , Ethyl (n- or iso-) propylphosphinic acid melamine salt, ethyl (n-, iso Or t-) butylphosphinic acid melamine salt, dipentylphosphinic acid melamine salt, dioctylphosphinic acid melamine salt, (2-carboxyethyl) methylphosphinic acid melamine salt, melamine melam memel double salt corresponding to these melamine salts, etc. And salts with aminotriazine compounds).

Specific examples of the organic phosphinic acid compound include organic phosphinic acid represented by the formula (1b) or a salt thereof such as 1-hydroxy-1H-phosphorane-1-oxide, 2-carboxy-1-hydroxy- Alkylene phosphinic acid (such as C _3-8 alkylene phosphinic acid) _optionally having a substituent such as 1H-phosphorane-1-oxide; Alkenylene phosphinic acid (such as C _3-8 alkenylene phosphinic acid); 1,3-cyclobutylene phosphinic acid, 1,3-cyclopentylene phosphinic acid, 1,4-cyclooctylene phosphinic acid, 1,5-cyclo Cycloalkylene phosphinic acids such as octylene phosphinic acid (C _4-10 cycloalkylene phosphinic acid, etc.) Or salts thereof (metal salts such as alkaline earth metal salts of 1-hydroxy-1H-phosphorane-1-oxide (Ca salts, Mg salts, etc.), Al salts, Ti salts, titanyl salts, Zn salts; melamine salts; Aminotriazine salts such as melamine, melam, melem double salt, etc.).

Among the preferred organic phosphinic acid compounds, specific examples of the polyvalent phosphinic acid include polyvalent phosphinic acids in which a plurality of phosphinic acids (or organic phosphinic acids) are linked by a polyvalent organic group, such as alkanebisphosphines. acid [such as ethane-1,2-bis (phosphinate) _{C 1-10} Arukanbisu (phosphinic acid), such as], _{C 1} such Arukanbisu (alkyl phosphinic acid) [ethane-1,2-bis (methyl phosphinic acid) _-10 alkanebis (C _1-6 alkylphosphinic acid) etc.], or a salt thereof. Examples of the salt include metals such as ethane-1,2-bisphosphinic acid Ca salt, ethane-1,2-bis (methylphosphinic acid) Ca salt, Mg salt, Al salt, Zn salt, Ti salt, or titanyl salt. Salt; ethane-1,2-bisphosphinic acid melamine salt, ethane-1,2-bis (methylphosphinic acid) melamine salt, melam salt, melem salt, salt with nitrogen-containing compound such as melamine melam memel double salt Etc.

  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. Gazette, JP-A-2004-238378, JP-A-2004-269526, JP-A-2004-269984, JP-A-2004-346325, JP-T-2001-513784, JP-A-2001-525327, JP 2001-525328 A, JP 2001-525329 A, JP 2001-540224 A, US Pat. No. 4,180,495, US Pat. No. 4,083,321, US Pat. No. 4,083,322, US Pat. No. 6,229,044, US Pat. No. 6,303,674 Compounds that are mounting the like.

(Flame retardant aid)
Flame retardant aids include aromatic resins [phenolic resins, aniline resins, polyphenylene oxide resins, aromatic epoxy resins (bisphenol A type epoxy resins, novolac type epoxy resins, etc.), phenoxy resins (bisphenol A type phenoxy resins). Polyphenylene sulfide resin, polycarbonate resin, polyarylate resin, aromatic polyamide resin, aromatic polyester resin that may be liquid crystalline, aromatic polyester amide resin that may be liquid crystalline, etc.], containing antimony 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 (Copper oxide And phosphorus-containing compounds [phosphorus-containing compounds other than (condensed) phosphate aminotriazine salts, such as phosphate esters, condensed phosphate esters, phosphate ester amides (phosphoramides, etc.), condensed phosphate ester amides, phosphonitrile compounds [For example, non-crosslinked or crosslinked aryloxyphosphazene such as (crosslinked) phenoxyphosphazene, (crosslinked) tolyloxyphosphazene, (crosslinked) xylyloxyphosphazene, (crosslinked) tolyloxyphenoxyphosphazene, (crosslinked) xylyloxyphenoxyphosphazene ], Organic phosphonic acid compounds or organic phosphonous acid compounds (for example, organic (phosphorous) phosphonic acid esters, organic (phosphorous) phosphonic acid aminotriazine salts, organic (phosphorous) phosphonic acid metal salts, etc.), etc .; red phosphorus , Boron phosphate, ( ) Inorganic compounds such as metal phosphates and metal hypophosphites], silicon-containing compounds [(poly) organosiloxane, layered silicates, etc.], sulfur-containing compounds (organic sulfonic acid compounds, perfluoroalkanesulfonic acids) Metal salts, sulfamic acid compounds or salts thereof, and fluorine-containing resins. These flame retardant aids can be used alone or in combination of two or more. In addition, as the flame retardant aid, components different from the base resin are usually used. In particular, when the flame retardant aid is a resinous flame retardant aid (aromatic resin such as aromatic polyester resin, aromatic polyamide resin, polycarbonate resin, polyphenylene oxide resin, polyphenylene sulfide resin, etc.) A resin different from the resin is used.

  Among these flame retardant aids, in particular, antimony-containing compounds, aromatic resins [phenolic resins, polyphenylene oxide resins, aromatic epoxy resins, phenoxy resins, polyphenylene sulfide resins, polycarbonate resins, polyarylate resins, aromatics Polyamide resins (polyamide resins in which all of the constituent monomer components are aromatic monomers, such as polyamides of aromatic dicarboxylic acid components and aromatic diamine components), aromatics that may be liquid crystalline Polyester resins (polyester resins in which all constituent monomer components are aromatic monomers, such as polyesters of aromatic dicarboxylic acids and aromatic diols) and aromatic polyester amide resins that may be liquid crystalline (Polyesteramide resin in which all constituent monomer components are aromatic monomers, etc. ] And phosphorus-containing compound to use at least one member selected from ((condensation) Phosphorus-containing compounds with the exception of phosphoric acid aminotriazine salts) preferred. When an antimony-containing compound is used, flame retardancy can be further improved, and when a fluorine-containing resin and / or a silicon-containing compound is used, dripping can be effectively prevented. The monomer components such as the aromatic dicarboxylic acid, aromatic diamine, and aromatic diol can use the components exemplified in the section of the base resin.

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

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

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

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

  Specific examples of the fluorine-containing resin 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. A fluorine-containing resin can be used individually or in combination of 2 or more types.

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

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

  Phosphorus-containing compounds include phosphorus-containing compounds other than (condensed) phosphate aminotriazine salts, such as phosphate esters or 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-xylyl phosphate), pentaerythritol diphenyl phosphate, pentaerythritol di-2,6-xylyl phosphate, 2,6,7-trioxa-1-phosphate Cyclo [2.2.2] octane-4-methanol-1-oxide, and phosphate ester compounds described in US Pat. Nos. 4,154,775 and 4,801,625], phosphate ester amides or condensation Phosphate ester amides [for example, 1,4-piperazinediyltetraphenyl phosphate, 1,4-piperazinediyltetra-2,6-xylylphosphate, N, N′-bis (neopentylenedioxyphosphinyl) piperazine, And phosphoric ester amides (phosphoramide etc.) described in JP-A-10-175985, JP-A-2001-139823 and JP-A-2001-354689, etc.], phosphonitrile compounds [for example, phenoxyphosphazene, tolyloxyphosphazene Xylyloxyphos Azene, phenoxytolyloxyphosphazene, cyclic and / or chain aryloxyphosphazenes such as phenoxyxylylphosphazene (non-bridged aryloxyphosphazenes), and their cross-linked products (for example, phenoxyphosphazenes cross-linked with bisphenol residues) Bridged aryloxyphosphazenes, etc.), and phosphazene compounds described in WO99 / 19383, WO00 / 9518, WO02 / 98886 and WO04 / 24844], organic (sub) phosphonic acid compounds [eg, organic (Sub-) phosphonic acid esters, organic (sub-) phosphonic acid metal salts (for example, alkali metal salts such as Li, Na and K; alkaline earth metal salts such as Mg, Ca and Sr; Group 3 of the periodic table such as Ce) Metal salts; Group 4 such as Ti and Zr Group 7 metal salts such as Mn; Group 8 metal salts such as Fe; Group 12 metal salts such as Zn; Group 13 metal salts such as Al; Group 14 metal salts such as Sn and Ge; Various metal salts such as Group 15 metal salts such as Sb and Bi), basic nitrogen compound salts of organic (phosphorous) phosphonic acid [melamine salts, guanamine salts, benzoguanamine salts and / or their condensate salts (melam salts, Aminotriazine salts such as melem salts and melamine condensate salts such as melon salts], and inorganic phosphorus compounds [eg, red phosphorus; phosphoric acids (phosphoric acid, phosphorous acid, hypophosphorous acid, etc.) and alkaline earth Metal salts or salts with periodic table group 13 metals (including double salts), for example, metal phosphates (calcium phosphate, aluminum phosphate, phosphoric acid / aluminum phosphite double salts, etc.), metal phosphites ( Phosphite calcium, Such as aluminum phosphate), hypophosphorous acid metal salt (calcium hypophosphite, hypophosphorous acid aluminum); boron phosphate, etc.] and the like. A phosphorus containing compound can be used individually or in combination of 2 or more types.

Of these phosphorus-containing compounds, organic (phosphorous) phosphonic acid compounds are particularly preferable. 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, pentylphosphonic acid, octylphosphonic acid, Hydroxyalkylphosphonic acids (hydroxymethylphosphonic acid, hydroxyethylphosphonic acid, hydroxypropylphosphonic acid, etc.), alkoxyalkylphosphonic acids (methoxymethylphosphonic acid, ethoxyethylphosphonic acid, etc.), carboxyalkylphosphonic acids (carboxymethylphosphonic acid, 2-carboxyethyl) Phosphonic acid, etc.), methylphosphonous acid, ethylphosphonous acid, n-propylphosphonous acid, isopropylphosphonous acid, n-butylphosphonous acid, isobutylphosphonous acid, Pentyl phosphonous acid, octyl nitrite substituent may be a have alkyl (sub) phosphonic acid (such as C _1-16 alkyl (sub) phosphonate) such as phosphonate; phenylphosphonic acid, Toriruhosuhon acid, phenyl phosphorous Aryl (sub) phosphonic acid (C _6-10 aryl (sub) phosphonic acid etc.) optionally having substituents such as phosphonic acid; Substitution of ethane-1,2-diphosphonic acid, hydroxyethane diphosphonic acid etc. Alkylenediphosphonic acid which may have a group (C _2-6 alkylenediphosphonic acid etc.); alkylidene diphosphonic acid which may have a substituent such as 1-hydroxyethylidene-1,1-diphosphonic acid (such as _{C 1-4} diphosphonic acid); 1,4-phenylene acid, such as 1,4-phenylene phosphonous Ally Nji (sub) (such as C _6-12 arylene (nitrite) phosphonate) phosphonate; nitrilotris (methylphosphonic acid) substituent (hydroxyl group) which may nitrilotris have such (alkylphosphonic acid) [nitrilotris (C _1-4 alkyl phosphonic acid), etc.]; oxy dimethyl phosphonic substituent (hydroxyl group) which may have a oxydiphthalic (alkylphosphonic acid) such as an acid [oxydiphthalic (C _1-4 alkylphosphonic Acid), etc.]; polymeric phosphonic acids such as polyvinyl phosphonic acid and polyallyl phosphonic acid; esters of these organic (phosphorous) phosphonic acids [methyl phosphonic acid monomethyl ester, ethyl 2-carboxyethylphosphonate, triethyl carboxymethylphosphonate, Such as triethyl carboxyethyl phosphonate Alkyl optionally having group (sub) mono- or polyalkyl esters (such as C _1-16 alkyl (sub) mono- or di-C _1-16 alkyl esters of phosphonic acid) phosphonic acid; pentaerythritol ester of methylphosphonic acid Alkyl (sub) phosphonic acid which may have a substituent such as 2-ethyl-2-hydroxymethyl-1,3-propanediol ester of methylphosphonic acid, hydroxyethyl poly (oxyethyl) phosphonic acid ester and polyvalent Esters with alcohol, etc.]; salts of these organic (sub) phosphonic acids [methyl (sub) phosphonic acid Ca salt, ethyl (sub) phosphonic acid Ca salt, n-propyl (sub) phosphonic acid Ca salt, isopropyl (suboxide) ) Phosphonic acid Ca salt, n-butyl (sub) phosphonic acid Ca salt, isobutyl (sub) phosphonic acid Ca , T-butyl (sub) phosphonic acid Ca salt, pentyl (sub) phosphonic acid Ca salt, alkyl (sub) phosphonic acid Ca salt such as octyl (sub) phosphonic acid Ca salt, and these alkyl (sub) phosphonic acid Ca salts Alkali earth metal salts such as alkyl (sub) phosphonic acid Mg salt, 1-hydroxyethylidene-1,1-diphosphonic acid Ca salt, nitrilotris (methylphosphonic acid) Ca salt, nitrilotris (methylphosphonic acid) Mg salt An alkyl (sub) phosphonic acid Ti salt, 1-hydroxyethylidene-1,1-diphosphonic acid Ti salt, nitrilotris (methylphosphonic acid) Ti salt corresponding to the alkyl (sub) phosphonic acid Ca salt, and these Ti salts; Corresponding titanium salt (including titanyl salt) such as corresponding titanyl salt; Al (phosphorous) phosphonic acid Al salt, ethane-1,2-diphosphonic acid Al salt, carboxymethylphosphonic acid Al salt, 2-carboxyethylphosphonic acid Al salt, methylphosphonic acid monomethyl ester Al salt, 1-hydroxyethylidene-1 , 1-diphosphonic acid Al salt, nitrilotris (methylphosphonic acid) Al salt and the like; alkyl (sub) phosphonic acid Zn salt corresponding to the above alkyl (sub) phosphonic acid Ca salt, 1-hydroxyethylidene-1,1 A zinc salt such as a diphosphonic acid Zn salt, nitrilotris (methylphosphonic acid) Zn salt; an alkyl (sub) phosphonic acid melamine salt corresponding to the alkyl (sub) phosphonic acid Ca salt, a melam salt corresponding to these melamine salts, Melem salt, melon salt, melamine, melam, melem double salt, melamine, mela Aminotriazine compounds (melamine or condensates thereof) such as lamb, melem, and melon double salts, mono- to tetramelamine salts of 1-hydroxyethylidene 1-1-diphosphonic acid, nitrilotris (methylphosphonic acid) mono to hexamelamine salts, and the like And the like]. Of these organic (sub) phosphonic acid compounds, 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, U.S. Pat. No. 3,789,091, U.S. Patent No. 3,849,368, and compounds described in U.S. Patent No. 4,390,477 may also be used.

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

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

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.).

Specific examples of the olefin resin include α-olefin resins [for example, homo- or copolymers of α-C _2-3 olefins such as polyethylene, polypropylene, propylene-ethylene copolymers; ethylene- (meta ) Acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid metal salt copolymer, ethylene- (meth) acrylic acid ester copolymer (ethylene-ethyl acrylate copolymer) Ethylene- (meth) acrylic acid alkyl copolymer; ethylene- (meth) acrylic acid glycidyl copolymer; ethylene- (meth) acrylic acid glycidyl- (meth) acrylic acid alkyl copolymer, etc.)- C _2-3 copolymer of an olefin and a copolymerizable monomer, etc.], an acid-modified olefin resin [e.g., Oleh A resin or a copolymer of α, β-unsaturated carboxylic acid ((meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, etc.) and / or an acid anhydride thereof. Modified acid-modified olefin resin etc.], cyclic olefin resin (for example, homopolymer of cyclic olefin, α-C _2-10 olefin-cyclic olefin copolymer, etc.) and the like. Olefin resins can be used alone or in combination of two or more.

Among these olefin resins, poly α-C _2-3 olefin (particularly polyethylene, polypropylene, propylene-ethylene block 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 copolymer (especially ethylene-ethyl acrylate copolymer), α-C _2-3 olefin-glycidyl (meth) acrylate copolymer Polymer (especially ethylene- (meth) acrylic acid glycidyl copolymer), α-C _2-3 olefin- (meth) acrylic acid glycidyl- (meth) acrylic acid C _1-4 alkyl copolymer (especially ethylene -Glycidyl (meth) acrylate-methyl (meth) acrylate copolymer, etc.)], acid-modified polyolefin (maleic anhydride-modified polymer). An acid-modified _{poly-C 2-3} olefin such as propylene) and the like are preferable.

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

(Electrical property improvement aid)
If necessary, the flame retardant resin composition of the present invention may further contain an additive (electric property improvement aid) for improving electric characteristics, such as a nitrogen-containing compound [aminotriazine compound (melamine; guanamine; melam, melem). Melamine condensates, etc.), salts of aminotriazine compounds (organic acids or inorganic acid salts of the aminotriazine compounds such as cyanurates such as melamine cyanurate), etc.], phosphorus-containing compounds [(poly) phosphoric acid Salts (salts with basic nitrogen-containing compounds, metal salts, etc.), organophosphates, polyphosphate amides, etc.], silicon-containing compounds [silicates (talc, kaolin, aluminum silicate, etc.), hydrotalcite, zeolite Etc.], inorganic metal compounds [inorganic acids (inorganic acids other than phosphoric acid and silicic acid, such as carbonic acid, boric acid, stannic acid, Metal salts (magnesium oxide, iron oxide, titanium oxide, zinc oxide, alumina, etc.), metal hydroxides (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate) (Such as boehmite), metal sulfide (such as zinc sulfide, molybdenum sulfide, tungsten sulfide)]. These electrical property improving aids can be used alone or in combination of two or more. In addition, as an electrical property improvement adjuvant, the compound different from the said organic phosphinic acid or its salt, and a flame retardant adjuvant is used normally.

  Among the electrical property improving aids, the phosphorus-containing compound includes (poly) phosphate [ammonium salt such as ammonium polyphosphate; salt of polyphosphoric acid (including pyrophosphoric acid) and aminotriazine compound (melamine polyphosphate) Salts of polyphosphoric acid and melamine condensates, such as melam polyphosphate, melem polyphosphate, melon polyphosphate, melamine polymelamine melam melem double salt, melamine polyphosphate melam melem melon double salt, melamine polymetaphosphate Metal salts of phosphoric acid or polyphosphoric acid (including pyrophosphoric acid) (hydrogen phosphate metal salts such as calcium hydrogen phosphate (alkaline earth metal salts)); ) (Poly) metal phosphates such as aluminum phosphate; aluminum pyrophosphate, phosphoric acid Metal pyrophosphates such as aluminum lophosphate double salts)], organic phosphates (aliphatic organic phosphates, such as alkyl phosphates such as trimethyl phosphate), polyphosphates ((poly) phosphates And / or a polymer compound obtained by baking and condensing an organic phosphoric acid and a cyanamide derivative in the presence of urea and / or urea phosphate. Further, as the metal constituting the inorganic metal compound, alkali metals (K, Na, etc.), alkaline earth metals (Mg, Ca, Ba, etc.), transition metals (Fe, Co, etc.), periodic table group 12 metals (Zn etc.) etc. are mentioned. Among inorganic metal compounds, inorganic acid metal salts include carbonates (such as alkaline earth metal salts such as calcium carbonate) and borates (such as anhydrous or hydrous zinc borate, anhydrous or hydrous calcium borate) ) Metal borate), stannate (anhydrous or hydrous zinc stannate (water) metal stannate), tungstate (zinc tungstate), sulfate (calcium sulfate, barium sulfate, etc.) Etc.

  Among the electrical property enhancement aids, metal oxides, metal sulfides, (hydrous) metal silicates, (hydrous) metal borate, (hydrous) metal stannates, metal hydrogen phosphates, pyrophosphates, At least one selected from polyphosphate, polymetaphosphate and polyphosphate amide is preferred. In particular, titanium oxide, zinc sulfide, talc, kaolin, (hydrous) zinc borate, (hydrous) calcium borate, (hydrous) zinc stannate, calcium hydrogen phosphate, melamine cyanurate, melamine polyphosphate, melam polyphosphate, At least one selected from melem polyphosphate, melon polyphosphate, melamine polymelate, melam, melem double salt, melamine polyphosphate, melam, melem, melon double salt, melamine polymetaphosphate and melamine polymetaphosphate, melam, melem double salt preferable.

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

  The ratio of the organic phosphinic acid compound is, for example, 1 to 30 parts by weight, preferably 3 to 28 parts by weight, and more preferably about 5 to 25 parts by weight with respect to 100 parts by weight of the base resin. The proportion of the organic phosphinic acid compound may be, for example, 5 to 500 parts by weight, preferably 10 to 300 parts by weight, and more preferably about 20 to 280 parts by weight with respect to 100 parts by weight of the halogen-based flame retardant. Good.

  The ratio of the flame retardant aid is, for example, about 0.1 to 30 parts by weight, preferably about 0.5 to 20 parts by weight, and more preferably about 1 to 15 parts by weight with respect to 100 parts by weight of the base resin. The ratio of the flame retardant aid is, for example, 0.1 to 200 parts by weight, preferably 0.2 to 150 parts by weight, and more preferably 0.5 to 120 parts with respect to 100 parts by weight of the halogen flame retardant. It may be about a part. The ratio (weight ratio) between the organic phosphinic acid or salt thereof and the flame retardant aid is organic phosphinic acid or salt thereof / flame retardant aid = 10/90 to 99.9 / 0.1, preferably 20 / It may be about 80 to 99/1, more preferably about 25/75 to 97/3.

  The proportion of the olefin resin may be, for example, 0 to 30 parts by weight, preferably 1 to 20 parts by weight, and more preferably about 2 to 15 parts by weight with respect to 100 parts by weight of the base resin. The proportion of the olefin resin is, for example, 0 to 300 parts by weight (for example, 0.5 to 200 parts by weight), preferably 1 to 150 parts by weight, more preferably 100 parts by weight of the halogen flame retardant. It may be about 5 to 120 parts by weight. Moreover, the ratio of the olefin resin is, for example, 1 to 150 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 parts per 100 parts by weight of the total amount of the halogen flame retardant and the organic phosphinic acid or a salt thereof. About 90 parts by weight.

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

  In the present invention, the flame retardant resin composition further includes other additives such as other flame retardants (nitrogen-based, phosphorus-based flame retardants, etc.), antioxidants (phenolic antioxidants, amine-based antioxidants). , Hydroquinone antioxidants, quinoline antioxidants, sulfur antioxidants, phosphorus antioxidants, stabilizers (ultraviolet absorbers, weathering (light) stabilizers, thermal stabilizers, processing stabilizers, phosphorus) System stabilizers, reactive stabilizers, etc.), antistatic agents, lubricants, mold release agents, crystallization nucleating agents, plasticizers, colorants (dyes, pigments, etc.), lubricants, anti-dripping agents, fillers (glass) It may contain fibrous inorganic fillers such as fibers and carbon fibers, non-fibrous inorganic fillers such as glass flakes, and the like. These other additives can be used alone or in combination of two or more.

  The resin composition preferably contains at least one selected from an antioxidant, a stabilizer (particularly, a phosphorus stabilizer, a reactive stabilizer), a lubricant, and a filler among the additives. Moreover, you may use a filler at least among the said additives.

  The ratio of the filler in the flame retardant resin composition is, for example, 0 to 100 parts by weight, preferably 0.5 to 80 parts by weight, and more preferably about 1 to 70 parts by weight with respect to 100 parts by weight of the base resin. There may be.

Among the antioxidants, phenolic antioxidants include hindered phenols such as 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. C _2-10 alkanediol-bis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate]; triethylene glycol-bis [3- (3-t-butyl) 5-methyl-4-hydroxyphenyl) propionate] di- or Toriokishi _{C 2-4} alkylene diol such as - bis [3- (3,5-di - branched _{C 3-6} alkyl-4-hydroxyphenyl) propionate]; _{C 3-8} Arukirento such as glycerin tris [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] All - bis [3- (3,5-di - branched _{C 3-6} alkyl-4-hydroxyphenyl) propionate]; pentaerythritol tetrakis [3- (3,5-di -t- butyl-4-hydroxyphenyl) C _4-8 alkylenetetraol tetrakis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate] such as propionate]; n-octadecyl [3- (3,5-di- C _10-35 alkyl [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate] such as t-butyl-4-hydroxyphenyl) propionate]; N, N′-hexa methylenebis (3,5-di -t- butyl-4-hydroxy hydrocinnamate raw bromide) N, such as, _{N'-C 2-10} alkylene bis (3,5 And di branched _{C 3-6} alkyl-4-hydroxy hydrocinnamate raw bromide) is preferred.

The amine-series antioxidant, a hindered amine, for example, tri- or tetra-C _1-3 alkyl piperidine or methoxy derivative thereof (4-position, benzoyloxy, phenoxy and the like may be substituted 2,2,6, 6-tetramethylpiperidine, etc.), bis (tri, tetra or penta C _1-3 alkylpiperidine) C _2-20 alkanedicarboxylic acid ester [eg bis (2,2,6,6-tetramethyl-4-piperidyl) Oxalate, malonate corresponding to oxalate, adipate, sebacate, terephthalate, etc .; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate], 1,2-bis (2,2,6,6- Tetramethyl-4-piperidyloxy) ethane, phenylnaphthylamine, N, N'-diphenyl-1 4- phenylenediamine, and the like N- phenyl -N'- cyclohexyl-1,4-phenylenediamine.

  Examples of the hydroquinone antioxidant include 2,5-di-t-butylhydroquinone, and examples of the quinoline antioxidant include 6-ethoxy-2,2,4-trimethyl-1,2. -Dihydroquinoline and the like are included. Examples of the sulfur-based antioxidant include dilauryl thiodipropionate and distearyl thiodipropionate.

  Examples of phosphorus stabilizers (or phosphorus antioxidants) include phosphite stabilizers (trialkyl phosphites, trisalkylaryl phosphites, tris (branched alkylphenyl) phosphites, (branched alkylphenyl) phenylphosphines). Phyto, bis (alkylaryl) pentaerythritol diphosphite, etc.), triphenyl phosphate stabilizers, diphosphonite stabilizers and the like.

  Examples of reactive stabilizers include epoxy reactive stabilizers (glycidyl ether compounds, epoxy group-containing acrylic polymers, etc.), oxazoline reactive stabilizers (1,3-phenylenebis (2-oxazoline), 1 , 4-phenylenebis (2-oxazoline)), carbodiimide-based reactive stabilizers (polyarylcarbodiimide, polyalkylarylcarbodiimide, poly [alkylenebis (alkyl or cycloalkylaryl) carbodiimide] and the like).

  These antioxidants and / or stabilizers can be used alone or in combination of two or more. The proportion of the antioxidant is in the range of 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably about 0.1 to 5 parts by weight with respect to 100 parts by weight of the base resin (A). You can choose from. The proportion of the stabilizer can also be selected from the same range as the proportion of the antioxidant.

Among the additives, the lubricant includes a long-chain fatty acid or a derivative thereof [monovalent saturated or unsaturated fatty acid (capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, such as _{C 10-34} saturated fatty acids such as montanic acid), a divalent saturated or unsaturated fatty acids (oleic acid, linoleic acid, linolenic acid, arachidonic acid, an unsaturated _{C 10-34} fatty acids, such as erucic acid) And their fatty acid esters and fatty acid amides], polyalkylene glycols [C _2-6 alkylene glycols (ethylene glycol, propylene glycol, tetramethylene glycol, etc.) or copolymers, or derivatives thereof], silicone-based Compound [dialkylsiloxane (such as dimethylsiloxane), al Monoaryl siloxanes such as diaryl siloxane (such as phenylmethyl siloxane), diaryl siloxane (such as diphenyl siloxane), or homopolymers or copolymers thereof (polyorganosiloxane), modified polyorganosiloxane, etc.], waxes [natural Paraffin, synthetic paraffin, micro wax, polyolefin wax (poly C _2-4 olefin wax such as polyethylene wax and polypropylene wax, olefin copolymer wax such as ethylene copolymer wax) and the like. A lubricant can be used individually or in combination of 2 or more types.

  The ratio of the lubricant is, for example, 0.01 to 20 parts by weight, preferably 0.01 to 15 parts by weight, more preferably 0.01 to 10 parts by weight (for example, relative to 100 parts by weight of the base resin (A). 0.1 to 10 parts by weight).

  The flame retardant resin composition of the present invention may be a powder mixture or a molten mixture, a base resin, a halogen flame retardant, an organic phosphinic acid or salt thereof, a flame retardant aid, and, if necessary. It can be prepared by mixing other components (olefin resin, electrical property improving aid, additive, etc.) by a conventional method. The present invention also includes a molded article formed from the flame retardant resin composition (for example, a resin composition (molded article) formed by solidifying the molten mixture).

  The flame-retardant resin composition and the molded product (molded body) are, for example, (1) a method of mixing each component, kneading and extruding with a uniaxial or biaxial extruder to prepare pellets, 2) A method of preparing pellets (master batches) having different compositions once, mixing (diluting) the pellets with a predetermined amount and using them for molding, and obtaining a molded product having a predetermined composition. A method of directly charging and molding one or two or more can be employed. All or a part of the components other than the base resin may be mixed in advance and mixed with the base resin, 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 article can be manufactured by melt-kneading a flame-retardant resin composition by a conventional method and molding by a conventional method such as extrusion molding, injection molding, or compression molding.

  Although the flame retardant resin composition (and molded product) of the present invention contains a halogen-based flame retardant, it can achieve both flame retardancy and electrical characteristics. When the resin composition and molded product of the present invention are measured with a test piece thickness of 1.6 mm, the flame retardancy based on the UL94 flammability test is V-1 or more, preferably V-0 or more. Moreover, the comparative tracking index (CTI) based on IEC112 (UL746A) is 300 V or more (for example, about 300 to 1000 V), preferably 350 V or more (for example, about 400 to 900 V). More preferably, it is 500 V or more (for example, about 500 to 800 V).

  The present invention includes (a) a flame retardant resin composition (and a molded product) having flame retardancy in accordance with UL94 of V-1 or higher and a comparative tracking index of 500 V or higher, (b) Measured at a flame retardant resin composition (and molded product) having flame retardancy in accordance with UL94 of V-0 or higher and the comparative tracking index of 350 V or higher, and (c) test piece thickness of 0.8 mm. In addition, a flame retardant resin composition (and a molded product) having a flame retardancy based on UL94 of V-0 or higher and a comparative tracking index of 300 V or higher is also included.

  In addition, the resin molded product (molded product) of the present invention is excellent in safety against electric fire inside the device, safety against fire of the molded product itself, mechanical characteristics, electrical characteristics, and the like. , Connectors, relays, disk drive chassis, transformers, electromagnetic switches, switch parts, outlet parts, sockets, plugs, capacitors, various cases, resistors, metal terminals or parts used in places where conductors are incorporated) Household appliance parts [e.g., housing for general household appliances, parts related to computers or peripheral equipment, lighting parts, parts related to telephone or facsimile equipment, air conditioner parts, audiovisual equipment for home use (TVs, digital versatile disc players, video Deck etc.), etc.], office automation (OA) equipment parts (computer-related parts, acoustic parts, lighting parts, telegraph or telephone equipment-related parts, facsimile parts, copying machine parts, air conditioning parts, optical equipment parts, etc.), mechanical mechanism parts (various gears, It is useful for various bearings, motor parts, etc.) and automobile parts (automotive ignition device parts, automobile connectors, various automobile electrical parts, etc.).

  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 electric / electronic parts, home appliance parts, office automation (OA) equipment parts, It can be suitably used for machine mechanism parts, automobile 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 test piece thickness of 1.6 mmt or 0.8 mmt.

[Comparison tracking index (CTI)]
Based on IEC112, the comparative tracking index (CTI) [unit: V] was evaluated using solution A.

  Further, the base resin (A), halogen-based flame retardant (B), organic phosphinic acid or its salt (C), flame retardant aid (D), olefin resin (E), and electricity used in Examples and Comparative Examples The property improving aid (F), filler (G), antioxidant (H), stabilizer (I), and lubricant (J) are as follows.

1. Base resin (A)
(A-1): Polybutylene terephthalate [Intrinsic viscosity = 0.85]
(A-2): Polyethylene terephthalate [Intrinsic viscosity = 0.75]
(A-3): Polypropylene terephthalate [Intrinsic viscosity = 0.85]
(A-4): Polyamide 66
2. Halogen flame retardant (B)
(B-1): Poly (pentabromobenzyl acrylate) [FR1025, manufactured by Bromchem Far East]
(B-2): Brominated polystyrene [Pyrocheck 68 PB, manufactured by Ferrochemicals, Inc.]
(B-3): Ethylenebistetrabromophthalimide [SYTEX BT-93, manufactured by Albemarle Corporation]
(B-4): Brominated epoxy resin [SRT5000, manufactured by Sakamoto Pharmaceutical Co., Ltd.]
(B-5): Brominated polycarbonate resin [Fireguard FG-7500, manufactured by Teijin Chemicals Ltd.]
3. Organic phosphinic acid or its salt (C)
(C-1): methylethylphosphinic acid aluminum salt (C-2): methylethylphosphinic acid calcium salt (C-3): dimethylphosphinic acid aluminum salt (C-4): 1-hydroxy-1H-phosphorane-1 -Aluminum salt of oxide (C-5): Melamine salt of dimethylphosphinic acid (C-6): Aluminum salt of (2-carboxyethyl) methylphosphinic acid (C-7): Aluminum salt of diethylphosphinic acid.

4). Flame retardant aid (D)
(I) Antimony-containing compound D1
(D1-1): Antimony trioxide (D1-2): Antimony pentoxide (D1-3): Sodium antimonate (ii) Fluorine-containing resin D2
(D2-1): Polytetrafluoroethylene (iii) Silicon-containing compound D3
(D3-1): Swellable synthetic fluorinated mica [ME-100, manufactured by Coop Chemical Co., Ltd.]
(D3-2): Montmorillonite (D3-3): Polydimethylsiloxane [7500 cSt (7.5 × 10 ⁻³ m ² s ⁻¹ )].

(Iv) Phosphorus-containing compound (D4)
(D4-1): ethylphosphonic acid aluminum salt (D4-2): ethylphosphonous acid aluminum salt (D4-3): resorcinol bis (di-2,6-xylylphosphate)
(D4-4): Cyclic phenoxyphosphazene (mixture of trimer and tetramer)
(D4-5): 1,4-piperazinediyltetraphenyl phosphate (D4-6): nitrilotris (methylphosphonic acid) calcium salt (v) aromatic resin (D5)
(D5-1): Polycarbonate resin [Panlite L1225, manufactured by Teijin Chemicals Ltd.]
(D5-2): Bisphenol-A type epoxy resin [Epicoat 1004K, manufactured by Yuka Shell Epoxy Co., Ltd.]
5. Olefin resin (E)
(E-1): Ethylene-ethyl acrylate copolymer [NUC-6570, manufactured by Nippon Unicar Co., Ltd.]
(E-2): Ethylene-glycidyl methacrylate copolymer [Bond First E, manufactured by Sumitomo Chemical Co., Ltd.]
6). Electric property improvement aid (F)
(F-1): Titanium oxide (F-2): Melamine polyphosphate [Melapur 200, manufactured by DSM]
(F-3): Zinc sulfide (F-4): Talc (F-5): Hydrous zinc borate [Fire Break ZB, manufactured by US Borax Co., Ltd.]
(F-6): Melamine cyanurate 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). Antioxidant (H)
(H-1): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] [Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.]
9. Stabilizer (I)
(I) Phosphorus stabilizer I1
(I1-1): Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite [Sand Stub P-EPQ, manufactured by Sand Corp.]
(I1-2): Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite [Adeka Stub PEP36, manufactured by Adeka Argus Co., Ltd.]
(I1-3): primary calcium phosphate (ii) reactive stabilizer I2
(I2-1): Bisphenol-A diglycidyl ether [Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.]
10. Lubricant (J)
(J-1): Polyethylene wax [Sun Wax, manufactured by Sanyo Chemical Co., Ltd.]
(J-2): Montanate ester [LUZA WAX-P, manufactured by Toyo Petrolite Co., Ltd.]
Reference Examples 1-6, 8-20, Example 7 and Comparative Examples 1-3
The above components were mixed in the proportions (parts by weight) shown in Tables 1 and 2, and kneaded and extruded with an extruder to prepare a pellet-shaped resin composition. Using the obtained pellets, test molded articles were produced by injection molding, and flammability (1.6 mmt) and tracking resistance (comparative tracking index) were evaluated. The results are shown in Tables 1 and 2.

参考例２１〜２３及び比較例４
上記成分を表３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（１．６ｍｍｔ）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３に示す。

Reference Examples 21 to 23 and Comparative Example 4
The above components were mixed in the proportions (parts by weight) shown in Table 3, and kneaded and extruded with an extruder to prepare a pellet-shaped resin composition. Using the obtained pellets, test molded articles were produced by injection molding, and flammability (1.6 mmt) and tracking resistance (comparative tracking index) were evaluated. The results are shown in Table 3.

参考例２４〜３２及び比較例５
上記成分を表４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（１．６ｍｍｔ）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４に示す。

Reference Examples 24-32 and Comparative Example 5
The above components were mixed in the proportions (parts by weight) shown in Table 4, and kneaded and extruded with an extruder to prepare a pellet-shaped resin composition. Using the obtained pellets, test molded articles were produced by injection molding, and flammability (1.6 mmt) and tracking resistance (comparative tracking index) were evaluated. The results are shown in Table 4.

参考例３３〜４１及び比較例６
上記成分を表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（１．６ｍｍｔ）及び耐トラッキング（比較トラッキング指数）を評価した。結果を表５に示す。

Reference Examples 33 to 41 and Comparative Example 6
The above components were mixed in the proportions (parts by weight) shown in Table 5, and kneaded and extruded with an extruder to prepare a pellet-shaped resin composition. Using the obtained pellets, test molded articles were produced by injection molding, and flammability (1.6 mmt) and tracking resistance (comparative tracking index) were evaluated. The results are shown in Table 5.

参考例４２〜５１及び比較例７〜１３
上記成分を表６及び表７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、射出形成により試験用成形品を作製し、燃焼性（０．８ｍｍｔ）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及び表７に示す。

Reference Examples 42 to 51 and Comparative Examples 7 to 13
The above components were mixed in the proportions (parts by weight) shown in Tables 6 and 7, 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 mmt) and tracking resistance (comparative tracking index) were evaluated. The results are shown in Tables 6 and 7.

Claims (18)

A flame retardant resin composition comprising a base resin, a halogen-based flame retardant, an organic phosphinic acid or a salt thereof, a flame retardant aid, and an electrical property improving aid, and having improved electrical properties,
The base resin is at least one thermoplastic resin selected from polyester resins and aliphatic polyamides;
The halogen flame retardant is at least one selected from a brominated polybenzyl (meth) acrylate resin, an alkylene brominated phthalimide, a brominated product of a styrene resin, and a brominated styrene monomer alone or a copolymer. ,
The flame retardant aid is (poly) organosiloxane, smectite layered silicate, swellable synthetic fluorine mica, aromatic resin , phosphate ester, condensed phosphate ester, phosphate ester amide, condensed phosphate ester amide, Non-bridged aryloxyphosphazenes, bridged aryloxyphosphazenes, organic (phosphite) phosphonates, organic (phosphorous) phosphonic acid aminotriazine salts, organic (phosphorous) phosphonic acid metal salts, (phosphorous) metal phosphates and hypophosphorous acid Including at least one selected from metal salts,
The aromatic resin is at least one selected from phenolic resins, polyphenylene oxide resins, aromatic epoxy resins, phenoxy resins, polyphenylene sulfide resins, polycarbonate resins, and aromatic polyamide resins;
The electrical property improving aid is titanium oxide, zinc sulfide, talc, kaolin, (hydrous) zinc borate, (hydrous) calcium borate, (hydrous) zinc stannate, calcium hydrogen phosphate, melamine cyanurate, polyphosphoric acid Melamine, Melam polyphosphate, Melem polyphosphate, Melon polyphosphate, Melamine / Melam / Melem double salt polyphosphate, Melamine / Melam / Melem / Melon polyphosphate, Melamine polymetaphosphate and Melamine / Melam / Melem polymetaphosphate At least one kind selected,
The resin composition whose ratio of the said organic phosphinic acid or its salt is 5-500 weight part with respect to 100 weight part of said halogenated flame retardants. The resin composition according to claim 1, wherein the base resin is 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. object. The resin composition according to claim 1, wherein the organic phosphinic acid is a compound represented by the following formula (1).

(In the formula, R ¹ and R ² are the same or different and each represents a hydrocarbon group which may have a substituent. R ¹ and R ² are bonded to each other to form a ring with an adjacent phosphorus atom. Also good)   The resin composition according to claim 1, wherein the salt of the organic phosphinic acid is a salt of the organic phosphinic acid and at least one selected from a nitrogen-containing compound having a metal and an amino group.   The organic phosphinic acid is at least selected from a dialkylphosphinic acid optionally having a substituent, an alkylenephosphinic acid optionally having a substituent, and a cycloalkylenephosphinic acid optionally having a substituent. One type of organic phosphinic acid salt is an organic phosphinic acid, a periodic table Group 1 metal, Group 2 metal, Group 4 metal, Group 8 metal, Group 12 metal, Group 13 metal, and amino The resin composition according to claim 1, which is a salt with at least one selected from triazine compounds.   The resin composition according to claim 1, wherein the flame retardant aid further comprises at least one selected from an antimony oxide, an antimonate, and a fluorine-containing monomer alone or a copolymer.   The proportion of the halogen-based flame retardant is 3 to 30 parts by weight with respect to 100 parts by weight of the base resin, the proportion of the organic phosphinic acid or a salt thereof is 1 to 30 parts by weight, and the proportion of the flame retardant aid is 0.00. The resin composition according to claim 1, which is 1 to 30 parts by weight.   The resin composition according to claim 1, wherein the proportion of the flame retardant aid is 0.1 to 200 parts by weight with respect to 100 parts by weight of the halogen flame retardant.   Furthermore, the resin composition of Claim 1 containing an olefin resin. The resin composition according to claim 9, wherein the olefin resin is an α-C _2-3 olefin- (meth) acrylic acid ester copolymer.   The resin composition according to claim 9, wherein the proportion of the olefin resin is 1-150 parts by weight with respect to 100 parts by weight of the total amount of the halogen-based flame retardant and the organic phosphinic acid or a salt thereof.   2. The resin composition according to claim 1, wherein the ratio (weight ratio) of the organic phosphinic acid or a salt thereof and the flame retardant aid is the former / the latter = 20/80 to 99/1.   The resin composition according to claim 1, further comprising at least one selected from an antioxidant, a stabilizer, a lubricant, and a filler.   The resin composition according to claim 1, wherein a comparative tracking index based on IEC112 is 350 V or more.   (i) When measured at a test piece thickness of 1.6 mm, the flame retardancy according to the UL94 flammability test is V-1 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 UL94 flammability test is V-0 or higher, and (ii) the comparative tracking index according to IEC112 is 350 V or higher. Item 2. The resin composition according to Item 1.   A molded article formed from the resin composition according to claim 1.   The molded article according to claim 17, wherein the molded article is at least one selected from electrical or electronic parts, home appliance parts, office automation equipment parts, mechanical mechanism parts, and automobile parts.