CN101218305B - Flame retardant resin composition - Google Patents

Flame retardant resin composition Download PDF

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Publication number
CN101218305B
CN101218305B CN2006800249249A CN200680024924A CN101218305B CN 101218305 B CN101218305 B CN 101218305B CN 2006800249249 A CN2006800249249 A CN 2006800249249A CN 200680024924 A CN200680024924 A CN 200680024924A CN 101218305 B CN101218305 B CN 101218305B
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acid
resin
salt
metal
flame retardant
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CN101218305A (en
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原科初彦
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Polyplastics Co Ltd
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Polyplastics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

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

Description

Flame retardant resin composition
Technical field
The present invention relates to resin combination that flame retardant resistance and plasticity are outstanding and electrical characteristic are improved and the molding that forms by said composition.
Background technology
In the middle of thermoplastic resin, polybutylene terephthalate polyester based resins such as (PBT) or polyamide-based resin etc. are because of having outstanding mechanical characteristics, electrical characteristic, weathering resistance, water tolerance, resistance to chemical reagents or solvent resistance, so obtained application in various uses such as electric-electronic unit, machine structural parts, trolley part.On the other hand, with regard to thermoplastic resin,,, consider, also be required to possess flame retardant resistance from secure context except being required to improve its mechanical characteristics along with the expansion of Application Areas.Usually the method that adopts is to add the method that non-halogen flame retardants such as halogen flame retardant or phosphorus series compound, nitrogenous compound are realized fire-retardantization in thermoplastic resin.Compare with non-halogen flame retardant, the flame retardant resistance height of halogen flame retardant can be to reach fire-retardantization of resin on a small quantity.
In addition, for this thermoplastic resin (composition), except requiring flame retardant resistance, also require it to possess high electrical characteristic according to purposes.In order to improve the electrical characteristic of this resin, open in the flat 10-251528 communique (patent documentation 1) the spy, a kind of anti-Characteristics of Spark Erosion excellent flame thermoplastic resin composition is disclosed, its by (a) thermoplastic resin 100 weight parts, to contain (b) ammonium polyphosphate 0.5-50 weight part, (c) bromine be that halogens such as polystyrene fire retardant are that high molecular weight flame retardant 5-50 weight part, (d) ANTIMONY TRIOXIDE SB 203 99.8 PCT 0-15 weight part, (e) inorganic filler 0-50 weight part are formed.In addition, open in the flat 11-343389 communique (patent documentation 2) the spy, a kind of anti-Characteristics of Spark Erosion excellent flame thermoplastic resin composition is disclosed, its by the melamine salt of (A) thermoplastic resin 100 weight parts, (B) mineral acid and/or condensation phosphamide 0.5-50 weight part, (C) bromine be fire retardant 5-50 weight parts such as halogen flame retardant such as high molecular weight flame retardant, (D) ANTIMONY TRIOXIDE SB 203 99.8 PCT 0-15 weight part and (E) inorganic filler 0-50 weight part form.But, even the resin combination of being put down in writing in these documents, under the situation of condition harshness, its electric erosion resistance to improve effect also abundant inadequately.
On the other hand, open in the 2004-339510 communique (patent documentation 3) the spy and to mention, by and with specific (two) phosphinates and halogen flame retardant, can improve the flame retardant resistance of thermoplastic resin.But, the electrical characteristic such as electric erosion resistance of the composition of being put down in writing in these documents to improve effect abundant inadequately.
In addition, open flat 10-114854 communique (patent documentation 4) and the spy opens in the flat 10-273589 communique (patent documentation 5) the spy, disclose a kind of flame retardant resin composition that improves electrical characteristic, it contains vibrin or polyamide resin and halogenated fire-retardants, inorganic filler and Na 3HP 2O 7, K 2H 2P 2O 7, Na 3H 2P 3O 10, KNaH 2P 2O 7, Na 2H 2P 2O 7, Na 8P 6O 19Deng (acidity) tetra-sodium or Tripyrophosphoric acid metal-salt.In the document, also mention if will improve galvanic corrosion index (CTI), also can contain ethene-olefin polymers such as (methyl) alkyl acrylate copolymer again.But the electric erosion resistance of the composition of putting down in writing in these documents also fails to improve fully.In addition, in these documents, CTI improves effect and can have greatly changed according to the kind of employed composition and amount etc., for example, in the composition of patent documentation 4 and patent documentation 5, anti-galvanic corrosion improve effect and be sufficient inadequately during with olefin polymer and tetra-sodium or Tripyrophosphoric acid an alkali metal salt, improve effect and when also having the inorganics (inorganic filler) of synergy in a large number again, can show with sulfuric acid alkali earth metal salt or talcum etc.Therefore, with regard to the composition of these documents, though can also can cause rerum natura obviously to descend simultaneously to a certain degree improving electric erosion resistance on (for example, the 425-600 volt) really.And, also use the tetra-sodium or the Tripyrophosphoric acid an alkali metal salt of poor heat stability in the method for in these documents, putting down in writing, so the thermostability of resin can descend also, the manufacturing of resin combination, plasticity are also undesirable.
Patent documentation 1: the spy opens flat 10-251528 communique (claim 1)
Patent documentation 2: the spy opens flat 11-343389 communique (claim 1)
Patent documentation 3: the spy opens 2004-339510 communique (claim 1)
Patent documentation 4: the spy open flat 10-114854 communique (claim 1, paragraph sequence number [0013], embodiment)
Patent documentation 5: the spy open flat 10-273589 communique (claim 1, claim 20, embodiment)
Summary of the invention
Can also improve the flame retardant resin composition and the molding thereof of electrical characteristic when therefore, the object of the present invention is to provide flame retardant resistance outstanding.
Another object of the present invention is to provide the flame retardant resin composition and the molding thereof that can improve electrical characteristic such as electric erosion resistance really with high level.
The inventor has carried out wholwe-hearted research in order to realize above-mentioned problem, found that halogen flame retardant, specific organic-inorganic hydrochlorate and when being selected from least a electrical characteristic activator combination of ethylene series resin, fluorine resin and group 4 metal compounds, can be under the condition of not damaging plasticity, really can improve or improve the flame retardant resistance and the electrical characteristic of matrix resin with high level, thereby finish the present invention.
Promptly, flame retardant resin composition of the present invention comprises matrix resin (A), halogen flame retardant (B), is selected from least a organic-inorganic hydrochlorate (C) and the electrical characteristic activator (D) of the oxysalt (C2) of organic secondary phosphine acid salt (C1) and basic nitrogen compound, and be the flame retardant resin composition that electrical characteristic are improved, above-mentioned electrical characteristic activator (D) comprises and is selected from least a of ethylene series resin, fluorine resin and periodictable group 4 metal compounds.
Above-mentioned matrix resin (A) can comprise that being selected from polyester based resin, polyamide-based resin, polycarbonate-based resin, polyphenylene oxide is that resin, polyphenylene sulfide are at least a thermoplastic resin of resin, phenylethylene resin series and vinyl resin.Especially, matrix resin (A) can comprise having the terephthalic acid of being selected from 1,4-cyclohexanedimethyleterephthalate ester, terephthalic acid C 2-4Alkylene ester and naphthalic acid C 2-4At least a unitary homopolymerization polyester or the copolyester of alkylene ester, specifically can comprise be selected from polybutylene terephthalate, with the mutual-phenenyl two acid bromide two alcohol ester unit be principal constituent copolyester, Poly(Trimethylene Terephthalate), be the copolyester, polyethylene terephthalate of principal constituent, be copolyester at least a of principal constituent with the ethylene glycol terephthalate unit with the propylene glycol ester terephthalate unit.
Above-mentioned halogen flame retardant (B) can be selected from contain bromine acrylic resin (for example, poly-(methyl) benzyl acrylate of bromination is a resin), the phenylethylene resin series that contains bromine (for example, the bromide of phenylethylene resin series, brominated styrene is that brominated styrenes such as monomeric homopolymer or multipolymer are resin etc.), the polycarbonate-based resin (brominated bisphenol type polycarbonate resin etc.) that contains bromine, epoxy compounds (the brominated bisphenol type Resins, epoxy that contains bromine, brominated bisphenol type phenoxy resin etc.), bromination polyaryl ether compound, the brominated aromatic imide compound [for example, the two bromination phthalimides of alkylidene group (for example, ethylenebis bromination phthalimide etc.) etc.], at least a fire retardant that contains bromine atoms of bromination bi-aromatic compounds and bromination three (aryloxy) triaizine compounds.
Above-mentioned organic secondary phosphine acid salt (C1) can be for example can have substituent aliphatics phosphinates and/or can have substituent alicyclic phosphinates.
In the above-mentioned flame retardant resin composition, above-mentioned organic secondary phosphine acid salt (C1) can be to be selected to have substituent dialkyl phosphinic acid, can have substituent bicyclic alkyl phospho acid, can have substituent alkylidene group phospho acid, can have substituent alkenylene phospho acid, can have substituent (two) ring alkylidene group phospho acid, and can have organic phospho acid of substituent alkane two (alkyl phosphinic acid) and be selected from periodictable the 1st family's metal, the periodictable group II metal, the periodictable group-4 metal, periodictable the 7th family's metal, periodictable the 8th family's metal, periodictable the 10th family's metal, periodictable the 11st family's metal, periodictable the 12nd family's metal, metal belonging to group 13 of periodic table, periodictable the 14th family's metal, periodictable the 15th family's metal, and the aminotriazine compound (for example, melamine, melam, melem and mellon) the salt of at least a material, above-mentioned oxysalt (C2) can be to be selected from condensed phosphoric acid, at least a oxygen acid of sulfuric acid and pyrosulfuric acid and be selected from ammonia, carbamide compound, the salt of at least a basic nitrogen compound of guanidine compound and aminotriazine compound.
As representative compound, above-mentioned organic secondary phosphine acid salt (C1) can be to be selected to have substituent dialkyl phosphinic acid, can have substituent bicyclic alkyl phospho acid, can have substituent alkylidene group phospho acid, can have substituent alkenylene phospho acid, and can have organic phospho acid of substituent alkane two (alkyl phosphinic acid) and be selected from the periodictable group II metal, metal belonging to group 13 of periodic table, melamine, melam, the salt of at least a material of melem and mellon, above-mentioned oxysalt (C2) can be the salt that is selected from Tripyrophosphoric acid and aminotriazine compound, the salt of sulfuric acid and aminotriazine compound, the salt of pyrosulfuric acid and aminotriazine compound, and the condensation phosphamide is at least a.
Above-mentioned organic-inorganic hydrochlorate (C) can comprise organic secondary phosphine acid salt (C1) and oxysalt (C2).
Above-mentioned electrical characteristic activator (D) can comprise ethylene series resin and/or periodictable group 4 metal compounds at least.In addition, electrical characteristic activator (D) can be to be selected from α-C 2-3The homopolymer of alkene or multipolymer, α-C 2-3Alkene-(methyl) acrylic copolymer, α-C 2-3Alkene-(methyl) acrylate copolymer (for example, α-C 2-3Alkene-(methyl) vinylformic acid C 1-4Alkyl ester copolymer, α-C 2-3Alkene-(methyl) glycidyl acrylate multipolymers etc.), sour modified olefin is resin, fluoridizes α-C 2-3The homopolymer of alkene or multipolymer and titanium oxide at least a.
In the above-mentioned resin combination, the ratio of halogen flame retardant (B) can be about 2-20 weight part with respect to matrix resin (A) 100 weight parts, and the ratio of organic-inorganic hydrochlorate (C) can be about 3-30 weight part with respect to matrix resin (A) 100 weight parts.In addition, in the above-mentioned resin combination, with respect to halogen flame retardant (B) 100 weight parts, the ratio of organic-inorganic hydrochlorate (C) is about 20-500 weight part, and the ratio of electrical characteristic activator (D) can be about 10-150 weight part.
Above-mentioned resin combination can also contain be selected from the aminotriazine compound salt (for example, melamine cyanurate etc.), (moisture) metal silicate (for example, talcum, kaolin etc.), (moisture) borate metal salt (for example, (moisture) zinc borate, (moisture) lime borate etc.), (moisture) stannic acid metal-salt (for example, (moisture) zinc etc.), metal oxide (for example, zinc oxide etc.), metallic sulfide (for example, zinc sulphide etc.) and at least a electrical characteristic of alkali earth metallic compound (for example, lime carbonate, secondary calcium phosphate etc.) improve auxiliary agent (E).
In addition, above-mentioned resin combination can also contain at least a flame retardant (F) that is selected from aromatics, P contained compound and antimony containing compounds.Above-mentioned aromatics (perhaps flame retardant (F)) can be selected from phenolic resin, polyphenylene oxide resinoid, aromatic epoxy resin, phenoxy resin, polyphenylene sulfide resinoid, polycarbonate resin, polyarylester resinoid (polyarylate), aromatic polyamide resinoid, aromatic polyester-based resin (aromatic polyester resins that can have liquid crystal liquid crystal property) and aromatic polyester amides resin (the aromatic polyester amide resins that can have liquid crystal liquid crystal property) at least a.In addition, above-mentioned P contained compound (perhaps flame retardant (F)) can be selected from (condensation) phosphoric acid ester, (condensation) phosphoric ester amides, (crosslinked) aryloxy phosphonitrile, (Asia) phosphate metal salt, hypophosphorous acid metal salt, organic (Asia) phosphonic acid ester, organic (Asia) phosphonic acid metal salt and organic (Asia) phosphonic acids aminotriazine salt at least a.Particularly, above-mentioned P contained compound (perhaps flame retardant (F)) can be selected from alkyl (Asia) phosphonic acid metal salt, (Asia) phosphate metal salt and hypophosphorous acid metal salt at least a.
In addition, above-mentioned resin combination can also contain at least a additive that is selected from weighting agent, heat-resisting stabilizing agent, processing stabilizers and reactive stablizer.
The flame retardant resistance of resin combination of the present invention and electrical characteristic excellence, for example [A] is (i) when measuring with the test film of thickness 0.8mm, flame retardant resistance based on the UL94 combustion test can be (particularly more than the V-0) more than the V-1, and (ii) can be 350V above (particularly more than the 400V) based on the comparison galvanic corrosion index of IEC (the International Electrotechnical Commi, below identical) 112.In addition, when resin combination of the present invention (i) is measured with the test film of thickness 1.6mm at [B], can be more than the V-2 based on the flame retardant resistance of UL94 flammability test and (to be preferably more than the V-1, be preferably more than the V-0 especially), and be (to be preferably more than the 650V) more than the 500V based on the comparison galvanic corrosion index of IEC112 (ii).
The present invention also comprises the molding that is formed by above-mentioned resin combination.This molding can be electrical and electronic parts, office automated machine parts, household electrical appliances machine part, trolley part or machine structural parts.
The invention effect
Flame retardant resin composition of the present invention because with matrix resin, halogen flame retardant, specific organic-inorganic hydrochlorate and the specific electrical characteristic activator that is used to improve electrical characteristic made up, so excellent in flame retardance can improve electrical characteristic simultaneously.In addition, among the present invention,, can improve electrical characteristic such as electric erosion resistance really with high level by aforesaid combination.
Embodiment
Flame retardant resin composition of the present invention comprises matrix resin, halogen flame retardant, specific organic-inorganic hydrochlorate and specific electrical characteristic activator at least.This resin combination not only improved flame retardant resistance, and improved electrical characteristic (electric erosion resistance of representing with galvanic corrosion index relatively etc. etc.).
[matrix resin (A)]
As matrix resin (A), be not particularly limited, can enumerate various resins, for example, thermoplastic resin [for example, polyester based resin, polyamide-based resin, polycarbonate-based resin, polyphenylene oxide is resin, polyphenylene sulfide is a resin, polyacetal resin, ketone resin, polysulfones is resin (for example, polysulfones etc.), polyetherketone is resin (polyetherketone etc.), polyetherimide, polyurethane series resin, polyimide, polyphenyl methyl alcohol, acrylic resin, phenylethylene resin series, vinyl resin, thermoplastic elastomer etc.], heat-curing resin (resol, aminoresin, the Thermocurable vibrin, Resins, epoxy, the silicone-based resin, vinyl acetate is a resin, polyurethane series resin etc.) etc.Below, representative matrix resin is described in detail.
(vibrin)
Polyester based resin is homopolymerization polyester or the copolyester that obtains by polycondensation of the polycondensation of the polycondensation of di-carboxylic acid composition and glycol component, hydroxycarboxylic acid or lactone or these compositions etc.As preferred polyester is resin, and generally including saturated polyester is resin, and particularly the aromatic series saturated polyester is a resin.
As the dicarboxylic acid composition, for example can enumerate aliphatic dicarboxylic acid (C such as succsinic acid, pentanedioic acid, hexanodioic acid, Thapsic acid, dimeracid 4～40Dicarboxylic acid, preferred C 4～14Dicarboxylic acid etc.), ester ring type dicarboxylic acid (hexahydrophthalic acid, six hydrogen terephthalic acids, norbornene dicarboxylic acids C such as (acid of Ha ィ ミ ッ Network) 8～12Dicarboxylic acid etc.), aromatic dicarboxylic acid [C 8～16Aromatic hydrocarbons dicarboxylic acid (phthalic acid, m-phthalic acid, terephthalic acid, 2,6-naphthalic acid etc.), xenyl-dicarboxylic acid (4,4 '-xenyl dicarboxylic acid, phenyl ether-4,4 '-dicarboxylic acid, diphenyl alkane dicarboxylic acid (4,4 '-ditan dicarboxylic acid etc.), or derivatives thereof (lower alkyl esters, acid anhydrides etc. can form the derivative of ester) etc. 4,4 '-benzophenone dicarboxylic acid etc.)].These dicarboxylic acid compositions may be used singly or two or more in combination.In addition in case of necessity, can also and use polycarboxylic acids such as trimellitic acid, Pyromellitic Acid.
Preferred dicarboxylic acid composition comprises aromatic dicarboxylic acids such as terephthalic acid, naphthalic acid.
As glycol component, for example can enumerate aliphatic diol [aklylene glycol (for example, ethylene glycol, 1, ammediol, propylene glycol, 1, C such as 4-butyleneglycol, hexylene glycol for example 2～12Aklylene glycol, preferred C 2～10Aklylene glycol), polyalkylene glycol [has a plurality of oxygen base C 2-4The glycol of alkylidene unit, for example glycol ether, dipropylene glycol, dibutylene glycol, triglycol, polytetramethylene glycol etc.], alicyclic diol [for example 1,4-cyclohexanediol, naphthenic hydrocarbon dialkanol (C such as 1,4 cyclohexane dimethanol 5-6Naphthenic hydrocarbon two C 1-2Alkanol etc.), Hydrogenated Bisphenol A etc.].But also can with quinhydrones, Resorcinol, biphenol, bisphenols or its C 2-3Aromatic diol and usefulness such as alkylene oxide affixture [2, two (4-hydroxy phenyl) propane, 2 of 2-, 2-pair-(4-(2-hydroxyl-oxethyl) phenyl) propane or their brominated derivative etc.], phenylene dimethyl glycol.These diol components may be used singly or two or more in combination.In addition in case of necessity, can also and use polyvalent alcohols such as glycerine, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane.
Preferred glycol component comprises C 2-6Aklylene glycol (ethylene glycol, 1, ammediol, propylene glycol, 1, straight chain shape aklylene glycols such as 4-butyleneglycol), the polyalkylene glycol with about 2～4 oxyalkylene repeat units [contain poly-(oxygen-C such as glycol ether 2-6Alkylidene group) unitary glycol], 1,4 cyclohexane dimethanol etc.
Hydroxycarboxylic acid comprises for example hydroxy-benzoic acid, hydroxynaphthoic acid, 4-carboxyl-4 '-xenol, hydroxyphenyl acetic acid, oxyacetic acid, D-, hydroxycarboxylic acid or derivatives thereofs such as L-or D/L-lactic acid, hydroxycaproic acid etc.
Lactone comprises C such as propiolactone, butyrolactone, valerolactone, caprolactone (for example 6-caprolactone etc.) 3-12Lactone etc.
As preferred polyester is resin, comprise and have the naphthenic hydrocarbon of being selected from two alkylidene aryl ester units (terephthalic acids 1,4-cyclohexanedimethyleterephthalate ester units etc.) and the alkylidene aryl ester units (terephthalic acid alkylene ester and/or alkylene naphthalate unit, for example, terephthalic acid C 2-4Alkylene ester unit, naphthalic acid C 2-4Alkylene ester unit etc.) at least a unit [for example, have (for example about 50～100 weight % as principal constituent, preferred about 75～100 weight %)] homopolymerization polyester or copolyester are [for example, poly terephthalic acid 1,4-cyclohexanedimethyleterephthalate ester, polyalkylene terephthalates (for example, polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT), polybutylene terephthalate poly terephthalic acid C such as (PBT) 2-4Alkylene ester), poly-alkylene naphthalate (poly-naphthalic acid C such as PEN, poly-naphthalic acid propylene glycol ester, PBN for example 2-4Alkylene ester) homopolymerization polyester such as; The copolyester that at least a unit that is selected from terephthalic acid naphthenic hydrocarbon two alkylene esters, terephthalic acid alkylene ester and alkylene naphthalate is contained as main component (for example more than the 50 weight %)].Particularly preferred polyester based resin comprises that the polybutylene terephthalate that the mutual-phenenyl two acid bromide two alcohol ester is contained as main component is a resin [polybutylene terephthalate for example, with the mutual-phenenyl two acid bromide two alcohol ester unit is copolyester (the polybutylene terephthalate copolyester: for example of principal constituent, the polybutylene terephthalate of isophthalate modified etc.)], with the propylene glycol ester terephthalate unit be the Poly(Trimethylene Terephthalate) of principal constituent be resin [for example, Poly(Trimethylene Terephthalate), with the propylene glycol ester terephthalate unit is the copolyester (Poly(Trimethylene Terephthalate) copolyester) of principal constituent], and with the ethylene glycol terephthalate unit as the PET series resin of main component [polyethylene terephthalate for example, with the ethylene glycol terephthalate unit is copolyester (the polyethylene terephthalate copolyester: for example of principal constituent, 1,4 cyclohexane dimethanol modification polyethylene terephthalate, 4-hydroxy-benzoic acid modification polyethylene terephthalate etc.)].Polyester based resin may be used singly or two or more in combination.
In addition, in copolyester,, can enumerate C as monomer that can copolymerization 2-6Aklylene glycol (straight chain shape aklylene glycol such as ethylene glycol etc.), (glycol ether, polytetramethylene glycol etc. contain poly-(oxygen-C to have the polyalkylene glycol of 2～4 left and right sides oxyalkylene repeat units 2-4Alkylidene group) C unitary glycol etc.), 4-12Aliphatic dicarboxylic acid (pentanedioic acid, hexanodioic acid, sebacic acid etc.), aliphatic diol (1,4 cyclohexane dimethanol etc.), aromatic diol [for example, 2, the C of bisphenols such as two (4-(2-hydroxyl-oxethyl) phenyl) propane of 2- 2-3The alkylene oxide affixture, quinhydrones, Resorcinol, 3,3 '-or 4,3 '-or 4,4 '-dihydroxyl phenylbenzene, 1,4-or 2,6-dihydroxy naphthlene etc.], aromatic dicarboxylic acid [(non-) symmetrical aromatic dicarboxylic acid (phthalic acid, m-phthalic acid, the single sodium salt of 5-sulfoisophthalic acid etc.), diphenyldicarboxylic acid (4,4 '-diphenyldicarboxylic acid etc.), naphthalene dicarboxylic acids (2,6-naphthalene dicarboxylic acids etc.) etc.], hydroxy-benzoic acid (3-or 4-hydroxy-benzoic acid etc.), hydroxynaphthoic acid (6-hydroxyl-2-naphthoic acid, 6-hydroxyl-1-naphthoic acid etc.), 4-carboxyl-4 '-xenol etc.] etc.In addition, as long as polyester based resin can be straight catenate without detriment to melt-shaping, also can have branched structure, can also be crosslinked shape.Polyester based resin can also be a liquid crystal polyester.In addition, as polyester based resin, comprise that also (liquid crystal) polyesteramide of using the monomer (for example, 3-or 4-amino-phenol, 3-or 4-benzaminic acid, tetramethylene-diamine, hexamethylene-diamine, nine methylene diamine, MXDP etc.) that contains amino to carry out modification is a resin.
Polyester based resin can be with manufacturings such as for example transesterify of customary way, direct esterification methods.The intrinsic viscosity of polyester based resin is preferably about 0.5-1.8 for for example about 0.4-2.0, more preferably about 0.6-1.5.
(polyamide-based resin)
As polymeric amide, comprise by diamines and dicarboxylic acid deutero-polymeric amide; By aminocarboxylic acid, as required and the polymeric amide that obtains with diamines and/or dicarboxylic acid; By lactan, as required by and with diamines and/or dicarboxylic acid deutero-polymeric amide.As polymeric amide, also comprise copolyamide.Diamines, dicarboxylic acid, aminocarboxylic acid, lactan can use separately or be used in combination more than two kinds respectively.
As diamines, can enumerate for example C such as tetramethylene-diamine, hexamethylene-diamine 3-10Alicyclic diamines such as aliphatie diamine, two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane (can have substituent two (amino C such as alkyl 5-8Cycloalkyl) C 1-4Alkane etc.).If desired, also can and use aromatic diamines such as phenylenediamine, MXDP.As dicarboxylic acid, can be exemplified as C such as hexanodioic acid, suberic acid, sebacic acid, 12 carbon alkane dicarboxylic acid 4-20Aliphatic dicarboxylic acid (C 6-16Alkane dicarboxylic acid etc.), Dimerized lipid acid (dimeracid); Hexanaphthene-1,4-dicarboxylic acid or hexanaphthene-1, ester ring type dicarboxylic acid such as 3-dicarboxylic acid; Aromatic dicarboxylic acids such as phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid or terephthalic acid, naphthalic acid etc.As aminocarboxylic acid, can be exemplified as C such as aminoheptylic acid, amino-nonanoic acid, amino hendecoic acid 4-20Aminocarboxylic acid.As lactan, can be exemplified as C such as hexanolactam, laurolactam 4-20Lactan.
As polyamide-based resin, can enumerate fatty polyamides such as polymeric amide 46, polyamide 6, polyamide 66, polyamide 6 10, polyamide 6 12, polymeric amide 11, polymeric amide 12; By two (aminocyclohexyl) C 1-3Alicyclic diamine and C such as alkanes 8-14The alicyclic polymeric amide that the aliphatic dicarboxylic acid of alkane dicarboxylic acid etc. obtains; The polymeric amide that obtains by aromatic dicarboxylic acid (for example, terephthalic acid and/or m-phthalic acid) and aliphatie diamine (for example, hexamethylene-diamine, nine methylene diamine etc.); Polymeric amide that obtains by aromatic series and aliphatic dicarboxylic acid (for example, terephthalic acid and hexanodioic acid) and aliphatie diamine (for example, hexamethylene-diamine) etc.These polymeric amide can use separately or be used in combination more than two kinds.
In these polyamide-based resins, preferred non-aromatic or fatty polyamide (polymeric amide 46, polyamide 6, polyamide 66, polyamide 6 10, polyamide 6 12, polymeric amide 11, polymeric amide 12 etc.), semiaromatic polyamide composition (polymeric amide MXD6, polymeric amide 9T etc.), semi-aromatic copolyamide (polyamide 6 T/6, polyamide 6 T/66, polyamide 6 T/11, polyamide 6 T/12, polyamide 6 I/6, polyamide 6 I/66, polyamide 6 T/6I, polyamide 6 T/6I/6, polyamide 6 T/6I/66, polyamide 6 T/M5T etc.) etc.
(polycarbonate-based resin)
In polycarbonate-based resin, comprise the polymkeric substance that the reaction by dihydroxy compound (ester ring type glycol or bisphenol cpd etc.) and carbonic ethers such as carbonyl chloride (phosgene) or diphenyl carbonate obtains.As bisphenol cpd, can enumerate two (4-hydroxyphenyl) methane, 2, two (hydroxyaryl) C such as two (4-hydroxyphenyl) propane of 2- 1-10Alkane; 1, two (hydroxyaryl) C such as two (4-hydroxyphenyl) hexanaphthenes of 1- 4-10Naphthenic hydrocarbon; 4,4 '-dihydroxydiphenyl ether; 4,4 '-dihydroxy-diphenyl sulfone; 4,4 '-dihydroxyl diphenylsulfide; 4,4 '-dihydroxyl diphenylketone etc.
As preferred polycarbonate-based resin, comprise bisphenol A polycarbonate.
(polyphenylene oxide is resin)
At polyphenylene oxide is in the resin (polyphenylene ether is a resin), comprises homopolymer and multipolymer.As homopolymer, can enumerate poly-(single, two or three C such as poly-(2,6-dimethyl-1,4-phenylene) oxide compound, poly-(2,5-dimethyl-1,4-phenylene) oxide compound, poly-(2,5-diethyl-1,4-phenylene) oxide compound 1-6The alkyl phenylene) oxide compound, poly-(single or two C 6-20The aryl phenylene) oxide compound, poly-(single C 1-6Alkyl-single C 6-20The aryl phenylene) oxide compound etc.
Multipolymer as polyphenylene oxide, can enumerate have the above-mentioned homopolymer monomeric unit more than 2 kinds multipolymer (for example, have 2,6-dimethyl-1,4 phenylene ether units, with 2,3,6-trimethylammonium-1, the random copolymers of 4 phenylene ether units etc.), the modified by alkyl phenol phenyl aldehyde resin segment that comprises alkylphenols such as making cresols and phenyl aldehyde resin (resol etc.) or alkylbenzene formaldehyde resin to react and obtain and as the polyphenylene oxide segmental modified polyphenyl ether copolymer of main-body structure, on polyphenylene oxide or its multipolymer grafting styrene based copolymer and/or unsaturated carboxylic acid or acid anhydrides ((methyl) vinylformic acid, maleic anhydride etc.) modified graft copolymer etc.
(polyphenylene sulfide is a resin)
As polyphenylene sulfide is resin (polyphenylene sulfide is a resin), comprises having the diphenyl sulfide skeleton-(Ar-S)-[in the formula, Ar represents phenylene] homopolymer and multipolymer.As phenylene (except to phenylene, metaphenylene and the adjacent phenylene, also can be that the phenylene that replaces (for example has C Ar-), 1-6Substituent alkyl phenylene such as alkyl has substituent aryl phenylenes such as phenyl) ,-Ar-A 1In-Ar-[the formula, Ar represents phenylene, A 1Expression Direct Bonding, O, CO or SO 2] etc.Polyphenylene sulfide is that resin can be the homopolymer that comprises the same repeating unit in the poly (phenylene sulfide) ether unit that this phenylene constitutes, and also can be to contain the not multipolymer of repeating unit of the same race.
As homopolymer, the preferred use with to the polymkeric substance that come down to line style of phenylene sulfenyl as repeating unit.And multipolymer can be combined and used in different two or more in the above-mentioned phenylene sulfenyl.As multipolymer, preferably with to the phenylene sulfenyl as main repeating unit, and contain the combination of metaphenylene sulfenyl, can be to contain the above multipolymer that comes down to line style of 60 moles of % (preferred 70 moles of %) to the phenylene sulfenyl.
Polyphenylene sulfide is that resin can be the polymkeric substance by the oxidation cross-linked or heat cross-linking of low-molecular-weight simple linear polymer is formed, and also can be the polymkeric substance of the linear structure in fact that obtained by the monomer polycondensation based on two functional monomers.Be resin as polyphenylene sulfide in addition, can also comprise side chain that the combination of monomers post polymerization that will have three above functional groups obtains or crosslinked polyphenylene sulfide, this resin and the mixed resin combination of above-mentioned simple linear polymer.
As polyphenylene sulfide is resin, except polyphenylene sulfide or poly-diphenyl sulfide (PBPS), can also use polyphenyl thioketones (PPSK), poly-diphenyl sulfide sulfone (PPSS) etc.
(phenylethylene resin series)
As phenylethylene resin series, can be exemplified as the homopolymer or the multipolymer of styrenic monomers (vinylbenzene, Vinyl toluene etc.); The multipolymer of styrenic monomers and vinyl monomer [α such as ((methyl) acrylic monomer (for example, methyl) vinyl cyanide, (methyl) acrylate, (methyl) vinylformic acid etc.), maleic anhydride, β-monoene unsaturated carboxylic acid or acid anhydrides or ester etc.]; Styrenic graft copolymer, vinylbenzene alkene block copolymer etc.
As preferred phenylethylene resin series, can enumerate polystyrene (GPPS), styrene-methylmethacrylate copolymer, vinylbenzene-(methyl) acrylic copolymer, styrene-acrylonitrile copolymer (AS resin), at rubber constituent (polyhutadiene, acrylic rubber, styrene-butadiene copolymer rubber, EPDM, EVA etc.) going up polymerizing styrene is that monomer is also gone back polymerization co-polymerized monomer (vinyl cyanide as required, methyl methacrylate etc.) graft copolymer [impact resistant polystyrene (HIPS), ABS resin, MBS resin etc.], comprise polystyrene block, multipolymer (for example, styrene-butadiene-styrene (SBS) segmented copolymer with diene or olefin block, styrene-isoprene block copolymer, styrene-isoprene-phenylethene (SIS) segmented copolymer, hydrogenation styrene-butadiene-styrene (SEBS) segmented copolymer, hydrogenation styrene-isoprene-phenylethene (SEPS) segmented copolymer, epoxidized SBS, epoxidation SIS etc.] etc.
(vinyl resin)
As vinyl resin, comprise ethene base system monomer (for example, vinyl ester such as vinyl acetate; Vinyl-chloride-containing base monomer (for example, vinylchlorid etc.); Vinyl ketones; Vinyl ethers; Vinyl amines such as N-vinylcarbazole etc.) homopolymer or multipolymer, or with other can copolymerization monomeric multipolymer etc.Can also use the derivative (for example, polyvinyl acetals such as polyvinyl alcohol, polyvinyl alcohol methylal, polyvinyl alcohol butyral, ethylene-vinyl acetate copolymer etc.) of above-mentioned vinyl resin.
These resins or macromolecular compound can be used in combination separately or more than two kinds.
As preferred matrix resin, can enumerate can be that polyester based resin, phenylethylene resin series, polyamide-based resin, the polyphenylene oxide of liquid crystal polyester is thermoplastic resins such as resin (particularly being selected from least a thermoplastic resin of polyamide-based resin and polyester based resin), more preferably enumerates polyester based resin (PBT is that resin, PPT are that resin, PET are resin etc.) etc.
The number-average molecular weight of matrix resin is not particularly limited, and can suitably select according to the kind or the purposes of resin, for example can be from 5 * 10 3～200 * 10 4, preferred 1 * 10 4～150 * 10 4, further preferred 1 * 10 4～100 * 10 4About scope select.In addition, when matrix resin was polyester based resin, number-average molecular weight for example can be 5 * 10 3～100 * 10 4, preferred 1 * 10 4～70 * 10 4, further preferred 1.2 * 10 4～30 * 10 4About.
[halogen flame retardant (B)]
As halogen flame retardant (B), can use Organohalogen compounds.Organohalogen compounds contain usually and are selected from least a of chlorine, bromine and iodine atom.
As the halogen flame retardant, [poly-(methyl) benzyl acrylate of halogenation is a resin can to enumerate the acrylic resin that for example contains halogen, for example, poly-(methyl) benzyl acrylate of poly-brominations such as ((methyl) vinylformic acid pentabromo-benzyl esters), the homopolymer of poly-(methyl) vinylformic acid halogenation benzyl esters such as ((methyl) vinylformic acid pentachloro-benzyl esters) or multipolymer etc.], the phenylethylene resin series that contains halogen [for example, phenylethylene resin series (cinnamic homopolymer or multipolymer) (is for example carried out halogenation treatment, chlorine, bromine, bromine chloride processing etc.) halogenide (brominated Polystyrene of the phenylethylene resin series that obtains, chlorinated polyphenyl ethene etc.), halogenated styrenes is monomeric homopolymer or multipolymer etc.], polycarbonate-based resin (the brominated polycarbonate that contains halogen, halogenation polycarbonate such as chlorination polycarbonate etc.), epoxy compounds (the brominated epoxy resin that contains halogen, halogenated epoxy resins such as chlorination Resins, epoxy; Halogenation phenoxy resins such as bromination phenoxy resin etc.), [for example, eight to two (halogenated aryl) ethers such as decabromodiphynly oxide, eight to ten chlorodiphenyl ethers (for example, two (halogenation phenyl) ether etc.) for halogenation polyaryl ether compound; The polyphenylene oxide that brominated polyphenylether etc. contain halogen is resin etc.], halogenated aromatic imide compound [for example, the two bromination phthalimides of alkylidene group (for example, C such as ethylenebis bromination phthalimide 2-6The two bromination phthalimides of alkylidene group etc.) wait brominated aromatic imide compound (for example, double imide compound etc.) etc.], halogenation bi-aromatic compounds [for example, couple (halogenation C such as brominated diphenyl base 6-10Aryl); Two (halogenation C such as brominated diphenyl methylmethane 6-10Aryl) C 1-4Alkane; Halogenation bisphenols or derivatives thereofs such as brominated bisphenol A (making bromination polyester that the ethylene oxide adduct polymerization of halogenation bisphenols obtains etc.) etc.], halogenation aliphatic hydrocarbon (the saturated or unsaturated halogenation clicyclic hydrocarbon of crosslinked ring type, for example, ten dichloro five rings 18-7, the poly-cyclic diolefine of halogenations such as 15-diene etc.), halogenation three (aryloxy) triaizine compounds bromination three (aryloxy) triaizine compounds such as [for example, etc.] bromination triple phenoxyl triazines etc.The halogen flame retardant can use separately or be used in combination more than two kinds.
As the halogen flame retardant, the compound that preferably contains chlorine atom and/or bromine atoms, especially preferably contain bromine atoms organic bromide [contain bromine acrylic resin, contain bromine phenylethylene resin series, contain bromine polycarbonate-based resin (for example, brominated bisphenol type polycarbonate resins such as brominated bisphenol A type polycarbonate resin), epoxy compounds (for example, the brominated bisphenol type Resins, epoxy brominated epoxy resins such as (brominated bisphenol a type epoxy resin etc.) that contains bromine; Brominated bisphenol type phenoxy resin bromination phenoxy resins such as (brominated bisphenol A type phenoxy resins etc.) etc.), bromination polyaryl ether compound (octabromodiphenyl ether etc. two (bromination aryl) ether compounds etc.), brominated aromatic imide compound, bromination bi-aromatic compounds, bromination three (aryloxy) triaizine compounds etc.] etc. contain the fire retardant of bromine atoms].These contain among the fire retardant of bromine atoms, being preferably selected from poly-(methyl) benzyl acrylate of bromination especially is resin, brominated styrene be resin [for example, the bromide of phenylethylene resin series such as brominated Polystyrene (perhaps phenylethylene resin series is carried out bromination and handle the bromide that forms), brominated styrene be monomeric homopolymer or multipolymer (for example, brominated polystyrene etc.) etc.], brominated bisphenol type polycarbonate resin, brominated bisphenol type Resins, epoxy, the two bromination phthalimides of brominated bisphenol type phenoxy resin and alkylidene group (for example, C such as ethylenebis bromination phthalimide 2-6The two bromination phthalimides of alkylidene group etc.) at least a etc.
The ratio of halogen flame retardant for example, for about the 1-30 weight part, is preferably about 2-25 weight part (for example, the 2-20 weight part), more preferably about 3-20 weight part (for example, 5-18 weight part) with respect to matrix resin 100 weight parts.
[organic-inorganic hydrochlorate (C)]
Organic-inorganic hydrochlorate (C) comprises at least a of the oxysalt (C2) (salt of oxygen acid and basic nitrogen compound) that is selected from organic secondary phosphine acid salt (C1) and basic nitrogen compound.
(organic secondary phosphine acid salt (C1))
As organic secondary phosphine acid salt (C1), can use and for example on phospho acid, be substituted with the salt [salt that forms with at least a salt formation composition that is selected from metal, boron, ammonium and basic nitrogen compound (metal-salt, boron salt (boryl compound etc.), ammonium salt, with the salt of the nitrogenous compound that contains amino etc.) etc.] etc. that organic radical that organic radical (can have substituent alkyl etc.) forms replaces phospho acid, polynary phospho acid organic phospho acid such as (connecting polynary phospho acid that a plurality of phospho acid form etc. with the multivalence organic radical).In addition, even organic secondary phosphine acid salt uses the halogen flame retardant, also can improve the electrical characteristic of resin.Therefore, organic secondary phosphine acid salt has the effect of electrical characteristic activator.In organic secondary phosphine acid salt; organic phospho acid { for example can have substituting group; hydroxyl, unsaturated group are [for example; carboxyl, acyl group, alkoxy carbonyl (methoxycarbonyl etc.) etc. contain the base of carbon-oxygen unsaturated link(age) etc.], alkyl (for example; alkyl such as methyl etc.), alkoxyl group (for example, methoxyl group etc.) etc. }.These substituting groups of organic phospho acid can use separately or make up more than two kinds.
In the organic secondary phosphine acid salt (C1),, can enumerate and for example can have substituent list or dialkyl phosphinic acid [dialkyl phosphinic acid class (two C as representative organic phospho acid 1-10Alkyl phosphinic acid etc.), for example, dialkyl phosphinic acids such as dimethyl phospho acid, methylethyl phospho acid, diethyl phospho acid, ethyl-butyl phospho acid (ethyl normal-butyl phospho acid, ethyl isobutylphosphinic, ethyl tert-butyl phospho acid etc.), dipropyl phospho acid (di phospho acid, di-isopropyl phospho acid etc.), dibutyl phospho acid (di-n-butyl phospho acid, diisobutylphosphinicacid acid, di-t-butyl phospho acid etc.), dioctylphosphinic acid(HDOP); (methylol) methyl phospho acid, (hydroxyethyl) methyl phospho acid, two (methylol) phospho acid, two (hydroxyethyl) phospho acid etc. contain the dialkyl phosphinic acid of hydroxyl; (2-carboxy ethyl) methyl phospho acid etc. contain the dialkyl phosphinic acid of carboxyl; (methoxymethyl) methyl phospho acid, two (methoxymethyl) phospho acid etc. contain the dialkyl phosphinic acid of alkoxyl group; (2-carboxy ethyl) methyl phospho acid, (2-carboxyl propyl group) methyl phospho acid, two (2-carboxy ethyl) phospho acid, two (2-carboxyl propyl group) phospho acid etc. contain the dialkyl phosphinic acid of carboxyl; (2-methoxycarbonyl ethyl) methyl phospho acid, [2-(beta-hydroxyethyl carbonyl) ethyl] methyl phospho acid, (2-methoxycarbonyl propyl group) methyl phospho acid, two (2-methoxycarbonyl ethyl) phospho acid, two (2-methoxycarbonyl propyl group) phospho acid etc. contain the dialkyl phosphinic acid of alkoxy carbonyl etc.], (for example can have substituent list or bicyclic alkyl phospho acid, the monocycle alkyl phosphinic acid (for example, cycloalkylalkyl phospho acid such as cyclohexyl methyl phospho acid), list or bicyclic alkyl phospho acid (single or two C such as bicyclic alkyl phospho acid (for example, dicyclohexyl phospho acid etc.) 5-10Cycloalkyl phospho acid etc.) etc.), can have substituent list or diaryl phospho acid [for example, C such as phenyl phosphinic acid 6-10Arylphosphinic acid; Two C such as diphenyl phosphonic acid 6-10Arylphosphinic acid; Alkylaryl phospho acid (C such as aminomethyl phenyl phospho acid 1-4Alkyl C 6-10Arylphosphinic acid etc.) list or diaryl phospho acid such as], can have substituent alkylidene group phospho acid (for example, 1-hydroxyl phospholane (ヒ De ロ キ シ ホ ス ホ ラ Application)-1-oxide compound, 1-hydroxy-3-methyl phospholane-1-oxide compound, 2-carboxyl-1-hydroxyl-1H-phospholane-C such as 1-oxide compound 3-8Alkylidene group phospho acid etc.), (for example can have substituent alkenylene phospho acid, 1-hydroxyl-2,3-dihydro-1H-phosphorus heterocycle amylene (ホ ス ホ one Le) 1-oxide compound, 1-hydroxyl-2,5-dihydro-1H-phosphorus heterocycle amylene 1-oxide compound, 1-hydroxy-3-methyl-2, ring such as 5-dihydro-1H-phosphorus heterocycle amylene 1-oxide compound C 3-8Alkenylene phospho acid etc.), can have substituent (two) ring alkylidene group phospho acid (for example, 1,3-ring butylidene phospho acid, 1,3-ring pentylidene phospho acid, 1,4-encircles octylene phospho acid, 1,5-encircles (two) C such as octylene phospho acid 4-10Ring alkylidene group phospho acid etc.), { for example can have polynary phospho acid that substituent two ring alkenylene phospho acid, a plurality of phospho acid (perhaps organic phospho acid) are connected to form by the multivalence organic radical, can have substituent alkane bisphosphinic acid [ethane-1, the two C such as (phospho acid) of 2- 1-10Alkane two (phospho acid) etc.], can have substituent alkane two (alkyl phosphinic acid) [ethane-1, the two C such as (methyl phospho acid) of 2- 1-10Two (the C of alkane 1-6Alkyl phosphinic acid) etc.] etc. } etc.
As the metal that forms organic secondary phosphine acid salt, can enumerate periodictable the 1st family's metal (basic metal) (lithium, potassium, sodium etc.), periodictable group II metal (alkaline-earth metal) (magnesium, calcium, barium etc.), periodictable group-4 metal (titanium, zirconium etc.), transition metal (periodictable the 7th family's metal such as manganese; Periodictables such as iron the 8th family's metal; Periodictables such as cobalt the 9th family's metal; Periodictables such as nickel the 10th family's metal; Periodictables such as copper the 11st family's metal etc.), periodictable the 15th family's metals such as periodictable the 14th family's metal, antimony such as periodictable the 13rd family's metal, tin such as periodictable the 12nd family's metal, aluminium such as zinc etc.These metals can use separately or be used in combination more than two kinds.In addition, metal-salt can be moisture salt, for example, and moisture magnesium salts, moisture calcium salt, moisture aluminium salt, moisture zinc salt etc.In addition, as metal-salt, also comprise the salt (for example, titanyl salt, zirconium oxonium salt etc.) of the oxidized formation of metal part.In addition, as the salifiable basic nitrogen compound of shape, can enumerate and for example contain amino nitrogenous compound [aminotriazine compound (melamine, guanamines, benzoguanamine and/or its condenses (melamine condensates such as melam, melem, mellon etc.) etc.), guanidine compound (guanidine etc.) etc.], carbamide compound (urea etc.) etc.Basic nitrogen compound can use separately or be used in combination more than two kinds.These salt formation compositions can make up and formation salt separately or more than two kinds.For example,, also comprise the double salt of organic phospho acid and multiple salt formation composition as organic secondary phosphine acid salt, for example, melamine melam melem double salt, melamine melam melem mellon double salt etc.
Among salifiable metal of these shapes and the nitrogenous compound, preferred cycle table the 1 family's metal, group II metal, group-4 metal, the 7th family's metal, the 8th family's metal, the 10th family's metal, the 11st family's metal, the 12nd family's metal, the 13rd family's metal, the 14th family's metal, the 15th family's metal and aminotriazine compound (melamine, melamine condensates etc.).
In addition, in the above-mentioned organic secondary phosphine acid salt, has some or all of can form (for example, can be carboxylic acid salinization) salt (the above-mentioned illustrative salt of acidic group (carboxyl etc.) as the acidic group of substituent organic phospho acid, for example, the salt of phospho acid and same metal or nitrogenous compound etc.).
As preferred organic secondary phosphine acid salt, can enumerate and to have substituent aliphatics hypophosphite and/or can have substituent alicyclic hypophosphite, for example, be selected from and have substituent dialkyl phosphinic acid, can have substituent bicyclic alkyl phospho acid, can have substituent alkylidene group phospho acid, can have substituent alkenylene phospho acid, can have substituent (two) ring alkylidene group phospho acid, and organic phospho acid that can have substituent alkane two (alkyl phosphinic acid), with be selected from periodictable the 1st family's metal, group II metal, group-4 metal, the 7th family's metal, the 8th family's metal, the 10th family's metal, the 11st family's metal, the 12nd family's metal, the 13rd family's metal, the 14th family's metal, the salt of at least a material of the 15th family's metal and aminotriazine compound { for example, can have substituent dialkylphosphinic salts [dimethyl phospho acid Ca salt, methylethyl phospho acid Ca salt, diethyl phospho acid Ca salt, ethyl-butyl phospho acid Ca salt, dibutyl phospho acid Ca salt, (2-propyloic) methyl phospho acid Ca salt, (2-carboxylic propyl group) methyl phospho acid Ca salt, two (2-propyloic) phospho acid Ca salt, two (2-carboxylic propyl group) phospho acid Ca salt and with alkali earth metal salts such as the corresponding Mg salt of these calcium salts; Aluminium salt such as dimethyl phospho acid Al salt, methylethyl phospho acid Al salt, diethyl phospho acid Al salt, ethyl-butyl phospho acid Al salt, dibutyl phospho acid Al salt, (2-propyloic) methyl phospho acid Al salt, (2-carboxylic propyl group) methyl phospho acid Al salt, two (2-propyloic) phospho acid Al salt, two (2-carboxylic propyl group) phospho acid Al salt; Methylethyl phospho acid Ti salt, diethyl phospho acid Ti salt, ethyl-butyl phospho acid Ti salt, dibutyl phospho acid Ti salt and the titanium salts such as titanyl salt corresponding with these salt; Diethyl phospho acid Zn salt, ethyl-butyl phospho acid Zn salt, dibutyl phospho acid Zn salt, methylethyl phospho acid Zn salt, zinc salts such as (2-propyloic) methyl phospho acid Zn salt etc.], the salt of aminotriazine compound (dimethyl phospho acid melamine salt, methylethyl phospho acid melamine salt, diethyl phospho acid melamine salt, ethyl-butyl phospho acid melamine salt, dibutyl phospho acid melamine salt, with salt of the corresponding melamine melam of these melamine salts melem double salt etc. and aminotriazine compound etc.) etc., can have substituent alkylidene group hypophosphite [for example, alkali earth metal salt (the Ca salt of 1-hydroxyl phospholane 1-oxide compound, Mg salt etc.), Al salt, Ti salt, titanyl salt, metal-salts such as Zn salt; Aminotriazine salt such as melamine salt, melamine melam melem double salt etc.] etc.
As particularly preferred organic secondary phosphine acid salt, comprise being selected from the salt that can have substituent dialkyl phosphinic acid, can have substituent bicyclic alkyl phospho acid, can have substituent alkylidene group phospho acid, can have substituent alkenylene phospho acid and can have organic phospho acid of substituent alkane two (alkyl phosphinic acid) and be selected from least a material of periodictable group II metal (calcium etc.), metal belonging to group 13 of periodic table (aluminium etc.), aminotriazine compound (melamine, melam, melem, mellon etc.).Organic secondary phosphine acid salt can use separately or make up more than two kinds.
As the concrete example of organic secondary phosphine acid salt, for example can enumerating, the spy opens clear 55-5979 communique, Te Kaiping 8-73720 communique, Te Kaiping 9-278784 communique, Te Kaiping 11-236392 communique, the spy opens the 2001-2686 communique, the spy opens the 2004-238378 communique, the spy opens the 2004-269526 communique, the spy opens the 2004-269884 communique, the spy opens the 2004-346325 communique, special table 2001-513784 communique, special table 2001-525327 communique, special table 2001-525328 communique, special table 2001-525329 communique, special table 2001-540224 communique, No. 4180495 communiques of United States Patent (USP), No. 4208321 communiques of United States Patent (USP), No. 4208322 communiques of United States Patent (USP), No. 6229044 communiques of United States Patent (USP), the compound of putting down in writing in No. 6303674 communiques of United States Patent (USP).
(oxysalt of basic nitrogen compound (C2))
As the oxygen acid that constitutes oxysalt (C2) (oxygen acid beyond above-mentioned organic phospho acid), comprise for example nitric acid, chloric acid (perchloric acid, chloric acid, chlorous acid, hypochlorous acid etc.), phosphoric acid [non-condensed phosphoric acids such as ortho-phosphoric acid, metaphosphoric acid, phosphorous acid, Hypophosporous Acid, 50; Tetra-sodium, triphosphoric acid, four phosphoric acid, many metaphosphoric acids, phosphoric anhydride condensed phosphoric acids such as (Vanadium Pentoxide in FLAKESs) (Tripyrophosphoric acid) etc.], (the part ester of above-mentioned phosphoric acid (Hypophosporous Acid, 50 beyond phosphoric acid) and alcohols such as alkanol, aklylene glycol (for example for organic phosphoric acid, mono phosphoric acid esters such as dimethyl phosphate or dialkyl etc.), sulfuric acid (non-condensation sulfuric acid such as peroxide one sulfuric acid, sulfuric acid, sulfurous acid, condensation sulfuric acid such as peroxo disulfate acid or pyrosulfuric acid etc.), boric acid (non-condensation boric acid such as orthoboric acid, metaboric acid; Condensation such as tetraboric acid, boron trioxide boric acid etc.), chromic acid, metaantimmonic acid, molybdic acid, wolframic acid etc.These oxygen acid can use separately or be used in combination more than two kinds.In these oxygen acid, preferred condensed phosphoric acid (tetra-sodium, Tripyrophosphoric acid, many metaphosphoric acids etc.), sulfuric acid, condensation sulfuric acid (pyrosulfuric acid etc.) etc.
As the basic nitrogen compound (nitrogenous compound) that constitutes oxysalt (C2), can enumerate and for example have and nitrogen-atoms bonded hydrogen atom (amino (NH 2) or imino-(hydrogen atom NH-), be active hydrogen atom) nitrogenous compound (chain or ring compound), for example, ammonia, carbamide compound (urea etc.), guanidine compound (Dyhard RU 100, guanidine, guanylurea etc.), aminotriazine compound [melamine, guanamines (guanamine), benzoguanamine and/or its condenses (melamine condensates such as melam, melem, mellon etc.) etc.] etc.These nitrogenous compounds can use separately or be used in combination more than two kinds.Among the above-mentioned nitrogenous compound, preferred ammonia, urea, guanidine, Dyhard RU 100, melamine, melamine condensates (melam, melem, mellon etc.).
Oxysalt (C2) also can be a polycondensate etc. so long as the reaction of oxygen acid and basic nitrogen compound (and sintering) resultant gets final product.Polycondensate as oxygen acid and above-mentioned nitrogenous compound, can enumerate the salt of above-mentioned oxygen acid and/or oxygen acid and above-mentioned nitrogenous compound and cyanamide derivative (have-N=C=N-or-N=C (the unitary compound of N＜=2 expressions, for example, polycondensate above-mentioned triaizine compounds, above-mentioned guanidine compound etc. such as melamine).This polycondensate can in most cases be the macromolecular compound with amido linkage by for example above-mentioned oxygen acid and above-mentioned cyanamide derivative being carried out sintering, condensation acquisition as required in the presence of wedding agent (urea and/or oxygen acid urea etc.).As this polycondensate, can use the condensed phosphoric acid acid amides (perhaps Tripyrophosphoric acid acid amides) etc. that except the above-mentioned phosphoric acid of enumerating, organic phosphoric acid, has used the phosphoric acid salt (ammonium polyphosphate, Ureaphil etc.) (particularly organic phosphoric acid and/or condensed phosphoric acid) of above-mentioned nitrogenous compound as above-mentioned oxygen acid usually.In addition, with regard to the Tripyrophosphoric acid acid amides, often use urea and/or Ureaphil as above-mentioned wedding agent.Above-mentioned polycondensate can use separately or be used in combination more than two kinds.In addition, about the Tripyrophosphoric acid acid amides, can open flat 7-138463 communique with reference to the spy.This Tripyrophosphoric acid acid amides can be used the manufacturings of putting down in writing in special public clear 51-39271 communique and the special public clear 53-2170 communique etc. such as method.The commercially available product of Tripyrophosphoric acid acid amides for example has " Si Misefu (ス ミ セ one Off) PM " [Sumitomo Chemical (strain)], " wearing grace (タ ィ ェ Application) S " [peaceful chemical industry (strain)] etc.
As preferred oxysalt, the salt that can enumerate for example Tripyrophosphoric acid and aminotriazine compound [for example, the Tripyrophosphoric acid melamine, the Tripyrophosphoric acid melam, the salt of Tripyrophosphoric acid such as Tripyrophosphoric acid melem and melamine and/or melamine condensates (particularly melamine or melamine condensates)], the salt of sulfuric acid and aminotriazine compound [for example, sulfuric acid (two) melamine, sulfuric acid (two) melam, sulfuric acid (two) melem, salt of sulfuric acid such as sulfuric acid melamine melam melem double salt and melamine and/or melamine condensates etc.], the salt of pyrosulfuric acid and aminotriazine compound [for example, pyrosulfuric acid (two) melamine, pyrosulfuric acid (two) melam, pyrosulfuric acid (two) melem, salt of pyrosulfuric acids such as pyrosulfuric acid melamine melam melem double salt and melamine and/or melamine condensates etc.], condensed phosphoric acid acid amides (perhaps Tripyrophosphoric acid acid amides) etc.
In the oxysalt, the ratio of oxygen acid and above-mentioned nitrogenous compound (mol ratio) for for example oxygen acid/nitrogenous compound=1/0.5-1/5 about, about preferred 1/0.7-1/4, more preferably about 1/0.8-1/3.
This oxysalt is even under the situation of using the halogen flame retardant, also can improve the resinous electricity characteristic.Therefore, above-mentioned oxysalt has the effect of electrical characteristic activator.
Organic-inorganic hydrochlorate (C) can use separately or make up more than two kinds.Particularly, organic-inorganic hydrochlorate (C) can comprise organic secondary phosphine acid salt (C1) and oxysalt (C2), so that further improve electrical characteristic.During with the combination of organic secondary phosphine acid salt (C1) and oxysalt (C2), the former/latter's (weight ratio)=99/1～1/99 about, be preferably about 95/5～5/95 more preferably about 90/10～10/90.
The ratio of organic-inorganic hydrochlorate (C) is with respect to matrix resin 100 weight parts, for example, for the 1-60 weight part (for example, the 2-50 weight part) about, is preferably about 3-40 weight part (for example, 4-35 weight part), more preferably about 3-30 weight part (for example, 8-25 weight part).In addition, the ratio of organic-inorganic hydrochlorate (C) is with respect to halogen flame retardant (B) 100 weight parts, for example, can be for about the 5-500 weight part, be preferably about the 10-350 weight part, more preferably about 20-300 weight part (for example, 30-280 weight part), particularly about the 40-270 weight part, usually can be for about the 20-500 weight part.
[electrical characteristic activator (D)]
Electrical characteristic activator (D) be used for by with the combination of (with the organic-inorganic hydrochlorate) of halogen flame retardant, improve the composition of matrix resin electrical characteristic high-levelly, comprise being selected from least a of ethylene series resin, fluorine resin and group 4 metal compounds.In addition, resinoid electrical characteristic activator (ethylene series resin, fluorine resin) is and the different resin of above-mentioned matrix resin (A).
(ethylene series resin)
As the ethylene series resin, for example can enumerate ethylene series monomer [alpha-olefins such as ethene, propylene, 1-butylene, 3-Methyl-1-pentene, 4-methyl isophthalic acid-butylene, 1-hexene, 1-octene (α-C particularly 2-10Alkene); Cyclic olefin { for example, cycloolefin (C such as cyclobutene, cyclopentenes, tetrahydrobenzene 3-10Cycloolefin etc.); C such as ring pentyne, cyclohexyne 3-10Cycloalkyne; Crosslinked ring type cycloolefin (two cyclic diolefines such as polycyclic olefin, Dicyclopentadiene (DCPD) such as norbornylene, four dicyclo laurylenes etc.); Perhaps their derivative (alkyl substituent, alkylidene group (ア Le キ リ デ Application) substituent, alkoxyl group substituent, acyl substituted thing, carboxyl substituted thing etc.) etc. } etc.] homopolymer or multipolymer, above-mentioned ethylene series monomer or polymkeric substance and co-polymerized monomer [vinyl monomer, for example, (methyl) vinylformic acid or its salt (metal-salt etc.), (methyl) acrylate acrylic monomers such as ((methyl) alkyl acrylate, (methyl) glycidyl acrylates etc.); Organic acid vinyl esters such as vinyl acetate are monomer; Fumaric acid, toxilic acid (acid anhydride), methylene-succinic acid (acid anhydride), pyrocitric acid (acid anhydride), nadic acid α such as (acid anhydrides), β-unsaturated dicarboxylic acid is a monomer; Vinyl cyanide base system monomers such as (methyl) vinyl cyanide etc.] multipolymer (random copolymers, segmented copolymer, graft copolymer etc.) etc.
As representative ethylene series resin, for example can enumerating, alpha-olefin is resin [for example, α-C such as polyethylene, polypropylene, propylene-ethylene copolymers 2-3The homopolymer of alkene or multipolymer; Metal-salt α-the C such as (ionomers etc.) of ethene-(methyl) acrylic copolymer, propylene-(methyl) acrylic copolymer, ethene-(methyl) acrylic copolymer 2-3Alkene-(methyl) acrylic copolymer, α-C 2-3Alkene-(methyl) acrylate copolymer (α-C such as ethylene-ethyl acrylate copolymer 2-3Alkene-(methyl) alkyl acrylate copolymer, ethene-(methyl) glycidyl acrylate multipolymer etc.) etc. α-C 2-3The multipolymer of alkene and co-polymerized monomer etc.], modified olefin be resin [for example, with ethylene series resin (homopolymer of alkene or multipolymer) (for example with sour composition, α, beta-unsaturated carboxylic acid ((methyl) vinylformic acid, toxilic acid, fumaric acid, methylene-succinic acid, pyrocitric acid, nadic acid etc.) and/or its acid anhydrides etc.) the sour modified olefin that forms of modification is resin etc.], annular ethylene series resin (for example, the homopolymer of cyclic olefin, α-C 2-10Alkene-cyclic olefin copolymer etc.) etc.The ethylene series resin can use separately or be used in combination more than two kinds.
Among these ethylene series resins, preferred α-C 2-3The homopolymer of alkene or multipolymer (polyethylene, polypropylene, ethylene/propene copolymer etc., particularly polypropylene, ethylene/propene copolymer), α-C 2-3Alkene-(methyl) acrylic copolymer, α-C 2-3Alkene-(methyl) acrylate copolymer [for example, α-C 2-3Alkene-(methyl) vinylformic acid C 1-4Alkyl ester copolymer (particularly ethylene-ethyl acrylate copolymer), α-C 2-3Alkene-(methyl) glycidyl acrylate multipolymer (particularly ethene-(methyl) glycidyl acrylate multipolymer) etc.], sour modified olefin is that resin is [for example, with α-C 2-3The ethylene series resin that the homopolymer of alkene or multipolymer form with sour composition modification sour modified polypropenes such as (particularly) maleic anhydride modified polypropylene etc.] etc.
The number-average molecular weight of ethylene series resin is not particularly limited, and can be for example 300-20 * 10 5About, be preferably 500-10 * 10 4About.
(fluorine resin)
As fluorine resin (fluorine resin), the homopolymer or the multipolymer that comprise fluorochemical monomer, for example, multipolymer of the homopolymer of fluorochemical monomer (tetrafluoroethylene, a chlorotrifluoroethylene, vinylidene, R 1216, perfluoroalkyl vinyl ether etc.) or multipolymer and above-mentioned fluorochemical monomer and other co-polymerized monomer (acrylic monomers such as ethylene series monomers such as ethene, propylene, (methyl) acrylate etc.) etc.As this fluorine resin, specifically, can enumerate homopolymer such as tetrafluoroethylene, polymonochlorotrifluoroethylene, polyvinylidene difluoride (PVDF); Multipolymers such as tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethene-one chlorotrifluoroethylcopolymer copolymer.As preferred fluorine resin, comprise and fluoridize α-C 2-3The homopolymer or the multipolymer of alkene (particularly tetrafluoroethylene).Fluorine resin can use separately or be used in combination more than two kinds.
In addition, above-mentioned fluorine resin can use with the particle shape, and median size can be preferably about 100-1000 μ m, more preferably about 100-700 μ m for for example about 10-5000 μ m.
(periodictable group 4 metal compounds)
The periodictable group 4 metal compounds comprises for example metallic compounds such as titanium, zirconium, hafnium, usually titanium or zirconium (particularly titanium) compound often.As representative periodictable group 4 metal compounds, [for example can enumerate titanium compound, the oxysalt (titanium sulfate etc.) of titanium oxide or oxyhydroxide titanium oxide such as (for example) titanium dioxide, halogenated titanium (titanium fluoride etc.), titanium, their hydrate (titanium oxide one or dihydrate etc.) etc.], with the corresponding zirconium compounds of these titanium compounds (zirconium white etc.) etc.As preferred periodictable group 4 metal compounds, comprise titanium oxide.These periodictable group 4 metal compounds can use separately or be used in combination more than two kinds.
The periodictable group 4 metal compounds can use with particle shape (perhaps powder shape), and the median size of powder granulous periodictable group 4 metal compounds can be preferably about 0.02-10 μ m, more preferably about 0.05-5 μ m for for example about 0.01-20 μ m.
Electrical characteristic activator (D) can use separately or be used in combination more than two kinds.With regard to preferred form, electrical characteristic activator (D) can comprise ethylene series resin and/or periodictable group 4 metal compounds (particularly ethylene series resin) at least.Especially when organic inorganic acid salt (C) when being organic secondary phosphine acid salt, electrical characteristic activator (D) in most cases comprises ethylene series resin and/or periodictable group 4 metal compounds at least.
The ratio of electrical characteristic activator (D) for example, for about 0.5-30 weight part (for example, the 1-25 weight part), is preferably about 2-20 weight part (for example, the 3-18 weight part), more preferably about the 3-15 weight part with respect to matrix resin 100 weight parts.In addition, the ratio of electrical characteristic activator (D) is with respect to halogen flame retardant 100 weight parts, for example, can be for about the 3-300 weight part, be preferably about the 5-200 weight part, more preferably about 10-150 weight part (for example, 15-130 weight part), usually can be for about 30-180 weight part (for example, 40-160 weight part, be preferably the 50-140 weight part).
[electrical characteristic are improved auxiliary agent (E)]
Resin combination of the present invention can also contain electrical characteristic and improve auxiliary agent.Improve auxiliary agent (E) as electrical characteristic, can enumerate do not belong in the mentioned component (B)-(D) any, as the compound that the auxiliary agent that is used to improve electrical characteristic uses, nitrogenous compound [aminotriazine compound (melamine is for example arranged; Guanamines; Melam, melamine condensates such as melem etc.), the salt of aminotriazine compound (organic acid of above-mentioned aminotriazine compound or inorganic acid salt, for example, cyanurates such as melamine cyanurate etc.) etc.], the mineral acid metallic compound { for example, the mineral acid metal-salt [for example, (moisture) metal silicate (talcum, kaolin, silica, diatomite, clay, wollastonite etc.), (moisture) borate metal salt (for example, (moisture) zinc borate, (moisture) lime borate, (moisture) aluminum borate etc.), (moisture) stannic acid metal-salt (for example, (moisture) zinc etc.), sulfuric acid metal-salt (calcium sulfate, sal epsom, barium sulfate etc.) etc.], metal oxide (magnesium oxide, ferric oxide, zinc oxide, aluminum oxide etc.), metal hydroxides (aluminium hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated alumina (boehmite) etc.), metallic sulfide (zinc sulphide, moly-sulfide, tungsten sulfide etc.), alkali earth metallic compound (for example, alkali earth metal salt (for example, lime carbonate, alkaline earth metals carbonates such as secondary calcium phosphate) etc.) etc. } etc.Wherein, improve auxiliary agent, comprise organic acid salt (particularly cyanurate), metal silicate, borate metal salt, alkali earth metallic compound of aminotriazine compound etc. as preferred electrical characteristic.These electrical characteristic are improved auxiliary agent and can be used separately or be used in combination more than two kinds.
Electrical characteristic are improved the ratio of auxiliary agent (E) with respect to matrix resin 100 weight parts, for example, can be preferably about the 0.5-20 weight part for about the 0-30 weight part, more preferably about 1-15 weight part (for example, 1.5-10 weight part).
[flame retardant (F)]
Resin combination of the present invention can also contain flame retardant (F) in addition.As flame retardant (F), can enumerate aromatics (phenol resin, aniline is resin, polyphenylene oxide is resin, aromatic epoxy resin (bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin etc.), phenoxy resin, polyphenylene sulfide is a resin, polycarbonate-based resin, poly-aryl ester resin, aromatic polyamide is a resin, aromatic polyester resin (for example, the aromatic polyester resin that can have liquid crystal liquid crystal property), the aromatic polyester acid amides is aromatic resins such as resin (for example, the aromatic polyester acid amides that can have a liquid crystal liquid crystal property is a resin)), P contained compound (organic phospho acid etc. do not belong to the P contained compound of above-mentioned organic-inorganic hydrochlorate (C) category), antimony containing compounds, molybdate compound (molybdenum oxide etc.), Tungstenic compound (Tungsten oxide 99.999 etc.), bismuth-containing compound (bismuth oxide etc.), sn-containing compound (stannic oxide etc.), iron containing compounds (ferric oxide etc.), copper-containing compound (cupric oxide etc.), silicon-containing compound [(gathering) organo-siloxane (polydimethylsiloxane, silicone resins such as PSI, silicone oil, polysilsesquioxane (polysilsesquioxane) etc.), (montmorillonite montmorillonites (smectite) such as (montmorillonite) is a layered silicate to layered silicate, Li type fluorine taincolite, Na type fluorine taincolite, Li type tetrasiuicic fluoromica, fluorine mica is synthesized in swellings such as Na type tetrasiuicic fluoromica, vermiculite, halloysite etc.) etc.], sulfocompound (organic sulfonic acid compound, the metal-salt of perfluoroalkane sulfonate, sulfamic acid compound or its salt etc.) etc.These flame retardants can use separately or be used in combination more than two kinds.
As P contained compound, [for example can enumerate (condensation) phosphoric acid ester, Resorcinol two (diphenyl phosphate), quinhydrones two (diphenyl phosphate), xenyl two (diphenyl phosphate), bisphenol-A (diphenyl phosphate), Resorcinol two (two-2,6-xylyl phosphoric acid ester), quinhydrones two (two-2,6-xylyl phosphoric acid ester), xenyl two (two-2,6-xylyl phosphoric acid ester), bisphenol-A (two-2,6-xylyl phosphoric acid ester), the tetramethylolmethane diphenyl phosphate, tetramethylolmethane two-2,6-xylyl phosphoric acid ester, 2,6,7-three oxygen-1-phosphorus two ring [2.2.2] octane-4-methyl alcohol-1-oxide compounds, and the phosphate compound of record in No. 4801625, No. 4154775 communiques of United States Patent (USP) and the United States Patent (USP) etc.], (condensation) phosphoric ester amides [for example, 1,4-piperazine two basic tetraphenylphosphonium acid esters, 1,4-piperazine two bases four-2,6-xylyl phosphoric acid ester, N, N,-two (inferior neo-pentyl dioxy phosphinyl) piperazine, and the spy opens flat 10-175985 communique, the spy opens the phosphoric ester amides (phosphamide etc.) of 2001-139823 communique and the record of Te Kai 2001-354689 communique etc.], phosphazene compound [for example, aryloxy phosphonitrile (phenoxy phosphazene, tolyl oxygen base phosphonitrile, xylyl oxygen base phosphonitrile, phenoxytoluene base oxygen base phosphonitrile, phenoxy group xylyl phosphonitrile etc.) ring-type and/or catenate phosphazene compound such as, their crosslinked phosphazene compound (for example, phenoxy phosphazene that is cross-linked to form with the bisphenols residue etc.), and WO99/19383 communique, the WO00/9518 communique, the phosphazene compound of putting down in writing in WO02/98886 communique and the WO04/24844 communique etc.], organic (Asia) phosphinic acid compounds [for example, Organophosphonate, organic (Asia) phosphonic acid metal salt (Li, Na, K, Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, metal-salts such as Mn), organic (Asia) phosphonic basic nitrogen compound salt (melamine salt, guanamines salt, benzocarbamidine amine salt and/or their condenses salt (melam, melem, melamine condensates such as mellon etc.) etc.), and inorganic phosphorous compound [for example, red phosphorus, (Asia) phosphate metal salt (phosphorous acid calcium, calcium propionate, aluminum phosphite, phosphoric acid aluminum phosphite double salt, borophosphoric acid etc.), hypophosphorous acid metal salt (calcium propionate, hypo-aluminum orthophosphate etc.) etc.] etc.Particularly preferred organic (Asia) phosphinic acid compounds is a P contained compound.
As the concrete example of organic (Asia) phosphinic acid compounds, can enumerate for example methyl-phosphorous acid, ethylphosphonic acid, the n-propyl phosphonic acids, the sec.-propyl phosphonic acids, the normal-butyl phosphonic acids, the isobutyl-phosphonic acids, octyl phosphonic acid, hydroxyalkyl phosphonic acids (hydroxymethyl phosphonic acid, the hydroxyethyl phosphonic acids, hydroxypropyl phosphonic acids etc.), alkoxyalkyl phosphonic acids (methoxymethyl phosphonic acids, ethoxyethyl group phosphonic acids etc.), carboxyalkyl phosphonic acids (carboxymethyl phosphonic acids, 2-propyloic phosphonic acids etc.), the methyl phosphonous acid, the ethyl phosphonous acid, the n-propyl phosphonous acid, the sec.-propyl phosphonous acid, the normal-butyl phosphonous acid, the isobutyl-phosphonous acid, octyl group phosphonous acid etc. can have substituent alkyl (Asia) phosphonic acids (C 1-16Alkyl (Asia) phosphonic acids etc.); Ethane-1,2-di 2 ethylhexyl phosphonic acid, hydroxyl ethane di 2 ethylhexyl phosphonic acid etc. can have substituent alkylidene group bisphosphate (C 2-6Alkylidene group di 2 ethylhexyl phosphonic acid etc.); 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid etc. can have substituent alkylidene di 2 ethylhexyl phosphonic acid (C 1-4Alkylidene di 2 ethylhexyl phosphonic acid etc.); Nitrilo (nitrilo) three (methyl-phosphorous acid) etc. can have nitrilo three (the alkyl phosphonic acid) [nitrilo three (C of substituting group (hydroxyl etc.) 1-4Alkyl phosphonic acid) etc.]; Oxygen connection (oxy) dimethyl phosphonic acids etc. can have oxygen di-(the alkyl phosphonic acid) [oxygen di-(C of substituting group (hydroxyl etc.) 1-4Alkyl phosphonic acid) etc. polymer phosphonic acids such as polyvinyl phosphonic acids, polyene propyl phosphonous acid]; [methyl-phosphorous acid mono-methyl, 2-propyloic phosphinic acid ethyl ester, carboxymethyl phosphonic acids triethyl, propyloic phosphonic acids triethyl etc. can have substituent alkyl (Asia) phosphonic list or multi-alkyl ester (C to these organic (Asia) phosphonic esters 1-16Alkyl (Asia) phosphonic list or two C 1-16Alkyl ester etc.); The pentaerythritol ester of methyl-phosphorous acid, the 2-of methyl-phosphorous acid ethyl-2-methylol-1, ammediol ester, poly-(the oxygen base ethyl) phosphonic acid ester etc. of hydroxyethyl can have the ester of substituent alkyl (Asia) phosphonic acids and polyvalent alcohol etc.]; These organic (Asia) phosphonic salt [methyl (Asia) phosphonic acids Ca salt, ethyl (Asia) phosphonic acids Ca salt, n-propyl (Asia) phosphonic acids Ca salt, sec.-propyl (Asia) phosphonic acids Ca salt, normal-butyl (Asia) phosphonic acids Ca salt, isobutyl-(Asia) phosphonic acids Ca salt, octyl group (Asia) phosphonic acids Ca salt, methyl (Asia) phosphonic acids Mg salt, ethyl (Asia) phosphonic acids Mg salt, n-propyl (Asia) phosphonic acids Mg salt, sec.-propyl (Asia) phosphonic acids Mg salt, normal-butyl (Asia) phosphonic acids Mg salt, isobutyl-(Asia) phosphonic acids Mg salt, octyl group (Asia) phosphonic acids Mg salt, 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid Ca salt, nitrilo three (methyl-phosphorous acid) Ca salt, alkali earth metal salts such as nitrilo three (methyl-phosphorous acid) Mg salt; Methyl (Asia) phosphonic acids Ti salt, ethyl (Asia) phosphonic acids Ti salt, n-propyl (Asia) phosphonic acids Ti salt, sec.-propyl (Asia) phosphonic acids Ti salt, normal-butyl (Asia) phosphonic acids Ti salt, isobutyl-(Asia) phosphonic acids Ti salt, octyl group (Asia) phosphonic acids Ti salt, 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid Ti salt, nitrilo three (methyl-phosphorous acid) Ti salt and the titanium salts (also comprise titanyl salt) such as titanyl salt corresponding with these Ti salt; Methyl (Asia) phosphonic acids Al salt, ethyl (Asia) phosphonic acids Al salt, n-propyl (Asia) phosphonic acids Al salt, sec.-propyl (Asia) phosphonic acids Al salt, normal-butyl (Asia) phosphonic acids Al salt, isobutyl-(Asia) phosphonic acids Al salt, octyl group (Asia) phosphonic acids Al salt, ethane-1,2-di 2 ethylhexyl phosphonic acid Al salt, carboxymethyl phosphonic acids Al salt, 2-propyloic phosphonic acids Al salt, the Al salt of methyl-phosphorous acid mono-methyl, 1-hydroxy ethylidene-1, aluminium salt such as 1-di 2 ethylhexyl phosphonic acid Al salt, nitrilo three (methyl-phosphorous acid) Al salt; Methyl (Asia) phosphonic acids Zn salt, ethyl (Asia) phosphonic acids Zn salt, n-propyl (Asia) phosphonic acids Zn salt, sec.-propyl (Asia) phosphonic acids Zn salt, normal-butyl (Asia) phosphonic acids Zn salt, isobutyl-(Asia) phosphonic acids Zn salt, octyl group (Asia) phosphonic acids Zn salt, 1-hydroxy ethylidene-1, organic (Asia) phosphonic acid metal salts such as zinc salt such as 1-di 2 ethylhexyl phosphonic acid Zn salt, nitrilo three (methyl-phosphorous acid) Zn salt; Methyl (Asia) phosphonic acids melamine salt, ethyl (Asia) phosphonic acids melamine salt, n-propyl (Asia) phosphonic acids melamine salt, sec.-propyl (Asia) phosphonic acids melamine salt, normal-butyl (Asia) phosphonic acids melamine salt, isobutyl-(Asia) phosphonic acids melamine salt, octyl group (Asia) phosphonic acids melamine salt, with the corresponding melam salt of these melamine salts, melem salt, mellon salt, melamine melam melem double salt, melamine melam melem mellon double salt, 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid Dan Zhisi melamine salt, salt (organic (Asia) phosphonic acids aminotriazine salt) of nitrilo three (methyl-phosphorous acid) Dan Zhiliu melamine salt etc. and aminotriazine compound (melamine or its condenses etc.) etc.] etc.Wherein, especially preferably organic (Asia) phosphonate.
In addition, as organic (Asia) phosphinic acid compounds, for example also can enumerating, the spy opens clear 48-57988 communique, the spy opens clear 55-5979 communique, the spy opens clear 56-84750 communique, the spy opens clear 63-22866 communique, Te Kaiping 1-226891 communique, Te Kaiping 2-180875 communique, Te Kaiping 4-234893 communique, Te Kaiping 7-224078 communique, Te Kaiping 7-247112 communique, Te Kaiping 8-59679 communique, Te Kaiping 8-245659 communique, Te Kaiping 9-272759 communique, the spy opens the 2000-63843 communique, the spy opens the 2001-2688 communique, the spy opens the 2001-64438 communique, the spy opens the 2001-64521 communique, the spy opens the 2001-98161 communique, the spy opens the 2001-98273 communique, the spy opens the 2001-106919 communique, the WO01/11108 communique, the WO01/57134 communique, No. 3789091 communiques of United States Patent (USP), No. 3849368 communiques of United States Patent (USP), the compound of putting down in writing in No. 4390477 communiques of United States Patent (USP).
These organic (Asia) phosphate cpds or its salt can use separately or be used in combination more than two kinds.
As preferred flame retardant (F), comprise and be selected from least a of (condensation) phosphoric acid ester, (condensation) phosphoric ester amides, (crosslinked) aryloxy phosphonitrile, (Asia) phosphate metal salt, hypophosphorous acid metal salt, organic (Asia) phosphonic acid ester, organic (Asia) phosphonic acid metal salt, organic (Asia) phosphonic acids aminotriazine salt, as particularly preferred flame retardant (F), comprise being selected from least a of alkyl (Asia) phosphonic acid metal salt, (Asia) phosphate metal salt and hypophosphorous acid metal salt.
As antimony containing compounds, can enumerate for example weisspiessglanz [ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb 2O 3Deng), antimony pentaoxide (xNa 2OSb 2O 5YH 2O (x=0-1, y=0-4) etc.) etc.], stibnate [metaantimmonic acid metal-salt (for example, alkali earth metal salts such as an alkali metal salt, metaantimmonic acid magnesium such as sodium antimonate etc.), ammonium antimonate etc.] etc.These antimony containing compounds can use separately or be used in combination more than two kinds.In the above-mentioned antimony containing compounds, an alkali metal salt of preferred weisspiessglanz and metaantimmonic acid etc.
In addition, antimony containing compounds can carry out using after the surface treatment with surface treatment agents such as epoxy compounds, silane compound, isocyanate compound and/or titanate compounds as required.
In addition, the median size of antimony containing compounds can be for example about 0.02-5 μ m, is preferably about 0.1-3 μ m.
In these flame retardants, preferred especially the use is selected from least a of aromatics, P contained compound and antimony containing compounds.Especially when using the oxysalt (C2) of basic nitrogen compound,, then can further improve flame retardant resistance if use antimony containing compounds as organic-inorganic hydrochlorate (C).In addition, resin combination of the present invention even do not contain such flame retardant, also can be guaranteed flame retardant resistance and excellent electrical characteristic with high level owing to made up mentioned component (B)-(D) simultaneously.
The ratio of flame retardant (F) is with respect to matrix resin (A) 100 weight parts, for example, can for the 0-30 weight part (for example, 0.05-20 weight part), be preferably about 0.1-20 weight part (for example, the 0.3-10 weight part), more preferably about the 0.5-5 weight part.
(other additive)
Flame retardant resin composition of the present invention can also contain other additives, for example, other fire retardant (nitrogen system, phosphorus flame retardant etc.), weighting agent, stablizer (UV light absorber, weather (light) stablizer, heat-resisting stabilizing agent, processing stabilizers, phosphorus are stablizer, reactive stablizer etc.), static inhibitor, antiseize paste, releasing agent, the agent of crystallization nuclear, softening agent, tinting material (dyestuff, pigment etc.), lubricant, Antidrip agent (dripping inhibitor) etc.These other additives can use separately or be used in combination more than two kinds.
Among these additives, above-mentioned resin combination preferably contains weighting agent, heat-resisting stabilizing agent, processing stabilizers etc.
[weighting agent]
As weighting agent, can enumerate weighting agents such as habitual fibrous, tabular, powder shape.As fibrous filler, can enumerate inorganic fibre (glass fibre, carbon fiber, boron fibre, potassium titanate fiber (must be brilliant) etc.), organic fibre (nylon etc.) etc.As tabular weighting agent, can enumerate sheet glass, mica, graphite, various tinsels etc.As powder shape weighting agent, can enumerate metal oxide (zinc oxide, aluminum oxide etc.), vitriol (calcium sulfate, sal epsom etc.), carbonate (lime carbonate etc.), category of glass (milled fibre, granulated glass sphere, glass sphere etc.), sulfide (molybdenumdisulphide, tungsten disulfide etc.), carbide (fluorographite, carborundum etc.), gac, boron nitride etc.As preferred weighting agent, comprise inorganic fibre (particularly glass fibre).Weighting agent can use separately or be used in combination more than two kinds.
The usage quantity of weighting agent for example, can be preferably about 1-80 weight part (for example, the 5-75 weight part) for about the 0-100 weight part, more preferably about 10-70 weight part (for example, 20-65 weight part) with respect to matrix resin 100 weight parts.
(heat-resisting stabilizing agent)
As heat-resisting stabilizing agent, can enumerate the hindered phenol based compound (hindered phenol be antioxidant [for example, 2,6-di-t-butyl-p-cresols, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), 4,4 '-thiobis (the 6-tertiary butyl-m-cresols), triglycol be two-(3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester), tetramethylolmethane four side chain C such as (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic esters) 3-6Induced by alkyl hydroxybenzene etc.], phosphorus series compound (phosphorous antioxidant) [phosphorous acid salt (two (C such as two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane diphosphorous acid salts 1-9Alkyl-aryl) tetramethylolmethane diphosphorous acid salts etc.), phosphonous acid salt (four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates etc.) etc.], chalcogenide compound (sulphur is antioxidant) [dilauryl thiodipropionate etc.], amine be antioxidant (amine is antioxidant) [for example, naphthylamines, phenyl naphthyl amines, 1, the 4-phenylenediamine, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) hindered amines such as sebate etc.], quinhydrones based compound (quinhydrones is an antioxidant) [for example, 2,5 di tert butylhydroquinone etc.], quinoline based compound (quinoline is an antioxidant) [for example, 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihydroquinoline etc.] etc. habitual antioxidant; Alkali or alkali earth metallic compound [for example, phosphoric acid hydrogen alkali or alkali earth metal salt (for example, primary magnesium phosphate, monocalcium phosphate, calcium monohydrogenphosphate (secondary calcium phosphate, CaHPO 4), phosphoric acid hydrogen (perhaps hydrogen or dihydro) alkali earth metal salt such as barium dihydrogen phosphate, phosphoric acid one hydrogen barium etc.)]; Inorganic metal or inorganic be stablizer (hydrotalcite, zeolite etc.) etc.
These heat-resisting stabilizing agents can use separately or be used in combination more than two kinds.
Particularly, can be used as heat-resisting stabilizing agent to the hindered phenol based compound at least.For example, heat-resisting stabilizing agent can be made of separately the hindered phenol based compound, also can comprise hindered phenol based compound and other heat-resisting stabilizing agent (for example, being selected from least a of phosphorus series compound, alkali or alkali earth metallic compound and hydrotalcite).
The ratio of heat-resisting stabilizing agent for example, can be about 0-15 weight part (for example, the 0.001-10 weight part) with respect to matrix resin 100 weight parts, is preferably about the 0.01-5 weight part, more preferably about the 0.05-2 weight part.In addition, when the heat-resisting stabilizing agent with hindered phenol based compound and other is used in combination, the ratio of the heat-resisting stabilizing agent of hindered phenol based compound and other is for the former/latter's (weight ratio)=99/1-1/99 about, be preferably about 98/2-10/90, more preferably about 95/5-20/80.
(processing stabilizers)
As processing stabilizers, can enumerate for example longer chain fatty acid (for example, C such as capric acid, lauric acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, stearic acid, eicosanoic acid, docosoic, montanic acid, oleic acid, linolic acid, linolenic acid, eicosatetraenoic acid, sinapinic acid, sebacic acid, dodecanedioic acid, tetradecane diacid 10-34Saturated or unsaturated fatty acids), long chain fatty acids amides (for example, capric acid acidamide, lauric amide, the tetradecanoic acid acid amides, palmitic amide, stearic amide, eicosanoic acid acid amides behenamide, amine hydroxybenzene, stearylstearic amide, the stearyl amine hydroxybenzene, quadrol-distearyl acid acid amides (ethylenebisstearamide), hexamethylene-diamine-distearyl acid acid amides, quadrol-two amine hydroxybenzene, quadrol-two sinapinic acid acid amides, quadrol-(stearic amide) amine hydroxybenzene etc.), long chain fatty acid ester (for example, Unister E 275, Zerol, the TriMethylolPropane(TMP) monostearate, pentaerythritol stearate, sorbitan monostearate, polyalkylene glycol monostearates such as (polyoxyethylene glycol etc.), with these corresponding cetylates, laurate docosoic ester, montanate, the above-mentioned long chain fatty acid ester of enumerating such as oleic acid ester), polyalkylene glycol (polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene-polyoxypropylene copolymer etc.), silicone compound, wax class [for example, native paraffin, synthetic paraffin, microcrystalline wax, polyolefin wax (polyethylene wax, Poly Propylene Wax etc.) etc.] etc.Processing stabilizers can use separately or be used in combination more than two kinds.
The ratio of processing stabilizers for example, can be preferably about the 0.1-10 weight part for about the 0-20 weight part, more preferably about the 0.5-5 weight part with respect to matrix resin 100 weight parts.
(reactive stablizer)
As reactive stablizer, for example can enumerate epoxy and be reactive stablizer [glycidyl ether compound (bisphenol A diglycidyl ether, phenyl glycidyl ether etc.), epihydric alcohol ester compound (phenylformic acid glycidyl ester, tertiary carbonic acid glycidyl ester etc.), contain the acrylic acid polymer of epoxy group(ing) etc.], trimethylene oxide and be reactive stablizer [1, two { [3-ethyl-3-trimethylene oxide ylmethoxy] methyl } benzene, two [1-ethyl (3-oxetanyl) methyl] ethers of 4-etc.],
Figure 2006800249249_0
The azoles quinoline be reactive stablizer [1, the two (2-of 3-phenylene
Figure 2006800249249_1
The azoles quinoline), 1, the two (2-of 4-phenylene The azoles quinoline) etc.], carbodiimide is a reactive stablizer [poly-aryl carbodiimide, polyoxyethylene alkyl aryl base carbodiimide, poly-polycarbodiimides such as [two (alkyl or cycloalkyl aryl) carbodiimide of alkylidene group]] etc.These reactive stablizers can use separately or be used in combination more than two kinds.
The ratio of reactive stablizer for example, can be preferably about the 0.05-8 weight part for about the 0-20 weight part, more preferably about the 0.1-5 weight part with respect to matrix resin 100 weight parts.
Flame retardant resin composition of the present invention also can be powder body mixture or molten mixture, can adopt conventional process that matrix resin (A), halogen flame retardant (B), organic-inorganic hydrochlorate (C), electrical characteristic activator (D) and other the composition (electrical characteristic are improved auxiliary agent, flame retardant, additive etc.) that adds are as required mixed and prepare.In addition, the present invention also comprises the molding (for example, the resin combination (molding) by above-mentioned molten mixture is solidified to form) that is formed by above-mentioned flame retardant resin composition.
Flame retardant resin composition and molding can adopt shapings such as following method, and for example (1) mixes each composition, carry out mixing, extruding by single shaft or double-shafted extruder, the method for modulation small-particle postforming; (2) after different small-particles (masterbatch) is formed in elder generation's modulation, mix the method for (dilution) this small-particle for the molding that obtains the regulation composition in shaping with specified amount; (3) method that directly putting into more than a kind or 2 kinds in each composition is formed in the forming mill etc.In addition, can all or part of being pre-mixed with the composition beyond the matrix resin after, mix with matrix resin again, also can not be pre-mixed the composition beyond the matrix resin, but directly mix with matrix resin.In addition, the interpolation order of the composition beyond the matrix resin also is not particularly limited, can in matrix resin, add all matrix resins composition in addition once, after also can in matrix resin, adding composition beyond the part matrix resin and mixing, add remaining composition (can be divided into several times as required) again.
In addition, molding can prepare according to flame retardant resin composition being carried out melting mixing with customary way and form by customary ways such as extrusion molding, injection forming, compression moldings.
Its plasticity of flame retardant resin composition of the present invention (and molding) is not affected, and, although contain the halogen flame retardant, can have flame retardant resistance and electrical characteristic concurrently with high level really.For example, when flame retardant resin composition of the present invention (and molding) is measured with the test film of thickness 1.6mm, be more than the V-2 based on the flame retardant resistance of UL94 flammability test, be preferably more than the V-1, more preferably be more than the V-0.In addition, in the flame retardant resin composition of the present invention (and molding), comparison galvanic corrosion index (CTI) based on IEC112 (UL746A) is that 400V is above (for example, about 400-1000V), it is above (for example to be preferably 450V, about 450-900V), more preferably more than the 500V (for example, about 500-850V).Particularly, in resin combination of the present invention, owing to made up halogen flame retardant, specific organic-inorganic hydrochlorate and specific electrical characteristic activator, so can significantly improve electrical characteristic with high level really, for example, can make above-mentioned relatively galvanic corrosion index (CTI) reach 600V above (for example, about 600-850V), be preferably 650V above (for example, about 650-750V).
In addition, when resin combination of the present invention (and molding) is measured with the test film of thickness 0.8mm, flame retardant resistance based on the UL94 flammability test is more than the V-1, to be preferably more than the V-0, and, comparison galvanic corrosion index (CTI) based on IEC112 (UL746A) is that 350V is above (for example, about 350-1000V), be preferably 400V above (for example, about 400-900V), more preferably more than the 450V (for example, about 450-850V).
Industrial utilizability
The flame retardant resistance of flame retardant resin composition of the present invention (and molding) and electrical characteristic excellence, go for various uses, for example, electrical and electronic parts, office automation (OA) machine part, household electrical appliances machine part, trolley part, machine structural parts etc.
Embodiment
Below, according to embodiment the present invention is described in more details, but the present invention is not limited to these embodiment.
In addition, according to following test, the flame retardant resistance and the electrical characteristic (relatively galvanic corrosion index) of resin combination have been estimated.
[flammability test]
According to UL94, estimate incendivity with the test film of thickness 1.6mm or 0.8mm.
[relatively galvanic corrosion index (CTI)]
According to IEC112 (UL746A), use relatively galvanic corrosion index (CTI) [unit: V] of ammonium chloride 0.1% aqueous solution evaluation.
In addition, the matrix resin that uses in embodiment and comparative example (A), halogen flame retardant (B), organic-inorganic hydrochlorate (C), electrical characteristic activator (D), electrical characteristic are improved auxiliary agent (E), flame retardant (F), weighting agent (G), heat-resisting stabilizing agent (H), processing stabilizers (I), (J) is as follows for reactive stablizer.
1. matrix resin (A)
(A-1): polybutylene terephthalate (intrinsic viscosity=0.85)
(A-2): Poly(Trimethylene Terephthalate) (intrinsic viscosity=0.85)
(A-3): polyethylene terephthalate (intrinsic viscosity=0.75)
(A-4): polyamide 66
(A-5): 12.5 moles of % isophthalate modified polybutylene terephthalates (intrinsic viscosity=0.80)
2. halogen flame retardant (B)
(B-1) poly-(vinylformic acid pentabromo-benzyl ester) [FR1025, Bu Mafasite company (Block ロ system ケ system Off ア-ィ-ス ト society) system]
(B-2) brominated Polystyrene [sending Luo Chi (パ ィ ロ チ ェ ッ Network) 68PB, Fu Luo chemical company (Off ェ ロ ケ ミ カ Le ズ society) system]
(B-3) brominated Polystyrene [SYTEX HP-7010P, Ai Erbaimaer company (ア Le ベ マ one Le society) system]
(B-4) ethylenebis tetrabromo phthalimide [SYTEX BT-93, Ai Erbaimaer company (ア Le ベ マ one Le society) system].
(B-5) brominated bisphenol a type epoxy resin [SRT5000, this pharmaceutical industries of slope (strain) system]
(B-6) brominated bisphenol A type polycarbonate resin [(the erg moral of boiling (Off ア ィ ャ ガ one De) FG-7500, Supreme Being people change into (strain) system].
3. organic-inorganic hydrochlorate (C)
Organic secondary phosphine acid salt (C1)
(C1-1): methylethyl phospho acid aluminium salt
(C1-2): methylethyl phospho acid calcium salt
(C1-3): dimethyl phospho acid aluminium salt
(C1-4): the aluminium salt of 1-hydroxyl phospholane 1-oxide compound
(C1-5): dimethyl phospho acid melamine salt
(C1-6): the aluminium salt of (2-propyloic) methyl phospho acid
(C1-7): diethyl phospho acid aluminium salt
Oxysalt (C2)
(C2-1): Tripyrophosphoric acid melamine [Melapur200, DSM society system]
(C2-2): condensed phosphoric acid acid amides [wearing grace (タ ィ ェ Application) S, peaceful chemical industry (strain) system]
(C2-3): sulfuric acid two melamines [Ah does (ア ピ ノ Application)-901, (strain) three and chemistry system]
Acid tetra-sodium metal-salt (C3: in comparative example, use)
(C3-1): acidic sodium pyrophosphate.
4. electrical characteristic activator (D)
Ethylene series resin (D1)
(D1-1): ethylene/ethyl acrylate multipolymer [NUC-6570, Japanese You Nika (ュ ニ カ-) (strain) system]
(D1-2): ethylene/methacrylic acid glycidyl ester copolymer [this spy of Bender process (ボ Application De Off ア-ス ト) E, Sumitomo Chemical (strain) system]
(D1-3): maleic anhydride modified polyolefine [many husbands horse (タ Off マ-) MP, Mitsui Chemicals (strain) system]
(D1-4): polypropylene [Nuo Bulian (ノ-Block レ Application) J, Sumitomo Chemical (strain) system]
(D1-5): ethylene/propene copolymer [J707ZB, Mitsui Chemicals (strain) system]
Fluorine resin (D2)
(D2-1): tetrafluoroethylene [teflon 6J, Mitsui Du Pont fluorine chemistry (strain) system]
The compound (D3) that contains the periodictable group-4 metal
(D3-1): titanium oxide [TITONE SR-1, Sakai chemical industry (strain) system]
5. electrical characteristic are improved auxiliary agent (E)
(E-1): talcum
(E-2): contain hydrate zinc borate [Firebrake ZB, Bora (ボ ラ ッ Network ス) Japan (strain) system]
(E-3): melamine cyanurate
(E-4): lime carbonate
6. flame retardant (F)
Aromatics (F1)
(F1-1): bisphenol A type epoxy resin [meaning can be special (1004K of ェ ピ コ-ト), your (シ ェ Le) epoxy (strain) system of oiling generation]
(F1-2): phenolic resin varnish type epoxy resin [EPPN-201, Japanese chemical drug (strain) system]
(F1-3): polycarbonate resin [roc comes special (パ Application ラ ィ ト) L1225, and Supreme Being people changes into (strain) system]
P contained compound (F2)
(F2-1): Resorcinol two (two-2,6-xylyl phosphoric acid ester) [PX200, big eight chemical industry (strain) system]
(F2-2): phenoxytoluene base oxygen base phosphonitrile [KEMIDANT302S, triumphant rice pul (ミ プ ロ) change into (strain) system]
(F2-3): ring-type phenoxy phosphazene (3-4 aggressiveness mixture)
(F2-4): 1,4-piperazine two basic tetraphenylphosphonium acid esters
(F2-5): ethylphosphonic acid aluminium salt
(F2-6): ethyl phosphonous acid aluminium salt
(F2-7): aluminum phosphite salt
(F2-8): phosphorous acid calcium
Antimony containing compounds (F3)
(F3-1): ANTIMONY TRIOXIDE SB 203 99.8 PCT
(F3-2): sodium antimonate
7. weighting agent (G)
(G-1): glass fibre (diameter 13 μ m, the chopped fibres of long 3mm)
(G-2): glass fibre (diameter 10 μ m, the chopped fibres of long 3mm)
8. heat-resisting stabilizing agent (H)
Hindered phenol is heat-resisting stabilizing agent (H1)
(H1-1): tetramethylolmethane four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester]
Heat-resisting stabilizing agent (H2)
(H2-1): two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites
(H2-2): four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene phosphinate
(H2-3): monocalcium phosphate
(H2-4): hydrotalcite [DHT-4A, consonance chemical industry (strain) system].
9. processing stabilizers (I)
(I-1): polyethylene wax [three waxes (サ Application ヮ ッ Network ス), Sanyo changes into industry (strain) system]
(I-2): montanate [LUZA WAX, Japan Petter sieve (ペ ト ロ ラ ィ ト) (strain) system]
10. reactive stablizer (J)
(J-1): bisphenol A diglycidyl ether [meaning can be special (ェ ピ コ-ト) 828, your (シ ェ Le) epoxy (strain) system of oiling generation]
(J-2): polycarbodiimide [Ka Erjite (カ Le ボ ジ ラ ィ ト) HMV-8CA, (strain) system of twisting flax fibers and weaving clearly day].
(embodiment 1-32, comparative example 1-12)
In matrix resin (A), halogen flame retardant (B), organic-inorganic hydrochlorate (C), electrical characteristic activator (D), electrical characteristic are improved auxiliary agent (E), flame retardant (F), weighting agent (G), heat-resisting stabilizing agent (H), processing stabilizers (I) according to the mixed shown in the table 1-4, double-shafted extruder with the 30mm diameter carries out melting mixing, resin composition modulation then.Use this resin combination to be configured as the test film of regulation, measure flame retardant resistance (1.6mm) and electrical characteristic by injection machine.In addition, in comparative example 10, with acidic sodium pyrophosphate when the extruding of the resin combination modulation and when shaping cause resin expanded.The results are shown in table 1-4.
Table 1
Figure G05832469220070328D000101
Table 2
Figure G05832469220070328D000102
Table 3
Comparative example
1 2 3 4 5 6 7 8 9 10
Matrix resin A weight part A-1100 A-1100 A-1100 A-1100 A-1100 A-1100 A-1100 A-1100 A-1100 A-1100
Halogen flame retardant B weight part B-112 B-112 B-115 B-112 B-112 B-112 - - B-112 B-115
Organic-inorganic hydrochlorate c weight part C1-110 C1-120 C2-120 C2-110 C2-310 - C1-120 - C1-1?C2-110 10 C3-120
Electrical characteristic activator D weight part - - - - - - - 01-110 - D1-110
Electrical characteristic are improved auxiliary agent E weight part - - - - - - - - - -
Flame retardant F weight part - - - F3-110 F3-110 - - - - F2-110
Weighting agent G weight part G-160 G-160 G-160 G-160 G-160 G-160 G-160 G-160 G-160 G-160
Heat-resisting stabilizing agent H weight part H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5
- - - - - - - - - -
Processing stabilizers I weight part I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 -
The UL94 combustion test HB V-0 V-1 V-0 V-0 HB HB HB V-0 V-1
CTI(V) 400 450 450 400 300 300 550 ＞650 450 300
Table 4
Embodiment Comparative example
30 31 32 11 12
Matrix resin A weight part A-4100 A-4100 A-4100 A-4100 A-4100
Halogen flame retardant B weight part B-115 B-220 B-210 B-115 B-220
Organic-inorganic hydrochlorate C weight part C4-120 C2-110 C1-1?C2-110?10 C1-120 C2-110
Electrical characteristic activator D weight part D1-110 D1-110 D1-110 - -
Electrical characteristic are improved auxiliary agent E weight part - - - - -
Flame retardant F weight part ?- F3-110 - - F3-110
Weighting agent G weight part G-160 G-160 G-160 G-160 G-160
Heat-resisting stabilizing agent H weight part H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5
- H2-40.5 H2-40.5 - -
Processing stabilizers I weight part I-12.0 I-12.0 I-12.0 I-12.0 I-12.0
The UL94 combustion test V-0 V-0 V-0 V-0 V-0
CTI(V) ＞650 ＞650 ＞650 400 350
(embodiment 33-48)
In matrix resin (A), halogen flame retardant (B), organic-inorganic hydrochlorate (C), electrical characteristic activator (D), electrical characteristic are improved auxiliary agent (E), flame retardant (F), weighting agent (G), heat-resisting stabilizing agent (H), processing stabilizers (I), reactive stablizer (J) mixes according to the ratio shown in the table 5 (weight part), carry out mixing extruding with extrusion machine then, thus the resin combination of particle modulator shape.The particle that use obtains is made the test molding by injection machine, estimates incendivity (1.6mm) and electric erosion resistance (relatively galvanic corrosion index).The results are shown in table 5.
Table 5
Figure G05832469220070328D000103
(embodiment 49-58, comparative example 13-14)
In matrix resin (A), halogen flame retardant (B), organic-inorganic hydrochlorate (C), electrical characteristic activator (D), electrical characteristic are improved auxiliary agent (E), flame retardant (F), weighting agent (G), heat-resisting stabilizing agent (H), processing stabilizers (I) mixes according to the ratio shown in the table 6 (weight part), carry out mixing extruding with extrusion machine then, thus the resin combination of particle modulator shape.The particle that use obtains is made the test molding by injection forming, estimates incendivity (0.8mm) and electric erosion resistance (relatively galvanic corrosion index).The results are shown in table 6.
Table 6
Embodiment Comparative example
49 50 51 52 53 54 55 56 57 58 13 14
Matrix resin A weight part A-1100 A-1100 A-1100 A-2100 A-5100 A-1100 A-1100 A-1100 A-1100 A-1100 A-1100 A-1100
Halogen flame retardant B weight part B-512 B-612 B-512 B-512 B-512 B-512 B-612 B-512 B-512 B-512 B-512 B-612
Organic-inorganic hydrochlorate C weight part C1-120 C1-120 C1-720 C1-720 C1-720 C1-720 C1-720 C1-720 C1-720 C1-7 C2-120?5 C1-120 C1-120
Electrical characteristic activator D weight part D1-18 D1-18 D1-18 D1-28 D1-18 D1-18 D1-28 D1-16 D1-16 D1-15 - -
Electrical characteristic are improved auxiliary agent E weight part - - - - - - - E-15.0 E-35.0 - - -
Flame retardant F weight part - - - - - F2-81.0 - - - - - -
Weighting agent G weight part G-160 G-160 G-160 G-160 G-160 G-160 G-160 G-160 G-160 G-160 G-160 G-160
Heat-resisting stabilizing agent H weight part H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5 H1-10.5
- H2-10.3 - - - - H2-20.3 H2-10.3 H2-10.3 - - H2-10.3
Processing stabilizers I weight part I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0 I-12.0
The UL94 combustion test V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
CTI(V) 400 400 400 400 400 400 400 450 450 450 300 300

Claims (27)

1. flame retardant resin composition, wherein comprise matrix resin (A), halogen flame retardant (B), be selected from least a organic-inorganic hydrochlorate (C) and the electrical characteristic activator (D) of the oxysalt (C2) of organic secondary phosphine acid salt (C1) and basic nitrogen compound, and described flame retardant resin composition is the composition that electrical characteristic are improved, and described electrical characteristic activator (D) comprises the ethylene series resin.
2. resin combination according to claim 1, wherein matrix resin (A) comprises that to be selected from polyester based resin, polyamide-based resin, polycarbonate-based resin, polyphenylene oxide be that resin, polyphenylene sulfide are at least a thermoplastic resin of resin, phenylethylene resin series and vinyl resin.
3. resin combination according to claim 1, wherein matrix resin (A) comprises and has the terephthalic acid of being selected from 1,4-hexanaphthene two methylene esters, terephthalic acid C 2-4Alkylene ester and naphthalic acid C 2-4At least a unitary homopolymerization polyester or the copolyester of alkylene ester.
4. resin combination according to claim 1, wherein matrix resin (A) comprise be selected from polybutylene terephthalate, with the mutual-phenenyl two acid bromide two alcohol ester unit be principal constituent copolyester, Poly(Trimethylene Terephthalate), be the copolyester, polyethylene terephthalate of principal constituent, be at least a material of the copolyester of principal constituent with the propylene glycol ester terephthalate unit with the ethylene glycol terephthalate unit.
5. resin combination according to claim 1, wherein halogen flame retardant (B) is at least a fire retardant that contains bromine atoms that is selected from acrylic resin, the phenylethylene resin series that contains bromine that contains bromine, the polycarbonate-based resin that contains bromine, the epoxy compounds that contains bromine, bromination polyaryl ether compound, brominated aromatic imide compound, bromination bi-aromatic compounds and bromination three (aryloxy) triaizine compounds.
6. resin combination according to claim 1, wherein halogen flame retardant (B) is that to be selected from poly-(methyl) benzyl acrylate of bromination be that resin, brominated styrene are at least a material of the two bromination phthalimides of resin, brominated bisphenol type polycarbonate resin, brominated bisphenol type Resins, epoxy, brominated bisphenol type phenoxy resin and alkylidene group.
7. resin combination according to claim 1, wherein organic secondary phosphine acid salt (C1) is not replace or have substituent aliphatics phosphinates and/or do not replace or have a substituent alicyclic phosphinates.
8. resin combination according to claim 1, wherein organic secondary phosphine acid salt (C1) is to be selected from not replace or have a substituent dialkyl phosphinic acid, do not replace or have substituent bicyclic alkyl phospho acid, do not replace or have substituent alkylidene group phospho acid, do not replace or have substituent alkenylene phospho acid, do not replace or have substituent (two) and encircle the alkylidene group phospho acid, and do not replace or have organic phospho acid of substituent alkane two (alkyl phosphinic acids) and be selected from periodictable the 1st family's metal, the periodictable group II metal, the periodictable group-4 metal, periodictable the 7th family's metal, periodictable the 8th family's metal, periodictable the 10th family's metal, periodictable the 11st family's metal, periodictable the 12nd family's metal, metal belonging to group 13 of periodic table, periodictable the 14th family's metal, periodictable the 15th family's metal, and the salt of at least a material of aminotriazine compound, oxysalt (C2) is selected from condensed phosphoric acid, at least a oxygen acid of sulfuric acid and pyrosulfuric acid and be selected from ammonia, carbamide compound, the salt of at least a basic nitrogen compound of guanidine compound and aminotriazine compound.
9. resin combination according to claim 1, wherein organic secondary phosphine acid salt (C1) is to be selected from not replace or have a substituent dialkyl phosphinic acid, do not replace or have substituent bicyclic alkyl phospho acid, do not replace or have substituent alkylidene group phospho acid, do not replace or have substituent alkenylene phospho acid, and do not replace or have organic phospho acid of substituent alkane two (alkyl phosphinic acids) and be selected from the periodictable group II metal, metal belonging to group 13 of periodic table, melamine, melam, the salt of at least a material of melem and mellon, oxysalt (C2) are the salt that is selected from Tripyrophosphoric acid and aminotriazine compound, the salt of sulfuric acid and aminotriazine compound, at least a material of the salt of pyrosulfuric acid and aminotriazine compound and condensation phosphamide.
10. resin combination according to claim 1, wherein organic-inorganic hydrochlorate (C) comprises organic secondary phosphine acid salt (C1) and oxysalt (C2).
11. resin combination according to claim 1, wherein electrical characteristic activator (D) also comprises the periodictable group 4 metal compounds.
12. resin combination according to claim 1, wherein electrical characteristic activator (D) also comprises fluorine resin.
13. resin combination according to claim 1, wherein electrical characteristic activator (D) is selected from α-C 2-3The homopolymer of alkene or multipolymer, α-C 2-3Alkene-(methyl) acrylic copolymer, α-C 2-3Alkene-(methyl) vinylformic acid C 1-4Alkyl ester copolymer, α-C 2 -3Alkene-(methyl) glycidyl acrylate multipolymer, sour modified olefin be resin, fluoridize α-C 2-3At least a material of the homopolymer of alkene or multipolymer.
14. resin combination according to claim 1, wherein with respect to matrix resin (A) 100 weight parts, the ratio of halogen flame retardant (B) is the 2-20 weight part, and the ratio of organic-inorganic hydrochlorate (C) is the 3-30 weight part.
15. resin combination according to claim 1, wherein with respect to halogen flame retardant (B) 100 weight parts, the ratio of organic-inorganic hydrochlorate (C) is the 20-500 weight part, and the ratio of electrical characteristic activator (D) is the 10-150 weight part.
16. resin combination according to claim 1, at least a electrical characteristic that wherein also contain the salt, (moisture) metal silicate, (moisture) borate metal salt, (moisture) stannic acid metal-salt, metal oxide, metallic sulfide and the alkali earth metallic compound that are selected from the aminotriazine compound are improved auxiliary agent (E).
17. resin combination according to claim 1 wherein also contains at least a electrical characteristic that are selected from melamine cyanurate, talcum, kaolin, (moisture) zinc borate, (moisture) lime borate, (moisture) zinc, zinc oxide, zinc sulphide, lime carbonate and secondary calcium phosphate and improves auxiliary agent (E).
18. resin combination according to claim 1 wherein also contains at least a flame retardant (F) that is selected from aromatics, P contained compound and antimony containing compounds.
19. resin combination according to claim 18, wherein flame retardant (F) is that to be selected from phenol resin, polyphenylene oxide be that resin, aromatic epoxy resin, phenoxy resin, polyphenylene sulfide are that resin, polycarbonate-based resin, polyarylester are that resin, aromatic polyamide are that resin, aromatic polyester resin and aromatic polyester acid amides are at least a material of resin.
20. resin combination according to claim 18, wherein flame retardant (F) is at least a material that is selected from (condensation) phosphoric acid ester, (condensation) phosphoric ester amides, (crosslinked) aryloxy phosphonitrile, (Asia) phosphate metal salt, hypophosphorous acid metal salt, organic (Asia) phosphonic acid ester, organic (Asia) phosphonic acid metal salt and organic (Asia) phosphonic acids aminotriazine salt.
21. resin combination according to claim 18, wherein flame retardant (F) is at least a material that is selected from alkyl (Asia) phosphonic acid metal salt, (Asia) phosphate metal salt and hypophosphorous acid metal salt.
22. resin combination according to claim 1 wherein also contains at least a additive that is selected from weighting agent, heat-resisting stabilizing agent, processing stabilizers and reactive stablizer.
23. resin combination according to claim 1, when described resin combination (i) is measured with the test film of thickness 0.8mm, flame retardant resistance based on the UL94 combustion test is more than the V-1, and is more than the 350V based on the comparison galvanic corrosion index of IEC112 (ii).
24. resin combination according to claim 1, when described resin combination (i) is measured with the test film of thickness 1.6mm, flame retardant resistance based on the UL94 flammability test is more than the V-2, and is more than the 500V based on the comparison galvanic corrosion index of IEC112 (ii).
25. resin combination according to claim 1, when described resin combination (i) is measured with the test film of thickness 1.6mm, flame retardant resistance based on the UL94 flammability test is more than the V-0, and is more than the 650V based on the comparison galvanic corrosion index of IEC112 (ii).
26. a molding, it is formed by the described resin combination of claim 1.
27. molding according to claim 26, it is electrical and electronic parts, office automated machine parts, household electrical appliances machine part, trolley part or machine structural parts.
CN2006800249249A 2005-07-08 2006-07-07 Flame retardant resin composition Expired - Fee Related CN101218305B (en)

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