JP2009215347A - Flame-retardant resin composition and coated electric wire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition having high heat resistance and flame retardancy, excellent in workability and flexibility or toughness, and useful especially to coat an electric wire. <P>SOLUTION: The flame-retardant resin composition comprises (A) 100 pts.wt. of polybutylene terephthalate resin, (B) 25-150 pts.wt. of a thermoplastic polyester elastomer, (C) 5-40 pts.wt. of at least one phosphinic acid selected from phosphinates, diphosphinates and polymers of these, having an average particle diameter of ≤10 μm, (D) 0.5-20 pts.wt. of an epoxy compound, and (E) 0.1-5 pts.wt. of an antioxidant, wherein the antioxidant (E) contains a phenolic antioxidant (e-1) as an essential component and further contains at least one selected from a phosphite-based antioxidant (e-2), a phosphonite-based antioxidant (e-3) and a thioether-based antioxidant (e-4). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has high heat resistance and flame retardancy although it does not contain a halogen-based flame retardant, etc., and has flexibility, durability (hydrolysis resistance, etc.) and moldability (extrudability, etc.). The present invention relates to an excellent flame retardant resin composition, and particularly to a flame retardant resin composition useful for coating electric wires and the like, and a covered electric wire.

  In recent years, in the automobile field, many electrical components are used for various purposes in order to improve fuel consumption, comfort, safety and the like. This application includes, for example, various electronic control devices and sensors for combustion or traveling systems represented by ECU (Electrica Control Unit), indoor and outdoor lighting related devices, air conditioning devices, motor drive devices such as wipers and power windows, etc. There are a wide variety. As the number of electrical components increases, the number of wiring in an automobile for transmitting electric power and control signals to drive the electrical components is also increasing. Such wiring materials (such as wiring coating materials) are required to have high durability and flame retardancy.

  Conventionally, polyvinyl chloride resin has been used as a material excellent in durability and flame retardancy. In terms of flame retardancy, it is known that the use of a halogen-based flame retardant makes it possible to highly flame retardant resins. However, from the viewpoint of environmental load, non-halogen materials such as materials based on flame retardant polyolefin, polyester elastomer, etc. (particularly, materials not containing halogen flame retardants) are attracting attention.

  As such a material, for example, JP-A-9-53007 (Patent Document 1) discloses polybutylene terephthalate as a hard segment, aromatic dicarboxylic acid as a soft segment, and a long-chain diol having 5 to 12 carbon atoms. A phosphorus block and / or a triazine compound (C) with respect to 100 parts by weight of a mixture of a polyester block copolymer (A) composed of a polyester having as a main component and, if necessary, a polyalkylene terephthalate resin (B). A flame retardant resin composition containing 5 to 150 parts by weight, and an electric wire having the resin composition as a coating material on the outside of a conductor are disclosed. JP-A-2002-30204 (Patent Document 2) discloses a high-melting-point crystalline polymer segment (a) containing a crystalline aromatic polyester unit and a low-melting-point polymer segment containing an aliphatic polyether unit ( b) 1 to 50 parts by weight of a phosphorus compound (B), a monocarbodiimide compound (C) and / or a polycarbodiimide compound with respect to 100 parts by weight of a polyetherester block copolymer (A) as a main constituent (D) It is disclosed that the flame-retardant polyester elastomer resin composition containing 0.01 to 10 parts by weight is suitable for covering an electric wire or an optical fiber.

  However, such a resin composition has low hydrolysis resistance, and it is necessary to add a large amount of a flame retardant in order to increase flame retardancy, and the properties of the resin are greatly impaired. Therefore, a material having characteristics required for a wide range of applications in the automobile field, such as toughness, heat resistance, hydrolysis resistance, and combustion resistance, is required.

  JP-A-2002-358837 (Patent Document 3) describes (A) 100 parts by weight of a thermoplastic aromatic polyester, (B) polytetramethylene terephthalate as a hard segment, and a soft segment. 10 to 120 parts by weight of a polyester block copolymer composed of an aromatic dicarboxylic acid and a polyester of a long-chain diol having 5 to 12 carbon atoms, and (C) an olefin-acrylate copolymer modified with a glycidyl compound A flat cable having an insulating coating made of a polyester resin composition containing 1 to 50 parts by weight is disclosed. This document also discloses that a phosphorus-based flame retardant and a polycarbodiimide compound may be included. However, such a resin composition has insufficient wear resistance and flame resistance.

  Japanese Patent Application Laid-Open No. 2001-256836 (Patent Document 4) discloses a dicarboxylic acid component mainly composed of terephthalic acid and / or an ester derivative thereof, and a diol component mainly composed of tetramethylene glycol and polytetramethylene oxide glycol. And 100 parts by weight of a polyester ether resin having an intrinsic viscosity of 1.0 to 1.7 and a terminal carboxyl group content of 30 μeq / g or less, and 0.05 to 3 parts by weight of a heat stabilizer and lubrication. A resin-coated wire formed by coating a polyester ether resin containing 0.05 to 5 parts by weight of an agent is disclosed. This document proposes a method using a phosphite compound, a hindered phenol compound, and a thioether compound as a heat stabilizer. However, such a resin composition has insufficient flame retardancy.

On the other hand, in Japanese translations of PCT publication No. 2004-537630 (patent document 5), phosphinic acid salts and / or diphosphinic acid salts and / or polymers thereof having an average particle size (d50-value) of 10 μm or less in a polyester resin are 1 to 40 mass. A method using% is proposed. However, such a resin composition can impart flame retardancy but has insufficient flexibility and toughness. In particular, due to the lack of these properties, it is not suitable for wire coating applications.
JP-A-9-53007 (Claims 1 and 2) JP 2002-30204 A (Claims 1 and 12) JP 2002-358837 A (Claims 1 and 4 to 6) JP 2001-256836 A (Claims 1 and 4 to 5) JP-T-2004-537630 (Claims 1 to 4 and 7)

  Accordingly, an object of the present invention is to provide a flame retardant resin composition that has high heat resistance and flame retardancy and is excellent in workability and flexibility or toughness, particularly useful for coating electric wires and the like. It is to provide a composition.

  Another object of the present invention is to provide a flame retardant resin composition which is excellent in durability, heat resistance and extrusion processability, and is useful for wire coating applications, and a coated electric wire coated with this flame retardant resin composition. It is in.

  Still another object of the present invention is to provide a flame retardant resin composition that is free from appearance defects on the surface of a molded product such as bumps, can suppress bleeding out even in a high temperature environment, and can maintain excellent characteristics. .

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that when specific five components are combined, even if they are non-halogen, they have high flame retardancy, moldability such as extrudability, and flexibility. The present invention has been completed by finding that a resin composition excellent in property or toughness and suitable for covering electric wires can be obtained.

That is, the present invention relates to (A) 25 to 150 parts by weight of (B) thermoplastic polyester elastomer and (C) phosphinic acid salt or diphosphinic acid salt having an average particle size of 10 μm or less based on 100 parts by weight of (A) polybutylene terephthalate resin. And 5 to 40 parts by weight of at least one phosphinic acid selected from these polymers, (D) 0.5 to 20 parts by weight of an epoxy compound, and (E) 0.1 to 5 parts by weight of an antioxidant. A flame retardant resin composition comprising an antioxidant (E) having a phenolic antioxidant (e-1) as an essential component, a phosphite antioxidant (e-2), and a phosphonite system. A flame retardant resin composition containing at least one selected from an antioxidant (e-3) and a thioether-based antioxidant (e-4), and the surface of the electric wire is the above flame retardant resin composition It is a covered electric wire covered with.

  Since the flame retardant resin composition of the present invention combines specific five components, even a non-halogen resin composition has high flame retardancy and is excellent in workability and flexibility or toughness. Moreover, since the flame retardant resin composition of the present invention is excellent in durability (such as hydrolysis resistance), heat resistance, surface smoothness, and extrusion processability, it is useful in wire coating applications. In addition, the flame retardant resin composition of the present invention can suppress bleed out even under a high temperature environment, and can maintain excellent characteristics.

The flame retardant resin composition of the present invention comprises five specific components, namely (A) polybutylene terephthalate resin, (B) thermoplastic polyester elastomer, (C) phosphinic acids, (D) epoxy compound, and (E) Consists of antioxidants.
(A) Polybutylene terephthalate (PBT) resin As a PBT resin that is a base resin, butylene terephthalate is a main component (for example, 50 to 100% by weight, preferably 60 to 100% by weight, more preferably about 70 to 100% by weight). ) Homopolyester or copolyester (polybutylene terephthalate, polybutylene terephthalate copolyester).

  As a copolymerizable monomer in the copolyester (butylene terephthalate copolymer or modified PBT resin) (hereinafter sometimes simply referred to as a copolymerizable monomer), dicarboxylic acid excluding terephthalic acid, 1,4-butanediol is used. Excluded diol, oxycarboxylic acid, lactone and the like. The copolymerizable monomers can be used alone or in combination of two or more.

  Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, dimer acid, etc. C4-40 dicarboxylic acids, preferably C4-14 dicarboxylic acids), alicyclic dicarboxylic acids (for example, C8-12 dicarboxylic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and hymic acid), Aromatic dicarboxylic acids other than terephthalic acid (eg, phthalic acid, isophthalic acid; naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid; 4,4′-diphenyldicarboxylic acid, 4,4′-diphenoxyether dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid 4,4′-diphenylmethanedicarboxylic acid, C8-16 dicarboxylic acid such as 4,4′-diphenylketone dicarboxylic acid), or reactive derivatives thereof [ester-forming derivatives such as lower alkyl esters (dimethylphthalic acid, Phthalic acid such as dimethylisophthalic acid (DMI) or C1-4 alkyl ester of isophthalic acid); acid chlorides; acid anhydrides; derivatives capable of forming an ester such as alkyl, alkoxy, or halogen substituents]. Of these, isophthalic acid is often used.

  Examples of the diol include aliphatic alkylene glycols other than 1,4-butanediol (for example, ethylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexanediol (1,6-hexanediol, etc.), octanediol ( 1,3-octanediol, etc.), lower alkylene glycols such as decanediol (C2-12 alkylene glycol, preferably C2-10 alkylene glycol, etc.), polyoxyalkylene glycols [glycols having a plurality of oxy C2-4 alkylene units, For example, diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol, etc.], alicyclic diols (for example, , 4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), aromatic diols [for example, C6-14 aromatic diols such as hydroquinone, resorcinol, naphthalenediol; biphenols (4,4′-dihydroxy) Biphenyl, etc.); bisphenols; xylylene glycol, etc.], and reactive derivatives thereof (such as ester-forming derivatives such as alkyl, alkoxy, or halogen-substituted products).

  The PBT resin may be a PBT resin [homopolyester (polybutylene terephthalate) and / or copolyester (copolymer) in which the proportion (modification amount) of the copolymerizable monomer is 30 mol% or less (for example, 0 to 30 mol%). )] Is preferred. In the copolymer, the proportion of the copolymerizable monomer can be selected from the range of, for example, about 0.01 to 30 mol%, and is usually 1 to 30 mol%, preferably 3 to 25 mol%, more preferably 5 to 5 mol%. It is about 20 mol% (for example, 5 to 15 mol%). PBT resin can be used individually or in combination of 2 or more types.

  The intrinsic viscosity (IV) of the PBT resin is not particularly limited, and may be, for example, about 0.6 to 1.4 when measured at 35 ° C. in o-chlorophenol. In terms of hydrolysis resistance and extrusion processability, the intrinsic viscosity may be preferably 0.8 to 1.3, and more preferably about 0.85 to 1.2. If the intrinsic viscosity is too low, desired hydrolysis resistance and extrusion processability (melt tension) may not be obtained. Further, if the intrinsic viscosity is too high, the load during extrusion may be increased.

PBT resin is a copolymer (polycondensation) of terephthalic acid or a reactive derivative thereof and 1,4-butanediol and a monomer that can be copolymerized if necessary by a conventional method such as transesterification or direct esterification. Can be manufactured.
(B) Thermoplastic polyester elastomer Generally, a thermoplastic polyester elastomer has a structure in which a hard polyester block (hard block or hard segment such as aromatic polyester) and a soft polyester block (soft block or soft segment) are bonded by an ester bond. Is a block copolymer. Thermoplastic polyester elastomers can be classified into two types, polyether type and polyester type, depending on the type of soft block, and any type can be used in the present invention.

  The hard polyester constituting the hard block can be obtained by polycondensation of dicarboxylic acids and diols, polycondensation of oxycarboxylic acid, etc., as in the case of the PBT resin, and usually contains at least an aromatic monomer component [the PBT Aromatic diols and reactive derivatives exemplified in the section of resin, aromatic dicarboxylic acids and terephthalic acids exemplified in the section of the PBT resin (and reactive derivatives of these aromatic dicarboxylic acids), and / or aromatics Group oxycarboxylic acids (oxybenzoic acid, oxynaphthoic acid, 4-carboxy-4′hydroxy-biphenyl, etc., and derivatives of these oxycarboxylic acids (alkyl, alkoxy, halogen substituted products, etc.) etc.)] were used. Aromatic polyester can be used. The said aromatic monomer component can be used individually or in combination of 2 or more types. In the aromatic polyester, a copolymerizable monomer (including 1,4-butanediol, terephthalic acid and the like in addition to the copolymerizable monomer exemplified in the section of the PBT resin) may be used in combination as necessary.

  The aromatic polyester may be at least an aromatic monomer component as a monomer component, for example, wholly aromatic polyester (polyester of aromatic dicarboxylic acid and aromatic diol, polyester of aromatic oxycarboxylic acid, etc.). Or a polyester of an aromatic dicarboxylic acid and a non-aromatic diol (1,4-butanediol, the aliphatic diol or alicyclic diol exemplified in the PBT resin section), a non-aromatic dicarboxylic acid (the above-mentioned A polyester of an aliphatic dicarboxylic acid and the like in the section of PBT resin) and an aromatic diol, an aromatic oxycarboxylic acid and a non-aromatic oxycarboxylic acid (an aliphatic oxycarboxylic acid such as glycolic acid and oxycaproic acid) Polyester or the like may be used.

  Among the hard polyesters, crystalline aromatic polyesters [for example, polyalkylene arylates (poly C2-4 alkylene arylates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerization components (isophthalic acid, etc. Modified poly C2-4 alkylene arylate modified or copolymerized at 1 to 30 mol% (for example, a ratio of about 3 to 25 mol%, preferably about 5 to 20 mol%)), etc. ], Liquid crystal polyester, particularly polybutylene terephthalate and the like are preferable.

  The soft polyester constituting the soft block of the polyester-type elastomer can be obtained by polycondensation of dicarboxylic acids and diols, polycondensation of oxycarboxylic acid or lactone, and the like, similar to the PBT resin. The soft polyester may be softer than the hard polyester constituting the hard block, and is usually at least an aliphatic monomer component [aliphatic diol (1,4-butanediol, aliphatic exemplified in the PBT resin section]. Diols and reactive derivatives thereof), aliphatic dicarboxylic acids (such as the aliphatic dicarboxylic acids and reactive derivatives thereof exemplified in the section of the PBT resin), aliphatic oxycarboxylic acids (such as glycolic acid and oxycaproic acid), Polyester etc. using lactone etc. exemplified in the section of PBT resin] can be used. If necessary, the aliphatic monomer component may be a copolymerizable monomer (usually a non-aromatic monomer component such as the alicyclic diol or alicyclic dicarboxylic acid exemplified in the section of the PBT resin, and these A reactive derivative or the like) may be used in combination.

  Of the soft polyesters, amorphous polyesters such as aliphatic polyesters using aliphatic dicarboxylic acids and aliphatic diols, and polylactones (ring-opening polymers of the lactones) are preferred.

  The soft segment of the polyether-type elastomer only needs to have at least a polyether unit, and is a polyether [for example, an aliphatic polyether having a polyoxyalkylene unit (polyoxyalkylene glycol exemplified in the section of the PBT resin). , Preferably poly C2-6 alkylene glycol etc.)] or polyester using this polyether. Of the polyethers, poly C2-4 alkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol are preferred. Examples of the polyester using the polyether include the polyether (polyoxyalkylene glycol and the like) and a dicarboxylic acid [usually non-aromatic dicarboxylic acid, for example, the aliphatic or alicyclic exemplified in the section of the PBT resin. And polyesters with dicarboxylic acids and their reactive derivatives].

  Among these soft blocks, a soft polyester block having at least one unit selected from polyether units (aliphatic polyether units, polyester units using aliphatic polyethers) and aliphatic polyester units is preferable.

  Specific examples of the thermoplastic polyester elastomer (B) include, for example, a polyester type (ie, polyester-polyester type) thermoplastic elastomer [eg, a homopolymer having a poly C2-4 alkylene arylate (particularly, polybutylene terephthalate unit, or Hard segments composed of aromatic crystalline polyesters and liquid crystalline polyesters such as copolymerized components (copolymers copolymerized with ethylene glycol, isophthalic acid, etc.) and aliphatic polyesters (polyethylene adipate, polybutylene adipate, etc.) Block copolymer of soft segment composed of polyester of C2-6 alkylene glycol and C6-12 alkanedicarboxylic acid, etc.], polyether type (ie polyester-polyether type) thermoplastic elastomer [ For example, a hard segment composed of the aromatic crystalline polyester or liquid crystal polyester and a soft segment composed of a polyether such as polyoxy C2-4 alkylene glycol such as polytetramethylene ether glycol (polyoxyalkylene glycol and dicarboxylic acid). And a block copolymer with an acid polyester or the like).

  Among the polyester elastomers (B), (b-1) an aliphatic polyether having a hard polyalkylene arylate block and (b-2) polycaprolactone and an oxy C2-6 alkylene unit (poly C2-6 alkylene glycol, etc.) And a block copolymer with a soft polyester block composed of aliphatic polyester. The said thermoplastic polyester elastomer (B) can be used individually or in combination of 2 or more types.

  In the thermoplastic elastomer, the weight ratio of the hard segment (or hard component) and the soft segment (or soft component) is usually the former / the latter = 10/90 to 90/10, preferably 20/80 to 80/20, More preferably, it is about 30/70 to 70/30 (for example, 40/60 to 60/40).

The thermoplastic polyester elastomer (B) has a flexural modulus of 1000 MPa or less, preferably in the range of about 50 to 400 MPa (particularly 100 to 300 MPa), for example, in applications where flexibility is required, such as wire coating applications. Is preferred. In such an application, if the flexural modulus is too small, there is a problem in the handleability in processing, and if it is too large, sufficient flexibility may not be obtained.
(C) Phosphinic acids Examples of phosphinic acids include salts such as phosphinic acid, diphosphinic acid, or polymers (or condensates such as polyphosphinic acid) [other than metal salts; boron salts (boryl compounds, etc.) , Ammonium salts, salts with amino group-containing nitrogen-containing compounds, and the like. Phosphinic acids can be used alone or in combination of two or more. The phosphinic acids may have a chain structure or a cyclic structure.

  The phosphinic acid, diphosphinic acid or a polymer thereof forming a salt may be a phosphinic acid having no organic group, diphosphinic acid, etc., but usually organic phosphinic acid, organic diphosphinic acid, organic diphosphinic acid polymerization It is often a product (or condensate). The said salt may contain 1 type of these phosphinic acids, and may contain it in combination of 2 or more types.

  Of the phosphinic acids, metal salts are particularly preferred. Salt forming metals include ant pottery metals (potassium, sodium, etc.), ants pottery earth metals (magnesium, calcium, etc.), transition metals (iron, cobalt, nickel, copper, etc.), periodic table group 12 metals (zinc, etc.) ), Periodic table group 13 metals (aluminum, etc.) and the like. The said metal salt may contain 1 type of these metals, and may contain it in combination of 2 or more types. Among the metals, ant-potent earth metals (magnesium, calcium, etc.) and periodic table group 13 metals (aluminum, etc.) are preferred.

  The valence of the metal is not particularly limited, and may be, for example, about 1 to 4 valences, preferably 2 to 4 valences, more preferably 2 or 3 valences.

  Specific examples of the phosphinic acid metal salt include a compound represented by the following formula (1), and a compound in which the diphosphinic acid metal salt is represented by the following formula (2).

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R ⁵ represents an alkylene group or an alicyclic divalent group. R ¹ and R ² may be bonded to each other to form a ring with an adjacent phosphorus atom, M ^{m +} represents a metal having a valence of m, and m represents 2 to 4 M ^{n +} represents a metal having a valence of n, and n is an integer of 2 to 4.)
As the hydrocarbon group represented by R ^{1 to} R ⁴ , an alkyl group (for example, a linear or branched C 1-6 alkyl group such as methyl, ethyl, isopropyl, n-butyl, t-butyl group), Cycloalkyl groups (C5-8 cycloalkyl groups such as cyclohexyl groups), aryl groups (C6-10 aryl groups such as phenyl groups), aralkyl groups (C6-10 aryl-C1-4 alkyl groups such as benzyl groups), etc. ) And the like. Of these groups, an alkyl group (preferably C1-4 alkyl group and the like) and an aryl group (phenyl group and the like) are usually preferred.

The ring formed by combining R ¹ and R ² together with the adjacent phosphorus atom is a heterocycle having the phosphorus atom as a hetero atom constituting the ring (phosphorus atom-containing heterocycle), and usually a 4- to 20-membered hetero ring. 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 a substituent.

Examples of the divalent hydrocarbon group represented by R ⁵ include alkylene groups (or alkylidene groups such as methylene, ethylene, phenylethylene, propylene, trimethylene, 1,4-butanediyl, 1,3-butanediyl groups and the like. A linear or branched C1-10 alkylene group which may have a substituent such as a -10 aryl group), an alicyclic divalent group (a cyclohexylene group, a cyclohexadimethylene group, etc.) Alicyclic divalent groups, etc.), aromatic divalent groups [C6-10 arylene groups optionally having substituents such as C1-4 alkyl groups such as phenylene groups and tolylene groups; arene rings such as xylylene groups; A C6-10 arylene C1-4 alkylene group optionally having a C1-4 alkyl group such as a methyl group; a bisaryl group optionally having a C1-4 alkyl group such as a methyl group on the arene ring ( Example For example, biphenylene group; linear or branched C1-4 alkane-diC6-10 arylene group such as metadiphenylene group; divalent group corresponding to C6-10 aryl ether such as diphenyl ether; diC6 such as diphenyl ketone Divalent sulfide corresponding to -10 aryl ketone; divalent group corresponding to diC6-10 aryl sulfide such as diphenyl sulfide) and the like. Of these divalent hydrocarbon groups, an alkylene group (particularly a C1-6 alkylene group) is preferred.

  Preferred metal salts (1) and (2) are polyvalent metal salts in which the valence (m and n) of the metal M is 2 to 3, respectively.

  Specific examples of the metal salt (1) of phosphinic acid include, for example, dialkylphosphinic acid Ca salts such as dimethylphosphinic acid Ca, methylethylphosphinic acid Ca and diethylphosphinic acid Ca (di-C1-10 alkylphosphinic acid Ca salts, etc.). Arylphosphinic acid Ca salts such as phenylphosphinic acid Ca and diphenylphosphinic acid Ca (mono or di C6-10 arylphosphinic acid Ca salts), alkylarylphosphinic acid Ca salts such as methylphenylphosphinic acid Ca (C1-4 alkyl) -C6-10 arylphosphinic acid Ca salt, etc.), 1-hydroxy-1H-phosphorane-1-oxide Ca salt, 2-carboxy-1-hydroxy-1H-phosphorane-1-oxide Ca salt, etc. Alkylphosphinic acid Ca salt (C3-8 alkylene) Such Sufin acid Ca salt), other Al salts corresponding to these Ca salts, and the like other metal salts.

  Specific examples of the metal salt (2) of diphosphinic acid include, for example, alkanebis (phosphinic acid) Ca salts such as ethane-1,2-bis (phosphinic acid) Ca salts [C1-10 alkanebis (phosphinic acid) Ca salts, etc. ], Alkanebis (alkylphosphinic acid) Ca salts such as ethane-1,2-bis (methylphosphinic acid) Ca salts [C1-10 alkanebis (C1-6 alkylphosphinic acid) Ca salts, etc.], corresponding to these Ca salts In addition to the Al salt, other metal salts are included.

  The metal salt of phosphinic acid also includes a polymer or condensate of these phosphinic acid polyvalent metal salts and / or diphosphinic acid polyvalent metal salts.

  The phosphinic acid is preferably at least one selected from a polyvalent metal salt of phosphinic acid, a polyvalent metal salt of diphosphinic acid, and a polyvalent metal salt of a polymer (or condensate) of diphosphinic acid.

  Preferred phosphinic acids are dialkylphosphinic acid metal salts (Ca salts, Al salts, etc.), alkanebisphosphinic acid metal salts (Ca salts, Al salts, etc.) among the metal salts represented by the above formula (1) or (2). ) Etc.

  The average particle size of the phosphinic acids needs to be 10 μm or less, preferably 8 μm or less, more preferably 5 μm or less. When the average particle diameter exceeds 10 μm, not only the surface roughness of the molded product is deteriorated, but also the effect of improving toughness and flame retardancy may be insufficient.

The average particle diameter of the phosphinic acids is obtained as a median diameter by a laser diffraction / scattering particle size distribution measuring device or the like.
(D) Epoxy Compound Examples of the epoxy compound (D) include polyfunctional epoxy compounds such as an epoxy resin (d-1) and a vinyl copolymer (d-2) having a glycidyl group. An epoxy compound can be used individually or in combination of 2 or more types.
(D-1) Epoxy Resin As the epoxy resin (d-1), for example, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin (diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethyl glycidyl phthalate, Dimethyl glycidyl hexahydrophthalate, dimer acid glycidyl ester, aromatic diglycidyl ester, cycloaliphatic diglycidyl ester, etc.), glycidyl amine type epoxy resin (tetraglycidyl diaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol) , Diglycidyl toluidine, tetraglycidyl metaxylylenediamine, diglycidyl tribromoaniline, tetra Glycidyl bisaminomethylcyclohexane), heterocyclic epoxy resins (triglycidyl isocyanurate (TGIC), hydantoin type epoxy resins, etc.), cyclic aliphatic epoxy resins (vinyl cyclohexene dioxide, dicyclopentadiene oxide, alicyclic diethylene) Epoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxycarboxylate, etc.), epoxidized polybutadiene and the like.

  Examples of the glycidyl ether type epoxy resins include glycidyl ethers of polyhydroxy compounds [bisphenol type epoxy resins (for example, bisphenol A type, bisphenol AD type, or bisphenol F type epoxy resins), and aromatic polyhydroxys such as resorcin type epoxy resins. Examples include glycidyl ethers of compounds; aliphatic epoxy resins (such as glycidyl ethers of alkylene glycol and polyoxyalkylene glycol), novolak type epoxy resins (such as phenol nopolac type and cresol novolak type epoxy resins), and the like.

  Of the epoxy resins (d-1), aromatic epoxy resins (bisphenol type epoxy resins, resorcin type epoxy resins, novolac type epoxy resins, etc.) and cyclic aliphatic epoxy resins are preferred. Among these, glycidyl ether type aromatic epoxy resins such as bisphenol type epoxy resins and novolak type epoxy resins are preferable.

  The epoxy equivalent of the epoxy resin may be, for example, about 250 to 1200 g / eq, preferably about 300 to 1100 g / eq, and more preferably about 400 to 1000 g / eq.

The number average molecular weight of the epoxy resin (d-1) may be, for example, 200 to 50,000, preferably 300 to 10,000, and more preferably about 400 to 6,000.
(D-2) Glycidyl group-containing vinyl copolymer (vinyl copolymer having a glycidyl group)
The vinyl copolymer (d-2) having a glycidyl group is a copolymer of a polymerizable monomer having a glycidyl group (such as a vinyl monomer having a glycidyl group) with another copolymerizable monomer. Consists of a polymer.

  The polymerizable monomer having a glycidyl group has at least one polymerizable group (such as an ethylenically unsaturated bond (such as a vinyl group) or an acetylene bond) together with the glycidyl group. Examples of such monomers include glycidyl ethers such as allyl glycidyl ether, vinyl glycidyl ether, chalcone glycidyl ether, and 2-cyclohexene-1-glycidyl ether; glycidyl (meth) acrylate, glycidyl maleate, glycidyl itaconate, vinyl benzoate Acid glycidyl ester, allylbenzoic acid glycidyl ester, cinnamic acid glycidyl ester, cinnamylidene acetic acid glycidyl ester, dimer acid glycidyl ester, epoxidized stearyl alcohol and acrylic acid or methacrylic acid ester, cycloaliphatic glycidyl ester (cyclohexene-4, Glycidyl or epoxy esters (especially glycidyl esters of α, β-unsaturated carboxylic acids) such as 5-diglycidyl carboxylate); Examples include epoxidized unsaturated linear or cyclic olefins such as poxyhexene and limonene oxide; N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and the like. Of these monomers, vinyl monomers having a glycidyl group, for example, glycidyl esters of α, β-unsaturated carboxylic acids are preferred. These glycidyl group-containing polymerizable monomers can be used alone or in combination of two or more.

  Examples of the glycidyl ester of the α, β-unsaturated carboxylic acid include a vinyl monomer having a glycidyl group represented by the following formula (3).

(Wherein R ⁶ represents a hydrogen atom or an alkyl group which may be substituted with a glycidyl ester group)
In the formula (3), examples of the alkyl group represented by R ⁶ include lower alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl groups (for example, C1-6 alkyl groups). In the alkyl group having a glycidyl ester group as a substituent, the number of glycidyl ester groups is not particularly limited, and may be, for example, 1 to 3, usually 1 or 2.

  Of the glycidyl esters of α, β-unsaturated carboxylic acids, glycidyl (meth) acrylate is preferred.

  Examples of the other copolymerizable monomer that can be copolymerized with the polymerizable monomer having a glycidyl group include olefin monomers (such as α-olefins such as ethylene, propylene, butene, and hexene), and diene systems. Monomers (such as conjugated dienes such as butadiene and isoprene), aromatic vinyl monomers (such as styrene monomers such as styrene, α-methylstyrene, vinyltoluene), acrylic monomers ((meth)) (Meth) acrylic acid alkyl esters such as acrylic acid and methyl methacrylate, acrylonitrile and the like), vinyl esters (such as vinyl acetate and vinyl propionate), and vinyl ethers. The copolymerizable monomer is preferably a monomer having an α, β-unsaturated double bond. These copolymerizable monomers can be used alone or in combination of two or more. Of the copolymerizable monomers, olefin monomers and acrylic monomers (such as (meth) acrylic acid and (meth) acrylic acid ester) are preferable.

  In the copolymer (d-2) having a glycidyl group, the proportion of the polymerizable monomer having a glycidyl group is 1 to 50% by weight, preferably 2 to 40% by weight, more preferably 2 to 30% by weight. It may be a degree. In addition, when using relatively low polymerizable monomers such as vinyl ethers, vinyl esters, (meth) acrylic acid esters, acrylonitrile, styrene monomers as copolymerizable monomers, a glycidyl group The proportion of the polymerizable monomer having s may be reduced (for example, about 1 to 40% by weight).

The copolymer (d-2) having a glycidyl group is preferably a copolymer obtained using at least an olefin monomer (such as C2-4 olefin such as ethylene) as the copolymerizable monomer. (Meth) acrylic monomers (such as (meth) acrylic acid C1-4 alkyl esters) may be combined. Specific examples of the copolymer include, for example, a C2-4 olefin- (meth) acrylic acid glycidyl ester copolymer such as an ethylene-methacrylic acid glycidyl ester copolymer; an ethylene-methyl acrylate-methacrylic acid glycidyl ester copolymer. Polymer, ethylene-ethyl acrylate-methacrylic acid glycidyl ester copolymer, ethylene-methyl methacrylate-methacrylic acid glycidyl ester copolymer, ethylene-ethyl methacrylate-methacrylic acid glycidyl ester copolymer, etc. -(Meth) acrylic acid C1-4 alkyl ester- (meth) acrylic acid glycidyl ester copolymer and the like.
(E) Antioxidant As the antioxidant (E), the phenolic antioxidant (e-1) is an essential component, and further, the phosphite antioxidant (e-2), the phosphonite antioxidant (e 3) and at least one selected from thioether-based antioxidants (e-4). In order to improve heat resistance, a combination of a phenolic antioxidant (e-1) and a thioether antioxidant (e-4) is preferred. Furthermore, in addition to the phenolic antioxidant (e-1) and the thioether antioxidant (e-4), it is preferable to use a phosphite antioxidant (e-2) in combination.
(E-1) Phenol-based antioxidant The phenol-based antioxidant (e-1) is a compound having one or more alkylphenol groups in its molecular structure. Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, stearyl (3,5-di-methyl-4-hydroxybenzyl) thioglycolate, stearyl-β- (4 -Hydroxy-3,5-di-t-butylphenyl) propionate, distearyl- (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, stearyl- (4-hydroxy-3-methyl-5- t-butyl) benzyl malonate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol),
4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], bis [3,3-bis (4-hydroxy) -3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5) -T-butylphenyl) butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3 5-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2-octyl Ruthio-4,6-di (4-hydroxy-3,5-di-t-butyl) phenoxy-1,3,5-triazine, 4,4′-thiobis (6-t-butyl-m-cresol), Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexyldiol-bis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], 2,4-bis-octylthio-6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-dihydrocinnamamide), 3 , 5 Di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,4-bis [(octylthio) ) Methyl] -o cresol and the like.

These can be used alone or in combination of two or more.
(E-2) Phosphite Antioxidant Examples of the phosphite antioxidant include those represented by the following general formula (4) or (5).

In the general formula (4), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are a C 1-25 alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and may be the same or different. Examples thereof include methyl group, ethyl group, butyl group, octyl group, decyl group, lauryl group, tridecyl group, stearyl group, phenyl group, alkyl and / or alkoxy-substituted phenyl group.

R ¹¹ is a C4-33 alkylene group, a substituted alkylene group, an arylene group or a substituted arylene group. For example, a butylene group, an octylene group, a phenylene group, a diphenylene group,

(Wherein, X represents an oxy group, a sulfonyl group, a carbonyl group, a methylene group, an ethylidene group, a butylidene group, an isopropylene group, a diazo group, etc.). Particularly preferred phosphite compounds include tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylene phosphite.

In the general formula (5), Ar and Ar ′ are C6-35 aryl groups or substituted aryl groups, which may be the same or different. Examples thereof include a phenyl group, a naphthyl group, a diphenyl group and the like, or alkyl, hydroxy and / or alkoxy substituted products thereof. Examples of specific compounds include bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphos. Phyto, bis (nonylphenyl) pentaerythritol diphosphite, 4-phenoxy-9-α- (4-hydroxyphenyl) -p-cumeroxy-3,5,8,10-tetraoxa-4,9-diphosphaspiro [5 5] and undecane. Of these, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite are particularly preferred.
(E-3) Phosphonite-based antioxidant Examples of the phosphonite-based antioxidant include those represented by the following general formula (6).

In the general formula (6), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an alkoxy group, and may be the same or different. Among them, R ^{12 to} R ¹⁵ are preferably a C6 or higher alkyl group, a substituted alkyl group, an alkoxy group, or an aryl group or a substituted aryl group from the viewpoint of stability during processing. Is particularly preferred.

R ¹⁶ is an alkylene group, a substituted alkylene group, an arylene group or a substituted arylene group, preferably an arylene group or a substituted arylene group. For example, a phenylene group, a naphthalene group, a biphenylene group, a terphenylene group, Or these alkyl, hydroxy, and / or alkoxy substitution products.

An example of a specific compound is tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite.
(E-4) Thioether-based antioxidant The thioether-based antioxidant (e-4) is a compound having at least one thioether bond in the molecular structure. Examples thereof include tetrakis [methylene-3- (dodecylthio) propionate] methane, dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. Alternatively, two or more kinds can be used in combination.
(F) Polycarbodiimide compound In the present invention, a polycarbodiimide compound (F) can be further used for the purpose of improving durability, particularly hydrolysis resistance.

  The polycarbodiimide compound (F) is a compound having at least two carbodiimide groups represented by (—N═C═N—) in the molecule, and a compound synthesized by a generally well-known method is used. For example, using an organophosphorus compound or organometallic compound as a catalyst, various polyisocyanates (diisocyanates) can be subjected to a decarboxylation condensation reaction at a temperature of about 70 ° C. or more in a solvent-free or inert solvent. Can be synthesized. As a method for producing a polycarbodiimide compound, U.S. Pat.No. 2,941,956, Japanese Patent Publication No. 47-33279, J. Org. Chem. 28, 2069-2075 (1963), Chemical Review 1981. Vol. 81. 4. Those described in p619-621 and the like are known.

  Examples of the organic diisocyanate that is a synthesis raw material in the production of the polycarbodiimide compound include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate and mixtures thereof. Specifically, hexamethylene diisocyanate, cyclohexane- Examples include 1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and methylcyclohexane diisocyanate.

  Moreover, in the case of the said polycarbodiimide compound, a polymerization reaction can be stopped on the way by cooling etc., and it can control to a suitable polymerization degree. In this case, the terminal is isocyanate. Further, in order to control the polymerization degree to an appropriate level, there is a method in which all or part of the remaining terminal isocyanate is sealed using a compound that reacts with the terminal isocyanate of an aliphatic polycarbodiimide compound such as monoisocyanate. By controlling the degree of polymerization, compatibility with the polymer and storage stability can be improved, which is preferable in terms of quality improvement.

  Examples of the monoisocyanate for controlling the degree of polymerization by sealing the end of such a polycarbodiimide compound include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, and butyl isocyanate.

  A preferred polycarbodiimide compound used in the present invention has a number average molecular weight of 1000 to 30000, preferably 2000 to 20000, and more preferably 3000 to 15000. If the number average molecular weight is too small, the heat resistance may be inferior. If it is too large, the resin may not be sufficiently dispersed and the hydrolysis resistance may not be sufficiently improved.

In addition, aromatic polycarbodiimides containing an aromatic component in the molecular chain skeleton are particularly preferably used because of their high hydrolysis resistance and high heat resistance, such as p-phenylene-bis-o-triylcarbodiimide and p-phenylene. -Bis-p-chlorophenylcarbodiimide, aromatic dicarbodiimide compounds such as ethylene-bis-diphenylcarbodiimide, poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (4,4′-diphenylmethanecarbodiimide), poly (3 , 3′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylphenylenecarbodiimide) ), Aromatic polycarbodiimide compounds such as poly (methyl-diisopropylphenylenecarbodiimide), poly (triethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), and the like.
(Ratio of each component)
In the resin composition of the present invention, the ratio of the thermoplastic polyester elastomer (B) is, for example, 25 to 150 parts by weight, preferably 50 to 140 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin (A). Preferably, it may be about 80 to 130 parts by weight. If the proportion of the component (B) is too small, the flexibility is poor and cracking may easily occur due to bending, and if it is too large, the heat resistance, hydrolysis resistance, and combustion resistance decrease significantly, and polybutylene There is a possibility that the effect of terephthalate cannot be obtained sufficiently.

  The ratio of the phosphinic acids (C) is, for example, about 5 to 40 parts by weight, preferably about 10 to 35 parts by weight, and more preferably about 10 to 30 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin (A). May be. If the proportion of the component (C) is too small, the flame retardancy improving effect may be insufficient. If it is too large, the flexibility and hydrolysis resistance will be significantly reduced, and the effect of polybutylene terephthalate will be sufficiently obtained. There is a risk of not being able to.

  The ratio of the epoxy compound (D) is, for example, 0.5 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 0.8 to 100 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin (A). It may be about 12 parts by weight. Further, the epoxy resin (d-1) is preferably 0.8 to 5 parts by weight, and the vinyl copolymer (d-2) having a glycidyl group is preferably 3 to 12 parts by weight. If the ratio is too small, the melt tension of the resin required for processing may be insufficient, and if it is too high, molding problems such as an increase in the viscosity of the resin may occur.

  The proportion of the antioxidant (E) is, for example, 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, more preferably 0.5 to 100 parts by weight of the polybutylene terephthalate resin (A). About 3 parts by weight may be used. If the proportion is too small, sufficient heat stability and long-term physical properties cannot be obtained, and if it is too large, not only is it uneconomical, but the improvement effect of the heat stability reaches saturation, and conversely, the moldability decreases. There is a risk that the strength may decrease.

  A polycarbodiimide compound (F) is mix | blended to 5 weight part with respect to 100 weight part of polybutylene terephthalate resin (A) as needed. Too much polycarbodiimide compound (F) is not only uneconomical, but also increases the amount of gas generated during the process and impairs the appearance.

  In a typical embodiment of the present invention, in the flame retardant resin composition, the polybutylene terephthalate resin (A) has an intrinsic viscosity of 0.8 to 1.3 dl / g, and the thermoplastic polyester elastomer (B) A block copolymer of a hard polybutylene terephthalate block (b-1) and a soft polyester block (b-2) having at least one unit selected from polyether units and aliphatic polyester units, and an epoxy compound (D) is (d-1) an aromatic epoxy resin having an epoxy equivalent of 250 to 1200 g / eq, and (d-2) a vinyl monomer having a glycidyl group and an α, β-unsaturated bond. This is a case of at least one selected from a copolymer with a polymerizable monomer.

  In the resin composition of the present invention, conventional additives, for example, stabilizers other than those described above (ultraviolet absorbers, light stabilizers, etc.), antistatic agents, lubricants, mold release agents, other flame retardants, flame retardant aids Agents, crystallization nucleating agents, colorants (such as dyes or pigments), lubricants, plasticizers, fillers, anti-dripping agents, and the like may be added.

  In the resin composition of the present invention, other resin components such as acrylic resin, fluororesin, polyamide resin, polyacetal resin, polysulfone, polyphenylene oxide, styrene resin (within a range not inhibiting the effect of the present invention) Thermoplastic resins such as polystyrene, AS resin, ABS resin); soft thermoplastic resins such as ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer; phenol resin, melamine resin, polyester resin (unsaturated polyester, etc.) ), Thermosetting resins such as silicone resins and epoxy resins may be added. These other resins can be used alone or in combination of two or more.

  The resin composition of the present invention may be a powder mixture or a molten mixture, or may be a molded body (such as a sheet or film-like composition) in which the molten mixture is solidified. The powder mixture is composed of (A) PBT resin, (B) thermoplastic polyester elastomer, (C) phosphinic acid, (D) epoxy compound, (E) antioxidant, and (F) polycarbodiimide compound as necessary. It can be prepared by mixing additives and / or other resin components in a conventional manner. For example, (1) A method in which each component is mixed, kneaded by a single or twin screw extruder and extruded to prepare pellets, and then molded. (2) A pellet (master batch) having a different composition is once prepared. A method of mixing (diluting) a predetermined amount of the pellets and subjecting the pellets to molding to obtain a molded product having a predetermined composition, (3) a method of directly charging one or more of each component into a molding machine, and the like can be employed. In the preparation of the composition used for the molded product, the powdery body of the resin component (in addition to the component (A), (B) or (D), the other resin, etc.) and other components are mixed. Melting and kneading is advantageous for improving the dispersion of other components.

  A molded product can be obtained by melt-kneading the resin composition of the present invention and molding the resin composition by a conventional method such as extrusion molding, injection molding, or compression molding. Since the resin composition is excellent in flame retardancy and molding processability, it can be used for the production of various molded articles and various uses such as electric / electronic parts, mechanical mechanism parts, automobile parts, packaging materials. It can be suitably used for a case or the like.

  In particular, since the resin composition of the present invention is excellent in properties such as combustion resistance, heat resistance, hydrolysis resistance, flexibility, etc., it is useful for coating electric wires (copper wires, platinum wires, etc.). In particular, the resin composition is excellent in hydrolysis resistance and flexibility in addition to combustion resistance, heat resistance, and the like, and further can impart appropriate adhesion to a conductor (electric wire). It is useful in applications for coating power transmission or transmission (wave transmission) wires (for example, as a flame-retardant resin composition for wire coating).

  A coated electric wire can be produced by coating an electric wire with the resin composition. The coating method is not particularly limited, and the coating can be performed by a conventional coating method such as extrusion molding or press working. For example, if necessary, the covered electric wire may be manufactured by sandwiching the electric wire between a sheet or a film-like resin composition and pressing it.

  Moreover, in this invention, the power transmission or transmission (wave transmission) line | wire (an electric wire, an optical fiber cable, etc.) coat | covered with the said resin composition is also disclosed.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
Examples 1-13 and Comparative Examples 1-8
Each component shown in Tables 1 and 2 was dry blended in the ratio shown in the table, and melt-kneaded at 260 ° C. using a twin screw extruder having a φ30 mm screw, and then pelletized to obtain a pellet-shaped resin composition. . The resin pellets were dried at 140 ° C. for 3 hours and then used for molding.

  An ASTM No. 4 type tensile test piece having a thickness of 1.0 mm was prepared using the obtained pellet-shaped resin composition.

  Further, the obtained pellet-shaped resin composition was melt-kneaded at 260 ° C. using a plastmill single screw extruder having a φ20 mm screw, and a φ0.9 mm copper wire was coated with a coating thickness of 0.2 mm. The coated electric wire was made.

The measurement method of characteristic evaluation is as follows.
<Evaluation by ASTM No. 4 type tensile test piece>
[Tensile strength and tensile elongation at break]
Tensile strength (MPa) and tensile elongation at break (%) were measured according to ASTM D-638.
[Hydrolysis resistance (tensile strength and elongation at break after wet heat test treatment)]
After exposure to a pressure cooker tester at 121 ° C./2 atm for 48 hours, the tensile strength (MPa) and the tensile elongation at break (%) were measured in accordance with ASTM D-638 to evaluate hydrolysis resistance. .
[Heat aging resistance]
After heat treatment in a hot air oven at 125 ° C. or 150 ° C. for a predetermined time, the tensile strength (MPa) was measured according to ASTM D-638. The heat aging resistance was evaluated by the time (days) until the tensile strength of the treated sample was reduced to 80%.

<Evaluation with covered wire>
[Extrudability]
The extrusion situation when the resin composition was coated (extruded) on a 0.9 mm copper wire was visually evaluated in the following two stages. In addition, bleed-out was not seen in the obtained extrusion-molded product.
O: The resin composition is uniformly coated x: The coating state of the resin composition is non-uniform, and the copper wire is exposed [coated wire surface properties]
The electric wire surface which coat | covered the resin composition on the 0.9 mm copper wire was visually evaluated in the following two steps.
O: The surface of the electric wire is smooth and no agglomerates are observed. X: The surface of the electric wire is not sufficiently smooth, and some of the agglomerates are observed on the surface [flame retardant]
Based on ISO6722-12 term, the 45 degree inclination combustion test was done and the combustibility of the resin composition was evaluated. The shorter the burning time, the better the flame retardancy.
[Self diameter winding test after aging treatment]
In accordance with ISO6722-10.2, a winding test was conducted after 3000 hours of treatment in an oven at 125 ° C. A sample in which no crack or the like was observed was marked with ◯, and a sample in which cracks were observed was marked with ×.
[Self-diameter winding test after hydrolysis resistance]
After being treated at 121 ° C./2 atm for 72 hours, a winding test was performed. A sample in which no crack or the like was observed was marked with ◯, and a sample in which cracks were observed was marked with ×.

The results of Examples and Comparative Examples are shown in Tables 1 and 2. In the examples and comparative examples, the following components were used.
(A) PBT resin (A-1) Polybutylene terephthalate (Intrinsic viscosity IV = 1.20 dl / g, manufactured by Wintech Polymer Co., Ltd.)
(B) Thermoplastic polyester elastomer (B-1) Toyobo Co., Ltd., “Perprene GP300”
Hard block; polybutylene terephthalate, soft block; polyether type soft polyester (B-2), manufactured by Teijin Chemicals Ltd., “Nuberan P4110AN”
Hard block; polybutylene terephthalate, soft block; polyester type soft polyester (C) phosphinic acid (C-1) 1,2-diethylphosphinic acid aluminum salt prepared by the following method 2106 g (19.5 mol) of 1,2 -Diethylphosphinic acid was dissolved in 6.5 liters of water, 507 g (6.5 mol) of aluminum hydroxide was added with vigorous stirring of the solution and the resulting mixture was heated to 85 ° C. The mixture was stirred at 80-90 ° C. for a total of 65 hours, then cooled to 60 ° C. and filtered with suction. After drying in a vacuum drying cabinet at 120 ° C. until the mass became constant, 2140 g of fine particle powder that did not melt below 300 ° C. was obtained. The yield was 95% of the theoretical value. The obtained particle powder was pulverized by a jet mill to prepare 1,2-diethylphosphinic acid aluminum salt having an average particle diameter of 4 μm.
The particle diameter was measured using a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) using distilled water as a dispersion medium, and the obtained median diameter was defined as the particle diameter. .
(C-2) 1,3-ethane-1,2-bismethylphosphinic acid calcium salt prepared by the following method: 500 ml of 325.5 g (1.75 mol) of ethane-1,2-bismethylphosphinic acid Dissolved in water, 129.5 g (1.75 mol) of calcium hydroxide was added in several portions over 1 hour with vigorous stirring of the solution. Next, the mixture was stirred at 90 to 95 ° C. for several hours, then cooled and filtered with suction. When dried in a vacuum drying cabinet at 150 ° C. until the mass was constant, 335 g of product was obtained. This was not melted below 380 ° C. The yield was 85% of theory. The obtained particle powder was pulverized with a jet mill to prepare 1,3-ethane-1,2-bismethylphosphinic acid calcium salt having an average particle diameter of 4 μm.
(C-3) Unground product of 1,2-diethylphosphinic acid aluminum salt 1,2-diethylphosphinic acid aluminum salt before the pulverization step described in (C-1). The average particle size was 55 μm.
(D) Epoxy compound (D-1), manufactured by Atofina Japan, “Rotada-AX8930”
Ethylene / acrylic acid / glycidyl methacrylate copolymer (D-2) manufactured by Sumitomo Chemical Co., Ltd., “Bond First BF7M”
Ethylene / Glycidyl methacrylate / Methyl acrylate copolymer (D-3) “Epicoat 1004” manufactured by Yuka Shell Epoxy Co., Ltd.
Epoxy resin (epoxy equivalent 875-975 g / eq)
(E) Antioxidant (E-1) Phenolic antioxidant; “Irganox 1010” manufactured by Ciba Specialty Chemicals Co., Ltd.
(E-2) Phosphite antioxidant; “Adeka Stub PEP-24G” manufactured by Adeka Co., Ltd.
(E-3) Phosphonite antioxidant; “SANDSTAB P-EPQ” manufactured by Clariant Co., Ltd.
(E-4) Thioether-based antioxidant; “ADEKA STAB AO412S” manufactured by ADEKA Corporation
(F) Polycarbodiimide compound (F-1) Aliphatic polycarbodiimide; Nisshinbo Co., Ltd., “Carbodilite HMV-8CA”
(F-2) Aromatic polycarbodiimide; manufactured by Rhein Chemie Japan Co., Ltd., “STABAKZOL P”

  In Comparative Examples 5 and 7, since the extrudability was insufficient, the coated wire surface properties and flame retardancy were not evaluated. In Comparative Example 8, the combustion time exceeded 180 seconds, resulting in poor flame retardancy.

Claims (6)

(A) With respect to 100 parts by weight of polybutylene terephthalate resin, (B) 25 to 150 parts by weight of thermoplastic polyester elastomer, (C) phosphinic acid salt, diphosphinic acid salt having an average particle size of 10 μm or less, and a polymer thereof. Flame retardancy comprising 5 to 40 parts by weight of at least one phosphinic acid selected from: (D) 0.5 to 20 parts by weight of an epoxy compound, and (E) 0.1 to 5 parts by weight of an antioxidant It is a resin composition, and the antioxidant (E) contains the phenolic antioxidant (e-1) as an essential component, and further includes a phosphite antioxidant (e-2) and a phosphonite antioxidant (e- A flame retardant resin composition containing at least one selected from 3) and a thioether-based antioxidant (e-4). The flame retardant resin composition according to claim 1, further comprising 5 parts by weight or less (F) of a polycarbodiimide compound (100 parts by weight of (A) polybutylene terephthalate resin). The thermoplastic polyester elastomer (B) is a hard polybutylene terephthalate block (b-1) and a soft polyester block (b-2) having at least one unit selected from a polyether unit and an aliphatic polyester unit. The flame retardant resin composition according to claim 1, which is a block copolymer. In the phosphinic acid (C), the phosphinic acid salt is represented by the following formula (1), and the diphosphinic acid salt is represented by the following formula (2). object.

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R ⁵ represents an alkylene group or an alicyclic divalent group. R ¹ and R ² may be bonded to each other to form a ring with an adjacent phosphorus atom, M ^{m +} represents a metal having a valence of m, and m represents 2 to 4 M ^{n +} represents a metal having a valence of n, and n is an integer of 2 to 4.) The epoxy compound (D) comprises (d-1) an aromatic epoxy resin having an epoxy equivalent of 250 to 1200 g / eq, and (d-2) a vinyl monomer having a glycidyl group and an α, β-unsaturated bond. The flame-retardant resin composition according to any one of claims 1 to 4, which is at least one selected from a copolymer with a copolymerizable monomer. A covered electric wire in which the surface of the electric wire is coated with the flame retardant resin composition according to any one of claims 1 to 5.