CN1234774C - Flame-retardant resin composition - Google Patents

Abstract

A flame-retardant resin composition which comprises a base resin and a flame retardant comprising (A) a calcium hydrogen phosphate and (B) at least one ingredient selected among (B1) a phosphorus compound, (B2) a nitrogen compound, (B3) a boron compound (such as a metal borate), (B4) a silicon compound (such as a (poly)organosiloxane or zeolite), and (B5) a metal compound (such as a metal hydroxide or metal oxide). The calcium hydrogen phosphate (A) may be, for example, a substantially anhydrous one. The phosphorus compound (B1) may be a (poly)phosphoric acid salt, a condensate of an organophosphorus compound, red phosphorus, etc. The nitrogen compound (B2) may be a salt of an aminated cyclic nitrogen compound with an oxyacid, a salt of an aminated cyclic nitrogen compound with a hydroxylated nitrogen compound, a urea compound, etc. The resin composition can have flame retardancy without the need of containing a halogenated flame retardant.

Description

Fire-proof resin composition

Technical field

The present invention relates to contain the fire-proof resin composition and preparation method thereof of base resin (ベ one ス Trees fat) and fire retardant and the molding that forms of fire-proof resin composition thus, this fire retardant is by secondary calcium phosphate salt (A) and is selected from least a component (B) formation of P contained compound (B1), nitrogenous compound (B2), boron-containing compound (B3), silicon-containing compound (B4) and metallic compound (B5).

Background technology

In the thermoplastic resin, polyester based resin such as polybutylene terephthalate and phenylethylene resin series etc. are owing to its good mechanical characteristics, electrical characteristic, weathering resistance, water tolerance, resistance to chemical reagents and solvent resistance are used for such as various uses such as electrical/electronic part, mechanical mechanism part, auto parts.In addition, for described thermoplastic resin,, consider its flame retardant resistance has been proposed requirement from secure context along with the expansion of Application Areas, the raising of mechanical characteristics.Known general fire-retardantization method is to add the fire retardant that has used halogen compounds and/or antimony compounds in thermoplastic resin.

But for the halogen flame retardant, the situation that has a large amount of dioxin based compounds to produce during combustion decomposition considers it is not preferred from the environment aspect.Therefore there is the people to propose to use the fire-retardantization method as non-halogen flame retardant such as phosphorus system, nitrogenous compound.

The spy opens in the clear 64-14277 communique and has announced a kind of fire-proof resin composition, wherein in thermoplastic resin (polypropylene), add specified quantitative by silicone oil, silicone resin and contain the fire retardant that phosphorus-nitrogen compound (ammonium polyphosphate) is formed.Announced at polyene to be the fire-proof resin composition of the resol that mixes specified quantitative in the resin, P contained compound (red phosphorus), expanded graphite in the Te Kaiping 9-111059 communique.In addition, the spy opens and has announced in the flat 10-195283 communique add the polyester and resin composition that the specific compound oxide compound of resol and iron, cobalt, nickel or copper (lacquer with) carries out fire-retardantization in right amount in having the phosphoric acid ester of ad hoc structure.Put down in writing the resin combination that constitutes by polybutylene terephthalate and polyphenylene oxide and resorcinol diphosphate in the Te Biaoping 6-504563 communique.

But, as non-halogen flame retardant, do not compare its poor fire with the halogen flame retardant, so must use a large amount of fire retardants though do not contain deleterious halogen.And the interpolation of a large amount of fire retardants can cause that surperficial frosting and resin mechanical characteristics reduce.Thereby flame retardant resistance and mechanical characteristics are improved simultaneously.When for example using expanded graphite simultaneously, the outward appearance during its moulding significantly reduces.When particularly using phosphoric acid ester, can cause surperficial frosting and stable on heating reduction as P contained compound.

This shows that usefulness method in the past is difficult in gives its flame retardant resistance under the situation that does not reduce resin properties.In addition, in above-mentioned fire retardant, but can not give very high flame retardant resistance for thermoplastic resin widely though can carry out fire-retardantization to specific resin.

, the objective of the invention is to for this reason, even the non-halogen that provides a spot of fire retardant also can carry out high-level fire-retardantization be fire-proof resin composition with and preparation method thereof.

Another object of the present invention is to, provide and do not reduce resin properties and flame retardant resin composition of fire-retardantization and preparation method thereof.

Another purpose of the present invention is,, economically excellent flame resin combination and manufacture method thereof little to carrying capacity of environment are provided.

The present invention also aims to, the formed body that has improved flame retardant resistance is provided.

Summary of the invention

Present inventors have carried out deep research in order to realize above-mentioned problem, found that, add specific non-halogen flame retardant and can carry out high-caliber fire-retardantization in thermoplastic resin, thereby finished the present invention.

That is to say, fire-proof resin composition of the present invention is the fire-proof resin composition that contains base resin and fire retardant, and described fire retardant is made of secondary calcium phosphate salt (A) and at least a component (B) that is selected from P contained compound (B1), nitrogenous compound (B2), boron-containing compound (B3), silicon-containing compound (B4) and metallic compound (B5).Comprising polyester based resin, alkene in the described thermoplastic resin and be resin, acrylic resin, phenylethylene resin series, polyamide-based resin, polycarbonate-based resin, polyphenylene oxide and be resin, vinyl resin, polyacetal is resin etc.Described secondary calcium phosphate salt (A) also can be anhydrous in fact.Described P contained compound (B1) can be phosphoric acid ester (condensed phosphoric acid esters), phosphoric ester amides, phosphazene compound, organic phospho acid compound, organic phosphinic compounds, (many) phosphoric acid salt, red phosphorus etc.Nitrogenous compound (B2) comprises salt (b), the salt (c) with amino nitrogenous ring compound and organic phosphoric acid that has amino nitrogenous ring compound (a), has amino nitrogenous ring compound and oxygen acid, nitrogenous ring compound and the salt (d) with nitrogenous compound of hydroxyl, Tripyrophosphoric acid acid amides (e), the carbamide compound (f) etc. with amino.Described boron-containing compound (B3) comprises the metal-salt of boric acid etc., and described silicon-containing compound (B4) comprises (gathering) organo-siloxane, zeolite etc.Described metallic compound (B5) comprises metal hydroxides, metal oxide etc.

It is resin (C2), aromatic epoxy resin aromatic resins (C) such as (C4) that aforementioned fire-proof resin composition also can further contain the resin (C1), the polyarylate that have a hydroxyl and/or amino aromatic ring at main chain or side chain, can contain the metal-salt of boric acid in addition.

It is that antioxidant, phosphorus are stablizer, fluorine resin, weighting agent etc. that aforementioned fire-proof resin composition can also further contain hindered phenol.

In addition, the present invention also comprises base resin and aforementioned fire retardant is mixed with the method for fire-proof resin composition and the formed body that forms with above-mentioned fire-proof resin composition.

The concrete form of implementation of invention

[base resin]

As base resin, have no particular limits, can enumerate various thermoplastic resins, heat reactive resin etc.As the thermoplastic resin that constitutes base resin, can use polyester based resin, ethylene series resin, acrylic resin, phenylethylene resin series, polyamide-based resin, polycarbonate-based resin, polyphenylene oxide is that resin, vinyl resin, polyacetal are resin etc.

(polyester based resin)

Polyester based resin is equal polyester or the copolyesters that is obtained by the polycondensation of polycondensation, hydroxy acid or the lactone of dicarboxylic acid component and diol component or the polycondensation of these components etc.Preferred polyester is that resin comprises that general saturated polyester is that resin, particularly aromatic series saturated polyester are resin.

As the dicarboxylic acid composition, for example can enumerate, aliphatic dicarboxylic acid (succsinic acid for example, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane dicarboxylic acid, dodecanedicarboxylic acid, the hexadecane dicarboxylic acid, the dicarboxylic acid of carbon numbers such as dimeracid about 6～40, the dicarboxylic acid of preferred carbon number about 1～14), the alicyclic dicarboxylic acid (for example, hexahydro-phthalic acid, the hexahydro-m-phthalic acid, hexahydroterephthalic acid, the dicarboxylic acid of himic acid carbon numbers about 8～12 such as (acid of Ha ィ ミ ッ Network)), aromatic dicarboxylic acid (for example, phthalic acid, m-phthalic acid, terephthalic acid, 2, naphthalene monocarboxylic acids such as 6-naphthalic acid, 4,4 '-phenylbenzene carboxylic acid, 4,4 '-two phenoxy ethers carboxylic acids, 4,4 '-ditan dicarboxylic acid, 4, the dicarboxylic acid of carbon numbers about 8～16 such as 4 '-diphenylketone dicarboxylic acid) or their derivative (for example, lower alkyl ester, acid anhydrides etc. can form the derivative of ester) etc.These dicarboxylic acid components can be used alone or in combination of two or more.In addition, can also and use polycarboxylic acids such as trimellitic acid, Pyromellitic Acid etc. as required.

Preferred dicarboxylic acid component comprises aromatic dicarboxylic acids such as terephthalic acid, naphthalic acid.

Can enumerate for diol component, for example the aliphatics alkylene glycol (for example, ethylene glycol, 1, ammediol, 1, the 2-propylene glycol, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, season pentanediol, hexylene glycol, ethohexadiol, the aliphatic dialcohol of carbon numbers such as decanediol about 2～12, the aliphatic dialcohol of preferred carbon number about 2～10), [carbon number of alkylene base is about 2～4 to the polyoxy alkylene glycol, glycol with a plurality of oxygen silane supporting units, glycol ether for example, dipropylene glycol, one dibutylene glycol that contracts, Triethylene glycol, tripropylene glycol, polytetramethylene glycol etc.], alicyclic diol (for example, 1, the 4-cyclohexanediol, 1, the 4-cyclohexanedimethanol, Hydrogenated Bisphenol A etc.).In addition, can also with Resorcinol, Resorcinol, xenol, 2,2-two (4-hydroxyphenyl) propane, 2, aromatic diols such as 2-two (4-(2-hydroxy ethoxy) phenyl) propane, xylylene-glycol are also used.These diol components can be used singly or in combination of two or more.In addition, as required also can how pure with glycerol, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane etc.

Preferred diol component comprises C _2-6Alkylene glycol (ethylene glycol, 1, ammediol, 1,2-propylene glycol, 1, straight chain alkylene glycols such as 4-butyleneglycol), to have repeat number be that [glycol ether etc. contain poly-(oxygen-C for the polyoxy alkylene glycol of about 2～4 oxygen silane supporting unit _2-4Alkylene) unitary glycol], 1,4-cyclohexanedimethanol etc.

Hydroxy acid for example comprises hydroxy acid such as hydroxy-benzoic acid, hydroxynaphthoic acid, hydroxyl phenylacetic acid, oxyacetic acid, hydroxycaproic acid or their derivative etc.

Lactone comprises C such as propionic acid lactone, butyrolactone, valeric acid lactone, caproic acid lactone (for example ε-caproic acid lactone etc.) _3-12Lactone etc.

Preferred polyester is that resin comprises, with alkylene base arylide such as terephthalic acid alkylene ester, naphthalic acid alkylene ester be the equal polyester of principal constituent (for example about 50～100 weight %, preferred 75～100 weight %) or copolyesters [for example, the polyalkylene terephthalates ester (for example, 1,4-hexanaphthene two methylene terephthalate (PCT), polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT), polybutylene terephthalate poly terephthalic acid C such as (PBT) _2-4The alkylene ester), poly-naphthalic acid alkylene ester (for example, poly-naphthalic acid C such as PEN, poly-naphthalic acid propylene glycol ester _2-4The alkylene ester) etc. equal polyester, be the copolyesters of principal constituent (for example more than the 50 weight %) with terephthalic acid alkylene ester and/or naphthalic acid alkylene ester units].Particularly preferred polyester based resin comprises, is that the polybutylene terephthalate of principal constituent is resin (for example polybutylene terephthalate, a polybutylene terephthalate copolyesters) with the mutual-phenenyl two acid bromide two alcohol ester unit.In addition, these polyester based resins can use separately also and can be used in combination of two or more.

In addition, in the copolyesters, can enumerate C as copolymerisable monomer _2-6Alkylene glycol (ethylene glycol, 1, ammediol, 1, straight chain alkylene glycols such as 4-butyleneglycol etc.), to have repeat number be that (glycol ether etc. contain poly-(oxygen-C for the polyoxy alkylene glycol of about 2～4 oxygen silane supporting unit _2-4Alkylene) C unitary glycol etc.), _6-12Aliphatic dicarboxylic acid (hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid etc.), aromatic dicarboxylic acid (phthalic acid, m-phthalic acid etc.), hydroxy acid (hydroxy-benzoic acid etc.) etc.In addition, polyester based resin only otherwise damage its melt molding etc., not only can have linear chain structure also can have branched structure, can also be crosslinked.Also can be liquid crystal polyester in addition.

Polyester based resin can wait and prepare by for example transesterify of method, direct esterification method commonly used.

(ethylene series resin)

Can enumerate as the ethylene series resin, for example 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) separately or their multipolymer.Can enumerate as preferred ethylene series resin, be the vinylite (for example polyethylene, ethylene-propylene copolymer, ethene-(methyl) acrylic copolymer etc.) of principal constituent (for example 75～100 weight %) with the ethylene unit, be propylene resin (for example polypropylene, propylene-ethylene copolymers, propylene-(methyl) acrylic copolymer etc.) of principal constituent (for example 75～100 weight %) etc. with the propylene units.The ethylene series resin can use separately maybe and can be used in combination of two or more.

(acrylic resin)

Acrylic resin comprises, for example (methyl) vinylformic acid C such as (methyl) vinylformic acid, (methyl) methyl acrylate _1～10(methyl) acrylic monomers such as alkyl ester, (methyl) acrylamide, (methyl) vinyl cyanide separately or the multipolymer (for example, acrylonitritrile-styrene resin, acrylonitrile-styrene-(methyl) acrylate copolymer etc.) of multipolymer or (methyl) acrylic monomer and other copolymerisable monomer etc.Can enumerate poly-(methyl) methyl acrylate, alkyl acrylate-methyl acrylate copolymer, (methyl) vinylformic acid-styrol copolymer, (methyl) methyl acrylate-styrol copolymer etc. as preferred acrylic resin.These acrylic resins can be used singly or in combination of two or more.

(phenylethylene resin series)

Can enumerate as phenylethylene resin series, for example styrenic monomers (for example vinylbenzene, Vinyl toluene, alpha-methyl styrene, chloro-styrene etc.) is independent or multipolymer; The multipolymer of styrenic monomers and vinyl monomer (for example α such as unsaturated nitrile, (methyl) acrylate, (methyl) vinylformic acid, maleic anhydride such as vinyl cyanide, β-monoolefine unsaturated carboxylic acid or acid anhydrides or their ester etc.); Styrenic graft copolymer, styrene block copolymer etc.

Preferred phenylethylene resin series comprises, polystyrene (GPPS), styrene-methylmethacrylate copolymer, vinylbenzene-(methyl) acrylic copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer (AS resin), in rubber components polymerization the impact resistant polystyrene of styrenic monomers (HIPS), polystyrene grafting or segmented copolymer etc.Can enumerate as the polystyrene graft copolymer, in rubber components at least graft polymerization the multipolymer of styrenic monomers and co-polymerized monomer (for example in polyhutadiene graft polymerization the ABS resin of vinylbenzene and vinyl cyanide, in acrylic rubber graft polymerization the AAS resin of vinylbenzene and vinyl cyanide, in chlorinatedpolyethylene graft polymerization the ACS resin of vinylbenzene and vinyl cyanide, in ethene-vinyl acetate copolymer graft polymerization the polymkeric substance of vinylbenzene and vinyl cyanide, in ethylene-propylene rubber graft polymerization the polymkeric substance of vinylbenzene and vinyl cyanide, in polyhutadiene graft polymerization the MBS resin of vinylbenzene and methyl methacrylate, in styrene-butadiene copolymer rubber graft polymerization the resin etc. of vinylbenzene and vinyl cyanide.Can enumerate multipolymer (for example styrene-butadiene-styrene (SBS) segmented copolymer, styrene-isoprene block copolymer, styrene-isoprene-phenylethene (SIS) segmented copolymer, hydrogenated styrene-butadiene-styrene (SEBS) segmented copolymer, hydrogenated styrene-isoprene-vinylbenzene (SEPS) segmented copolymer) that constitutes by polystyrene block and diene or olefin block etc. as segmented copolymer.These phenylethylene resin series can be used singly or in combination of two or more.

(polyamide-based resin)

Polymeric amide comprises, by diamines and dicarboxylic acid deutero-polymeric amide; By aminocarboxylic acid and as required with diamines and/or dicarboxylic acid and with and the polymeric amide that obtains; By lactan and as required with diamines and/or dicarboxylic acid and with and the deutero-polymeric amide.Polymeric amide also comprises by at least two kinds of different formed copolyamides of the component that forms polymeric amide.

Can enumerate for example trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylene diamine, 2,2,4-trimethylammonium hexamethylene diamine, 2,4, aliphatie diamines such as 4-trimethylammonium hexamethylene diamine, hot methylene diamines as diamines; Alicyclic diamines such as two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane.Can and use aromatic diamines such as penylene diamines, a penylene dimethylamine in addition.These diamines can use a kind of or be used in combination of two or more.

Can enumerate as dicarboxylic acid, for example C such as pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, octadecane diacid _4-20Aliphatic dicarboxylic acid; Dimer (fatty acid) yl (dimeracid); Hexanaphthene-1,4-dicarboxylic acid and hexanaphthene-1, alicyclic ring dicarboxylic acid such as 3-dicarboxylic acid; Aromatic dicarboxylic acids such as phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, naphthalene monocarboxylic acid etc.

Can enumerate as aminocarboxylic acid, for example C such as aminoheptylic acid, amino-nonanoic acid, amino undecanoic acid _4-20Aminocarboxylic acid.Aminocarboxylic acid can use one or more to be used in combination.

Can enumerate as lactan, for example C such as butyrolactam, Valerolactim, hexanolactam, spicy inner formyl amine, oenantholactam, 11 lactan, laurolactam _4-20Lactan.These lactan can use and a kind ofly also can be used in combination of two or more.

Can enumerate as polyamide-based resin, for example nylon 46, nylon 6, nylon 66, NYLON610, nylon 612, Ni Long11, nylon 12 fatty polyamides such as grade, 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), by aromatic series and aliphatic dicarboxylic acid (for example terephthalic acid and hexanodioic acid) and aliphatie diamine (hexamethylene diamine for example, nine methylene diamines etc.) polymeric amide that obtains, the polymeric amide that obtains by aliphatic dicarboxylic acid (for example hexanodioic acid) and aromatic diamine (for example xylylene diamines) etc.These polymeric amide can use separately also can mix use.Preferred polymeric amide comprises non-aromatic and fatty polyamide (nylon 6, nylon 66, NYLON610, nylon 612, Ni Long11, nylon 12 etc.), semiaromatic polyamide composition (nylon MXD 6, nylon 9 T etc.), semi-aromatic copolyamide (nylon 6T/6, nylon 6T/66, nylon 6T/12, nylon 6I/6, nylon 6I/66, nylon 6T/6I, nylon 6T/6I/6, nylon 6T/6I/66, nylon 6T/M5T etc.) etc.Polyamide-based resin can use and a kind ofly also can be used in combination of two or more.

(polycarbonate-based resin)

Polycarbonate-based resin comprises the polymkeric substance that is obtained by carbonate reactions such as dihydroxy compound and phosgene or diphenyl carbonates.Dihydroxy compound also can be an alicyclic compound etc., preferred bisphenol cpd.

Bisphenol cpd can be enumerated, two (4-hydroxyphenyl) methane (Bisphenol F etc.), two (hydroxyphenyl) ethane (dihydroxyphenyl propane D etc.), 1,1-two (4-hydroxyphenyl) propane, 2,2-two (4-hydroxyphenyl) propane (dihydroxyphenyl propane), 2,2-two (4-hydroxy-3-methyl phenyl) propane, 2,2-two (4-hydroxyphenyl) butane, 2,2-two (4-hydroxyphenyl)-3-methylpropane, 2,2-two (4-hydroxyphenyl) hexane, 2, two (hydroxyaryl) C such as 2-two (4-hydroxyphenyl)-4 methylpentanes _1-6Paraffinic hydrocarbons; 1,1-two (4-hydroxyphenyl) pentamethylene, 1, two (hydroxyaryl) C such as 1-two (4-hydroxyphenyl) hexanaphthene _4-10Naphthenic hydrocarbon; 4,4 '-dihydroxydiphenyl ether; 4,4 '-dihydroxy-diphenyl sulfone; 4,4 '-dihydroxyl diphenylsulfide; 4,4 '-dihydroxyl diphenylketone etc.Comprise (gathering) organic siloxane modified polycarbonate-based resin (for example special resin that flat 6-100684 number, spy open record such as flat 10-182832 communique etc. of opening) etc. in addition.Aforementioned (gathering) organic siloxane modified polycarbonate-based resin for example can use " the Off ロ Application AC1030 " of " bright dipping petroleum chemistry (company) " production etc.

Preferred polycarbonate-based resin comprises bisphenol A polycarbonate.Polycarbonate-based resin can use and a kind ofly also can be used in combination of two or more.

(polyphenylene oxide is resin)

Polyphenylene oxide is that resin (polyphenylene ether is a resin) comprises single polymers and multipolymer.Can enumerate poly-(2 as single polymers, 6-dimethyl-1, the 4-phenylene) oxide compound, poly-(2,5-dimethyl-1, the 4-phenylene) oxide compound, poly-(2,5-diethyl-1, the 4-phenylene) oxide compound, poly-(2-methyl-6-ethyl-1, the 4-phenylene) oxide compound, poly-(2,6-two-n-propyl group-1, the 4-phenylene) oxide compound, poly-(2-ethyl-6-sec.-propyl-1,4-phenylene) oxide compound, poly-(2-methyl-6-methoxyl group-1, the 4-phenylene) oxide compound, poly-(2-methyl-6-hydroxyethyl-1, the 4-phenylene) oxide compound, poly-(2-methyl-6-chloroethyl-1,4-phenylene) oxide compound, poly-(2,3,6-trimethylammonium-1,4-phenylene) oxide compound etc. poly-(one, two or three C _1-6Alkyl-phenylene) (C such as oxide compound, poly-(2-methyl-6-phenyl-1,4-phenylene) oxide compound _1-6Alkyl-one C _6-10Aryl-phenylene) (one or two C such as oxide compound, poly-(2,6-phenylbenzene-1,4-phenylene) oxide compound _6-10Aryl-phenylene) oxide compound etc.

Multipolymer as polyphenylene oxide can be enumerated, multipolymer with monomeric unit of aforementioned single polymers more than 2 (for example has 2,6-dimethyl-1,4-phenylene oxide unit and 2,3,6-trimethylammonium-1, the unitary random copolymers of 4-phenylene oxide etc.), by making cresols, the modified by alkyl phenol phenyl aldehyde resin block of alkylphenol such as p-tert-butylphenol and phenyl aldehyde resin or alkylbenzene formaldehyde resin reaction gained and as the modified polyphenyl ether copolymer of the polyphenylether segmented formation of agent structure, graft phenylethene based polymer in polyphenylene oxide or its multipolymer and modified graft copolymer etc.Polyphenylene oxide is that resin can use and a kind ofly also can be used in combination of two or more.

(vinyl resin)

Vinyl resin comprises ethene base system monomer (vinyl ester such as vinyl-acetic ester, propionate, butenoic acid vinyl acetate, vinyl benzoate for example; Vinyl-chloride-containing base monomer (for example vinylchlorid); Fluorine-containing vinyl monomer (for example vinyl fluoride, chloroprene etc.); Vinyl ketones such as methyl vinyl ketone, methyl isopropenyl ketone; Vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether; Vinyl amines such as N-vinylcarbazole, N-vinyl pyrrolidone etc.) separately or its multipolymer or with the formed multipolymer of other copolymerisable monomers etc.

Also can use the derivative (for example polyvinyl acetals such as polyvinyl alcohol, polyvinyl formal, polyvinyl butyral acetal, ethene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer etc.) of aforementioned vinyl resin.These vinyl resins can use and a kind ofly also can be used in combination of two or more.

(polyacetal is a resin)

Polyacetal is that resin is with oxidation methylene base (CH ₂O-) be the unitary macromolecular compound of main composition, comprise poly-acetic ester homopolymer or polyoxymethylene (for example du pont company manufacturing, commodity " デ Le リ Application " by name, Asahi Chemical Industry's industry (company) manufacturing, commodity " テ Na ッ Network 4010 " by name etc.), contain oxidation methylene unit and the unitary poly-acetate copolymer of comonomer (for example gathering plastics (company) manufacturing, commodity " ジ ェ ゥ コ Application " by name etc.).For multipolymer, the comonomer unit comprises the oxidation silane supporting unit (oxidation ethylene group (CH for example of carbon number about 2～6 (preferred carbon number about 2～4) ₂CH ₂O-), oxidation trimethylene base, oxidation fourth support base etc.).The unitary content of comonomer is a small amount of, is that the resin total amount can be selected 0.01～20 mole of %, preferred 0.03～10 mole of % (for example 0.05～5 mole of %), the more preferably scope about 0.1～5 mole of % with respect to polyacetal for example.

Terpolymer that Copolyacetal also can constitute for the multipolymer that is made of two components, by three components etc.Copolyacetal is except for can also being segmented copolymer (for example special fair 2-24307 communique, Asahi Chemical Industry's industry (company) manufacturing, trade(brand)name " テ Na ッ Network LA " " テ Na ッ Network LM " etc.), graft copolymer etc. the random copolymers.In addition, polyacetal is that resin not only can be that linear structure can also be branched structure, also can have crosslinking structure.Also have the urethaneization that polyacetal is esterification that the end group of resin also can be by for example carrying out with carboxylic acid such as acetate, propionic acid or their acid anhydrides, carry out with isocyanic ester, esterification etc. and stabilization.Can melt molding as long as the polymerization degree of polyacetal, the degree of branching, degree of crosslinking have no particular limits.The molecular weight of polyacetal resin has no particular limits, and for example weight average molecular weight 5,000～500, and 000, preferred about 10,000～400,000.

Aforementioned polyacetal is that resin can be by for example aldehydes such as formaldehyde, paraformaldehyde, trioxane, ethylene oxide, propylene oxide, oxybutylene, Styrene oxide 98min., cyclohexene oxide, 1,3-two oxa-s penta ring, glycol ether formal, 1, cyclic ester, cyclic formals polymerizations such as 4-butyleneglycol formal make.In addition, can use alkyl or aryl glycidyl ether (for example methyl glycidyl ether, ethyl ether, phenyl glycidyl ether, naphthyl glycidyl ether etc.), alkylene base or polyoxygenated alkylene base glycol diglycidylether (for example ethylene glycol diglycidylether, triethylene glycol diglycidylether, butanediol diglycidyl ether etc.), alkyl or aryl glycidic alcohol, cyclic ester (for example beta-propiolactone etc.) and vinyl compound (for example vinylbenzene, vinyl ether etc.) as the copolymerization component.

(other resin)

Can enumerate as other resin, aliphatic polyketone is that resin (ketone resin), polyphenylene sulfide are resin (for example polyphenylene sulfide, polyphenyl thioketones, poly-biphenyl are embraced thioether, polyphenylene sulfide sulfone etc.); Polysulfones (for example thermoplasticity polysulfones, poly-(ether sulfone), poly-(4,4 '-bis-phenol ether sulfone etc.); (liquid crystal) polyesteramide; Polyestercarbonate; Polyetherketone; Poly-(ether ether ketone); Polyetherimide; The plastic poly-urethane of heat is resin (for example the polymkeric substance that is obtained by diisocyanate cpd such as toluene support vulcabond and aforementioned glycol and/or aforementioned diamine reactant, can also have poly-chemglaze partly such as polytetramethylene glycol etc.); Thermoplastic polyimide; Polyoxygenated benzyl support base; Thermoplastic elastomer etc.

Can enumerate as thermosetting resin, resol, aminoresin (trimeric cyanamide is that resin, urea are resin etc.), thermosetting polyester are that resin (Synolac, unsaturated polyester resin etc.), Resins, epoxy, silicon-type resin, vinyl ester are resin, poly-urethane resin etc.

These resins or macromolecular compound can separately or be used in combination of two or more.

Can enumerate as preferred base resin, can be that resin, vinyl resin, polyacetal are thermoplastic resins such as resin for polyester based resin, phenylethylene resin series, polyamide-based resin, polycarbonate-based resin, the polyphenylene oxide of liquid crystal polyester, more preferably can enumerate polyester based resin, polyphenylene oxide is resin, phenylethylene resin series, polycarbonate-based resin.Special preferred polyester is resin (PBT is a resin etc.).Also can with polyester based resin (a) and polycarbonate-based resin, phenylethylene resin series with and/or polyphenylene oxide be resin (b) and use.At this moment, in the base resin content of resin (b) be 0.01～95 weight %, preferred 1～60 weight %, more preferably about 5～40 weight % (particularly 10～40 weight %).Use under the situation of polycarbonate-based resin, aforementioned content also can be for about 0.01～10 weight %, preferred 0.5～5 weight %.

The number-average molecular weight of above-mentioned base resin has no particular limits, and can do appropriate selection according to the kind and the purposes of resin, for example can select 5 * 10 ³～200 * 10 ⁴, preferred 1 * 10 ⁴～150 * 10 ⁴, further preferred 1 * 10 ⁴～100 * 10 ⁴About.In addition, base resin is under the situation of polyester based resin, and number-average molecular weight for example can be 5 * 10 ³～100 * 10 ⁴, preferred 1 * 10 ⁴～70 * 10 ⁴, more preferably 1.2 * 10 ⁴～30 * 10 ⁴About.

[fire retardant]

The fire retardant that uses among the present invention is made of secondary calcium phosphate salt (A) and at least a component (B) (fire retardant (B)) that is selected from P contained compound (B1), nitrogenous compound (B2), boron-containing compound (B3), silicon-containing compound (B4) and metallic compound (B5).

(A) secondary calcium phosphate salt

The non-condensed phosphoric acid that comprises peroxophosphoric acid, ortho-phosphoric acid, metaphosphoric acid, phosphorous acid (phosphonic acids), ortho phosphorous acid (phospho acid) etc. as the phosphoric acid of secondary calcium phosphate salt; Poly-metaphosphoric acid (HPO ₃) _m(in the formula, m represents the integer more than 2), Hypophosporous Acid, 50, phosphoric anhydride condensed phosphoric acids such as (Vanadium Pentoxide in FLAKESs) (Tripyrophosphoric acid) etc.In addition, also comprise the condensed phosphoric acid class of expression in the following formula (1) in the aforementioned Tripyrophosphoric acid,

(n represents the integer more than 2 in the formula).

N is the integer more than 2, preferred 3～8 integer in the preceding formula.Such Tripyrophosphoric acid can be enumerated tetra-sodium, triphosphoric acid, four phosphoric acid etc.

Have a plurality of phosphoric acid that form the salt position, at least a portion position can form part salt (the part salt of dehydroamino acids such as ammonium polyphosphate, Tripyrophosphoric acid urea with other the aminocompound that contains such as amine, urea; The part salt of non-dehydroamino acids such as ortho-phosphoric acid urea etc.).

Can enumerate as secondary calcium phosphate salt, the calcium phosphate salt that are made of aforementioned phosphoric acid and calcium are ortho-phosphoric acid hydrogen calcium, Tripyrophosphoric acid hydrogen calcium etc. for example, particularly, and preferably anhydrous in fact secondary calcium phosphate salt, monocalcium phosphate, calcium monohydrogenphosphate (CaHPO ₄) etc.

In addition, can also natural goods (for example monetite) except synthetics as secondary calcium phosphate salt.In addition, functional compound (epoxy based compound for example also can be used in the surface of secondary calcium phosphate salt, the silane based compound, titanic acid ester based compound etc.), thermoplastic resin, thermosetting resin (resol for example, melamine resin, Resins, epoxy, unsaturated polyester resin, aniline resin, furane resin, Synolac, xylene resin, silicone resin etc.), can form the compound processing that is covered such as [for example special compounds that contains silicon and/or metal component and acid introduced in the 2001-131292 communique (the colloidal sol shape composition that generates by the alkoxide solution of siliceous and/or metal component etc.) etc. of opening] of glass-ceramic through heating etc.

These secondary calcium phosphate salt safety performance excellences do not have carrying capacity of environment fully, and are very favourable economically.Compare as the situation of fire retardant with independent use component (B) (system or two or more paralled system separately), with secondary calcium phosphate salt (A) and component (B) (fire retardant (B)) and when being used as fire retardant, flame retardant resistance can be significantly improved, oozing out of fire retardant can also be effectively suppressed simultaneously.

(B) component (fire retardant (B))

(B1) P contained compound

P contained compound can be enumerated organo phosphorous compounds (haplotype organo phosphorous compounds, polymer-type organo phosphorous compounds etc.), inorganic phosphorous compound etc.

Aforementioned organo phosphorous compounds comprises that (triphenylphosphine, trimethylphenyl phosphine etc. can possess substituent three C for phosphoric acid ester, phosphoric ester amides, phosphazene compound, organic phospho acid compound (phosphonic acid ester etc.), organic phosphinic compounds, organic phosphine compound _6-10Aryl phosphines etc.), (triphenylphosphine oxide, trimethylphenyl phosphine oxide etc. can possess substituent three C to the organic oxidation phosphine compound _6-10Aryl oxidized phosphine etc.), (many) phosphoric acid salt (salt of Tripyrophosphoric acid and organic bases etc.) etc.

(phosphoric acid ester)

Phosphoric acid ester can be enumerated, aliphatic phosphate ester [tricresyl phosphate C such as trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate, three iso-butyl ester of phosphoric acid, phosphoric acid pentaerythritol ester (for example Great Lakes NH-1197 etc.) _1-10Alkyl ester; Di(2-ethylhexyl)phosphate C corresponding to aforementioned phosphotriester _1-10Alkyl ester and phosphoric acid one C _1-10Alkyl ester etc.], aromatic phosphoric ester [tricresyl phosphate C such as triphenylphosphate, Tritolyl Phosphate, trixylyl phosphate, di(2-ethylhexyl)phosphate phenyl one tolyl ester, tricresyl phosphate (isopropyl benzene), di(2-ethylhexyl)phosphate phenyl one ethyltoluene base ester _6-20Aryl ester etc.], aliphatic-aromatic phosphoric acid ester [phosphoric acid methyldiphenyl base ester, phosphoric acid diethylamino phenyl base ester etc.] etc.

(phosphoric ester amides)

Phosphoric ester amides comprises the combination of phosphoric acid ester and phosphoamide, can use the phosphoric ester amides shown in the following formula (2) etc.,

(R in the formula ¹, R ², R ³And R ⁴, can be identical or different, expression-OR ⁵(R ⁵Expression alkyl, cycloalkyl or aryl, these groups also can have substituting group) or-NR ⁶R ⁷, (R ⁶, R ⁷Can be identical or different, expression hydrogen atom, alkyl, cycloalkyl or aryl, these groups also can have substituting group, R ⁶And R ⁷Also can interosculate into ring), A ¹Expression diamines residue and arylene dioxy base, p are represented integer, 0～20 the integer for example more than 0.But, R ¹～R ⁴Be simultaneously-OR ⁵The time A ¹Be the diamines residue.)。

In the formula (2), R ⁵, R ⁶And R ⁷The alkyl of expression can be enumerated C such as methyl, ethyl, butyl, t-butyl, hexyl, octyl group, nonyl, dodecyl _1-20Alkyl, preferred C _1-12Alkyl, more preferably C _1-6Alkyl.Cycloalkyl can be enumerated C such as cyclohexyl _5-20Cycloalkyl, preferred C _6-12Cycloalkyl etc.R ⁵, R ⁶And R ⁷The aryl of expression can be enumerated C such as phenyl, naphthyl _6-20Aryl etc., substituted aryl (alkyl substituting aromatic bases such as aminomethyl phenyl, ethylphenyl, hydroxyphenyl etc.).In addition, R ⁶And R ⁷Also can interosculate into ring (for example the nitrogen-atoms with adjacency is heteroatomic 4～10 yuan of heterocycles etc.).Also have, these groups can also possess substituting group (C for example _1-4Alkyl, particularly C _1-3Alkyl; Hydroxyl etc.).

-OR ⁵Base can be enumerated any monovalent organic radical group, for example phenoxy group, list, two or three C _1-4Alkyl phenoxy (for example tolyloxy, dimethyl phenoxy, trimethylammonium phenoxy group, diethyl phenoxy group etc.) etc. can have substituting group (C _1-3Alkyl etc.) phenoxy group.

-NR ⁶R ⁷Base can be enumerated, single or two C such as 1 valency amido, for example methylamino, dibutyl amido _1-4Alkyl amine group; Single or two C such as cyclohexyl amido _4-12The cycloalkyl substituted amido; Single or two C such as phenyl amido _6-20Arylamine group; C such as aminomethyl phenyl amido _1-4Alkyl C _6-20Arylamine group; Pyrrolidyl, 2-methylpyrrole alkyl, piperidyl, pipecoline base (pipecoline base), 3-methyl piperidine base, 4-methyl piperidine base, piperazinyl etc. are heteroatomic 4～10 yuan (preferred 5～8 yuan) heterocyclic radicals etc. with at least one nitrogen-atoms.

In addition, R adjacent to each other ¹And R ², R adjacent to each other ³And R ⁴Interosculate into ring respectively, for example can form alkylene dioxy (for example methylene dioxy, two methylene dioxies, trimethylene dioxy, 2,2-dimethyl-1,3-trimethylene dioxy, 2-ethyl-2-methyl isophthalic acid, 3-trimethylene dioxy, 2,2-diethyl-1, C such as 3-trimethylene dioxy _2-10The alkylene dioxy) etc.

In the formula (2), A ¹Also can be the divalent group shown in following formula (3) or (4),

(R in the formula ⁸And R ⁹Can be identical or different, expression hydrogen atom, alkyl, cycloalkyl, R ⁸And R ⁹Also can interosculate into ring.Z ¹Expression alkylene base, ring alkylene base or divalence aromaticity group.Z ²Expression divalence aromaticity group).

R ⁸And R ⁹Alkyl, the cycloalkyl of expression can be enumerated the alkyl (C such as methyl, ethyl that exemplify previously _1-6Alkyl etc.) cycloalkyl (C such as cyclohexyl _4-10Cycloalkyl etc.).R in addition ⁸And R ⁹C such as forming ethylene, trimethylene, tetramethylene, hexamethylene also can interosculate _1-6Alkylene etc.

Z ¹The alkylene of expression can be enumerated C such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene _1-6Alkylene base, preferred C _1-4Alkylene base, the ring alkylene base can be enumerated C such as cyclohexalene _4-20The ring alkylene base, preferred C _6-12The ring alkylene base.Z ¹And Z ²The divalence aromaticity group of expression can be arylene base (C such as penylene, naphthylene base for example _6-20Arylene bases etc.), [bisphenols is (the bis-phenol that exemplifies in aforementioned polycarbonate-based resin item to have the group of a plurality of aforementioned arylene bases, also has bis-phenol D, 2,2-two (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-two (4-hydroxyphenyl) butane, 2,2 '-diethyl-4, two (hydroxyaryl) paraffinic hydrocarbonss such as 4 '-dihydroxyl ditan; Two (hydroxyaryl) naphthenic hydrocarbon that exemplifies in the aforementioned polycarbonate-based resin item; 1, two (hydroxyaryl alkyl) benzene classes such as 4-two (4-hydroxyphenyl sec.-propyl) benzene; Two (hydroxyaryl) sulfone classes such as two (4-hydroxyphenyl) sulfone, two (3,5-dimethyl-4-hydroxyphenyl) sulfone; Two (4-hydroxyphenyl) ether, two (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4 '-dihydroxydiphenyl ether etc. two (hydroxyaryl) ethers; 4,4 '-dihydroxyl benzoyl benzene, 3,3 ', 5,5 '-tetramethyl--4, two (hydroxyaryl) ketones such as 4 '-dihydroxyl benzoyl benzene; Two (hydroxyaryl) thioether classes such as two (4-hydroxyphenyl) thioether, two (3-methyl-4-hydroxyphenyl) thioether; Two (hydroxyaryl) sulfoxide classes such as two (4-hydroxyphenyl) sulfoxide; 4, dihydroxyl hexichol base class such as 4 '-dihydroxyl phenylbenzene etc.) remove group behind the hydroxyl, two penylene bases etc. by bisphenols].

A ²The diamines residue of expression can be enumerated diamines [for example quadrol, piperazine, N, C such as N-dimethyl-ethylenediamine _2-4The alkylene base diamines; 1,3-piperazine, 1,4-piperazine, 2-methyl isophthalic acid, piperazines, 1 such as 4 piperazines, C such as 4-cyclohexyl diamines _4-8The cycloalkyl diamines; Penylene diamines (for example 1,4-penylene diamines etc.); Tolylene diamine (for example 2,4 di amino toluene, 3,5-diethyl-2,4 di amino toluene etc.); Xylylene diamines (for example 1,4-xylylene diamines etc.); Diaminodiphenyl-methane (for example 4,4 '-diaminodiphenyl-methane, 2,2 '-diethyl-4,4 '-diaminodiphenyl-methane, 3,3 '-diethyl-4,4 '-diaminodiphenyl-methane etc.); Diamino-diphenyl ether (for example 4,4 '-diamino-diphenyl ether, 2,2 '-dimethyl-4,4 '-diamino-diphenyl ether etc.); Diamino diphenyl sulfone (for example 4,4 '-diamino diphenyl sulfone, 3,3-dimethyl-4,4 '-diamino diphenyl sulfone etc.); The diamino-diphenyl thioether (for example 4,4 '-diamino-diphenyl thioether etc.] residue.

In addition, A ²The arylene dioxy base of expression can be enumerated arylene dioxy base, bisphenols (aforementioned Z such as Resorcinol residue, Resorcinol residue ¹And Z ²Bisphenols, for example dihydroxyl diaryl paraffinic, dihydroxyl diaryl ethers, dihydroxyl diaryl sulfide class and the dihydroxyl diaryl sulfone class etc. that exemplify in) residue etc.

Preferred phosphoric ester amides comprises that p is 0 or 1 in the formula (2), particularly p is 1 compound.P be 1 compound as shown in the formula shown in (5),

(R in the formula ¹, R ², R ³, R ⁴And A ¹As hereinbefore).

Phosphoric ester amides can be enumerated for example C _2-6(リ-ェ-ト) (aryl is piperazine two acyls four aryl phosphate esters, Edamine two acyls four C of phenyl, tolyl, xylyl etc. to Le ホ ス Off to ァ Le キ レ Application ジ ァ ミ Application ジ ィ Le テ ト テ ァ to alkylene diamine two acyls four aryl phosphate esters _6-10Aryl phosphate ester, N, N '-ethylene dimethyl diamines two acyls four C _6-10Aryl phosphate ester etc.); Also can have substituent C _6-10Arylene diamines two acyls four C _6-10Aryl phosphate ester (arylene is that penylene, penylene dimethyl etc., aryl are arylene diamines two acyl tetraphenylphosphonium acid esters, Resorcinol triphenyl phenylbenzene acid amides, Resorcinol triphenyl phenylbenzene acid amides of phenyl etc. etc.); Bis-phenol phosphoric acid ester two C such as dihydroxyphenyl propane triphenyl dibutyl acid amides _1-6Alkylamide; Bis-phenol phosphoric acid ester C such as dihydroxyphenyl propane triphenyl phenylbenzene acid amides _6-10Arylamide; Diphenyl phosphoester two C such as diphenyl phosphoester dibutyl acid amides _1-6Alkylamide; Diphenyl phosphoester C such as diphenyl phosphoester aminomethyl phenyl acid amides, diphenyl phosphoester phenylbenzene acid amides _6-10Arylamide; Aryl is piperidyl two C of phenyl, tolyl, xylyl etc. _6-10Aryl phosphate ester and pipecoline base two C _6-10Aryl phosphate ester etc.These phosphoric ester amides can be used in combination separately or with two or more.

The preparation method of aforementioned phosphoric ester amides has no particular limits, and can open 2000-154277 communique, spy with reference to the spy and open that flat 10-175985 communique, Jornal of chem.Soc.C, 3614 (1971), spy are opened flat 8-59888 communique, the spy opens clear 63-235363 communique etc. and makes.The method that method, (5) diphenyl phosphoester and the amine that for example can be after making the reaction of oxyhalogenation phosphorus and phenols in the presence of amine catalyst or the metal chloride, by (1) method, (4) halogen diphenyl phosphate and amine with the reacted method of phenols, (3) dihalo-phenyl-phosphate and amine reaction is reacted with method, (2) of amine reaction again reacts etc. obtains.

Phosphoric ester amides also can commodity in use the commodity of " phosphoric ester amides flame retardant SP series (for example SP-601, SP-703 etc.) " by name (four countries change into industry (company) preparation).

(phosphazene compound)

Can use compound as phosphazene compound with the repeating unit shown in the following formula (6).Phosphazene compound can for straight chain shape and cyclic any,

(R in the formula ¹⁰And R ¹¹Can be identical or different, represent halogen atom, alkyl, aryl, aralkyl, substituted oxy, substituted-amino or thiocyanogen, q is the integer more than 3).

R ¹⁰And R ¹¹The alkyl and the aryl of expression can be enumerated the R of preceding formula (3) ⁵The alkyl that is exemplified in (C particularly _1-4Alkyl etc.) and aryl (C particularly _6-10Aryl).Aralkyl can be enumerated C such as benzyl, styroyl _6-14Aryl-C _1-6Alkyl (C particularly _6-10Aryl-C _1-4Alkyl) etc.Substituted oxy can be enumerated alkoxyl group (C such as methoxyl group _1-4Alkoxyl group etc.), aryloxy (C such as phenoxy group _6-10Aryloxy etc.), C _6-10Aryl-C _1-4Alkoxyl group etc.Substituted-amino comprises amino, particularly disubstituted amido (two C such as dimethylamino that replaced with aforesaid alkyl, aryl etc. _1-4Alkylamino; Two C such as diphenyl amino _6-10Arylamino; C such as aminomethyl phenyl amino _1-4Alkyl C _6-10Arylamino etc.).

Q is more than 3, preferred 3～100, more preferably about 3～20 integer.

(organic phospho acid compound)

Organic phospho acid (phosphorous acid) compound for example comprises that (aryl is the tricresyl phosphite C of phenyl, tolyl, xylyl etc. to the aromatic series phosphorous acid ester _6-20Aryl esters etc.), (alkyl is aforementioned R to aliphatic phosphites ⁵～R ⁷The tricresyl phosphite C of the alkyl that exemplifies in etc. _1-10Alkyl ester; The phosphorous acid two or a C of corresponding aforementioned trialkyl phosphite _1-10Alkyl esters etc.), [for example alkyl is that the aforementioned alkyl that exemplifies, aryl are the C of phenyl, tolyl, xylyl etc. to the organophosphite of also available alkyl or aryl replacement _1-6Alkyl phosphonic acid two C _1-6Alkyl ester, C _1-6Alkyl phosphonic acid two C _6-10Aryl ester, C _1-6Alkyl phosphonic acid C _1-6Alkyl C _6-10Alkyl phosphonic acid diester such as aryl ester; The C of corresponding aforesaid alkyl phosphonic acid diester _6-10Aryl-phosphonic acid diester, C _6-10Arylphosphonic acid-ester (10-hydroxyl-9 for example, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphine-10-oxide compound); Phosphono carboxylicesters (the C of corresponding aforesaid alkyl phosphonic acid diester such as methoxycarbonyl dimethyl methyl phosphonate _1-4Alkoxy carbonyl oxygen C _1-4The alkyl phosphonic acid diester) phosphono carboxylic acid three esters such as] etc. various phosphonic acid esters.Comprise the phosphorous acid of available alkyl or aryl replacement or the metal-salt (for example Ca, Mg, Zn, Ba, Al salt etc.) of phosphono carboxylic acid etc. in addition.The phosphorous acid or the phosphono carboxylic acid that form aforementioned metal salt can be enumerated for example alkyl phosphonic acid (methyl-phosphorous acid etc.), alkyl phosphonic acid one alkyl ester (methyl-phosphorous acid one methyl esters etc.), alkyl phosphonic acid one aryl ester, arylphosphonic acid (phenyl-phosphonic acid etc.), arylphosphonic acid one alkyl ester (phenyl-phosphonic acid one phenyl etc.), arylphosphonic acid one aryl ester, 1-hydroxyl (1,1)-ethylidene-1, the 1-di 2 ethylhexyl phosphonic acid, nitrilo three (methylene phosphonic acid) (ニ ト リ ロ ト リ ス (acid of メ チ レ Application ホ ス ホ Application)), 10-hydroxyl-9,10-dihydro-9-oxy are mixed-the assorted phenanthrene of 10-phosphine-10-oxide compound, the phosphono carboxylic acid, phosphono carboxylicesters (phosphonoacetic acid ethyl ester, phosphono alkyl carboxylates such as 3-phosphono ethyl propionate etc.) etc.The detailed description of the metal-salt of these phosphorous acid or phosphono carboxylic acid can reference example such as the spy open that clear 63-22866 communique, spy are opened flat 1-226891 communique, the spy opens flat 4-234893 communique etc.

(organic phosphinic compounds)

Organic phosphinic compounds comprises can be by alkyl (C _1-6Alkyl etc.) or aryl (C _6-10Aryl etc.) phosphinate (the phospho acid C such as phospho acid methyl esters that replaces (replace or two replace) _1-6Phospho acid C such as alkyl ester, phospho acid phenylester _6-10Aryl ester, 9, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphine-10-oxide compound, 10-C _1-30Alkyl or C _6-20Aryl replacement-9-10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphine-ring-type phosphinates such as 10-oxide compound etc.) etc.The ester that comprises the phosphinico-carboxylic acid (for example 3-methyl acid phosphate subunit propionic acid, 3-phosphenylic acid subunit propionic acid etc.) that can be replaced by alkyl or aryl in addition.

Comprising in addition can be by alkyl (C _1-6Alkyl etc.) or aryl replace phospho acid [the dimethyl phospho acid for example of (replace or two replace), the methylethyl phospho acid, the diethyl phospho acid, the ethyl-butyl phospho acid, the dibutyl phospho acid, ethane-1,2-two dialkyl phosphinic acids such as (methyl phospho acid), alkylaryl phospho acid such as aminomethyl phenyl phospho acid, dialkyl phosphinic acids such as diphenyl phosphonic acid, 1-hydroxyl dihydro phosphono oxide compound (1-ヒ De ロ キ シ ジ ヒ De ロ ホ ス ホ ニ Le ォ キ シ De), the positive phosphine oxide of 1-hydroxyl (1-ヒ De ロ キ シ ホ ス ホ ラ Application ォ キ シ De) etc.] and the metal-salt of aforementioned phosphinico-carboxylic acid (Ca for example, Mg, Zn, Ba, Al salt etc.) etc.The detailed description of the metal-salt of these Hypophosporous Acid, 50, phosphinico-carboxylic acid can reference example such as the spy open clear 55-5979 communique, spy and open that flat 11-60924 communique, spy are opened flat 11-140228 communique, the spy opens 2001-2686 communique etc.

((many) phosphoric acid salt)

The salt of (many) phosphoric acid salt, particularly (many) phosphoric acid and organic bases comprises the salt of organic amines such as the phosphoric acid that exemplifies in the aforementioned secondary calcium phosphate salt item and carbamide compound (urea, alkyl replace urea etc.), guanidine.

Aforementioned polymer type organo phosphorous compounds can use the condenses of haplotype organo phosphorous compounds.

The condenses of organo phosphorous compounds can be the compound shown in the following formula (7),

(R in the formula ¹²～R ¹⁵Expression also can have substituent aryl, Z ³Be divalence aromaticity group.R represents the integer more than 1).

R in the formula (7) ¹²～R ¹⁵The aryl of expression can be enumerated the R of preceding formula (2) ⁵～R ⁷The C that exemplifies in _6-20Aryl and substituted aryl.In addition as Z ³The divalence aromaticity group of expression is except aforementioned Z ¹And Z ²The C that exemplifies in _6-20Also can enumerate two penylene bases, bisphenol residue (two (hydroxyaryl) alkane residues of dihydroxyphenyl propane, bis-phenol D, dihydroxyphenyl propane D etc., bisphenol S etc.) etc. beyond the arylene base.

Aforementioned r is (for example 1～30), preferred 1～20, more preferably 1～10, preferred especially 1～5 integer more than 1.

Compound shown in the following formula (7) (particularly condensed phosphoric acid esters) can be enumerated for example Resorcinol two (diphenyl phosphoester), Resorcinol two (two tolyl phosphoric acid ester), Resorcinol two resorcin phosphates such as (bis-xylene base phosphoric acid ester); Resorcinol phosphoric acid ester, bis-phenol phosphoric acid ester and the dihydroxyphenyl propane phosphoric acid ester etc. of corresponding these resorcin phosphates.

In addition, aforementioned polymer type organo phosphorous compounds also can be the phosphoric acid ester of polymkeric substance (resol etc.) with hydroxyl.The phosphoric acid ester of these polymkeric substance can be enumerated the polymkeric substance that for example has the structural unit shown in the following formula (8),

(R in the formula ¹⁶And R ¹⁷The expression aryl).

Aforementioned aryl can be enumerated the aryl (C that exemplifies previously _6-20Aryl, particularly phenyl) and substituted aryl (alkyl substituting aromatic base).

Aforementioned polymer type organo phosphorous compounds also comprises polyphosphoric acid subunit carboxylicesters, polyphosphonic acid acid amides in addition.The polyphosphonic acid acid amides can be enumerated the polymkeric substance that for example has the structural unit shown in the following formula (9),

(in the formula, Z ⁴Expression alkylene base, arylene base or aralkylene group base.R ¹⁸Expression alkyl, cycloalkyl, aryl, aralkyl, R ¹⁹And R ²⁰Can be identical or different, expression hydrogen atom, alkyl or aryl.In addition, R ¹⁹And R ²⁰Can directly connect ground Cheng Huan.)。

Z ⁴The alkylene base and the arylene base of representative are except aforementioned Z ¹And Z ²Beyond the alkylene base and arylene base that exemplifies in, can also enumerate phenylbenzene, bisphenol residue (aforementioned Z ¹Or Z ²The residue of the dihydroxyl aromatic yl paraffin that exemplifies etc. in), the aralkylene group base can enumerate that these alkylene bases are connected with the arylene base and the group that forms (C particularly _1-4Alkylene-C _6-10Arylene base etc.).R ¹⁹And R ²⁰Can interosculate and form aforementioned R ⁸And R ⁹The alkylene base that exemplifies in.

Aforementioned inorganic phosphorous compound comprises for example red phosphorus, (many) phosphoric acid salt (salt of non-condensed phosphoric acid such as ammonium phosphate, ammonium polyphosphate, zinc phosphate, Tripyrophosphoric acid zinc, aluminum phosphate, Tripyrophosphoric acid aluminium or condensed phosphoric acid and mineral alkali etc.) etc.Aluminate or phosphate is that zeolite etc. is also included within the aforementioned inorganic phosphorous compound in addition.

Preferred P contained compound can be enumerated the salt, inorganic phosphorous compound (red phosphorus etc.) of phosphoric acid ester (aliphatic phosphate ester, aromatic phosphoric ester and condensed phosphoric acid esters, particularly condensed phosphoric acid esters etc.), phosphoric ester amides, phosphazene compound, organic phospho acid compound, organic phosphinic compounds, (many) phosphoric acid and organic bases etc., especially preferably condensed phosphoric acid esters.

The flame retardant effect height of red phosphorus is even also can give the resin flame retardant resistance on a small quantity.In addition owing to obtaining effect on a small quantity, so can nondestructively carry out fire-retardantization to the characteristic (for example mechanical characteristics and electrical characteristic) of resin.Red phosphorus preferably uses the red phosphorus that has carried out stabilization treatment.Particularly; the reactive high plane of disruption ground that preferred use do not carry out the pulverizing of red phosphorus, do not form on the red phosphorus surface with water and oxygen carries out the resulting red phosphorus of micronize, further the red phosphorus that preferably is covered through resin (for example thermosetting resin, thermoplastic resin), metal, metallic compound independent or two or more combinations such as (for example metal hydroxides, metal oxides etc.) on the red phosphorus surface.

It is that resin, urea are that resin, Synolac, unsaturated polyester resin, Resins, epoxy, silicon are resin etc. that thermosetting resin can be enumerated resol, trimeric cyanamide, and thermoplastic resin can be enumerated polyester based resin, polyamide-based resin, acrylic resin, ethylene series resin etc.Metal hydroxides can be enumerated aluminium hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, titanium hydroxide etc., and metal oxide can be enumerated aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, zirconium white, cupric oxide, ferric oxide, molybdenum oxide, Tungsten oxide 99.999, manganese oxide, stannic oxide etc.

In addition, method of stabilizing can be enumerated with coating metal red phosphorus surface, the method that is covered with metal (iron, nickel, copper, aluminium, zinc, manganese, tin, titanium, zirconium etc.) or their alloy by the electroless plating embrane method.The method on other lining red phosphorus surface also has, and with the solution-treated red phosphorus of metal-salt (salt of aluminium, magnesium, zinc, titanium, copper, silver, iron, nickel etc.), forms the metal phosphorizing compound and method of stabilizing on the red phosphorus surface.

Particularly; the preferred red phosphorus that uses through following processing; promptly; use does not form the plane of disruption ground red phosphorus is carried out micronized method, the tunicle of metal component (metal hydroxides or metal oxide) and resin coating combined carry out the multilayer lining and handle on the red phosphorus surface, particularly carrying out multiple lining processing with metal component tunicle lining back with resin-coated.The heat-resistant stability of the red phosphorus of these stabilizations, hydrolytic resistance excellence, because of moisture exist down or the high temperature phosphine that decomposition reaction generated down few significantly, the secure context when making resin combination of the present invention and make moulding product is considered preferably this red phosphorus of use.

The preparation of the red phosphorus of these stabilizations can be opened 2000-169120 communique, spy with reference to the spy and be opened flat 5-229806 communique, spy and open flat 3-259956 communique, spy and open flat 2-209991 communique, spy and open flat 1-150309 communique, spy and open that clear 63-110254 communique, spy are opened clear 62-21704 communique, the spy opens clear 52-125489 communique, EP296501A1 communique, EP249723A2 communique etc.

Red phosphorus can use stabilization red phosphorus usually under the powder shape.The particle diameter of stabilization red phosphorus for example is 0.01～100 μ m, preferred 0.1～70 μ m, more preferably about 0.1～50 μ m.

(B2) nitrogenous compound

Nitrogenous compound (B2) can use salt (b), the salt (c) with amino nitrogenous ring compound and organic phosphoric acid that has amino nitrogenous ring compound (a), has amino nitrogenous ring compound and oxygen acid, nitrogenous ring compound and the salt (d) with nitrogenous compound of hydroxyl, Tripyrophosphoric acid acid amides (e), the carbamide compound (f) etc. with amino.

(a) has amino nitrogenous ring compound

Have amino nitrogenous ring compound and comprise that to have at least one amino and be the heteroatomic heterogeneous ring compound of ring with at least one nitrogen-atoms, heterocycle can also have other heteroatoms such as sulphur, oxygen except nitrogen.These nitrogen heterocyclic rings comprise that imidazoles, thiadiazoles, Thiadiazoline (チ ァ ジ ァ ゾ リ Application), furazan, triazole, thiadiazine, pyrazine, pyrimidine, pyridazine, triazine, purine etc. are with the 5 or 6 yuan unsaturated nitrogen heterocyclic rings etc. of a plurality of nitrogen-atoms as the constituting atom of ring.These contain in the azo-cycle preferably is 5 or 6 yuan of unsaturated azo-cycle, preferred especially triazole and triazines of containing of the constituting atom of ring with a plurality of nitrogen-atoms.

Triazole compounds can be enumerated 1,2,3-triazoles class (1H-1,2,3-triazole species; 2H-1,2,3-triazole species etc.) and 1,2,4-triazole species (1H-1 such as guanazole, 2,4-triazole species; 4H-1 such as guanidine azine, 2,4-triazole species etc.), amino also can (nitrogen-atoms and carbon atom, particularly carbon atom) replace on the appropriate location of triazole ring.Amino number has no particular limits, and can be 1～3, particularly about 1～2.

Triaizine compounds can enumerate 1,3,5-triazines [the cocondensation resin trimeric cyanamide or derivatives thereofs such as (melamine formaldehyde resin, phenol-melamine resin, benzo guanamine-melamine resin, aromatic series polyamine-melamine resins etc.) of trimeric cyanamide, substituted melamine (alkyl melamine, amidino groups trimeric cyanamide etc. such as 2-methyl melamine), trimeric cyanamide condenses (melam, melem, mellon etc.), trimeric cyanamide; Cyanurodiamide; tricyanic acid amidess such as cyanuramide; guanamines; methylguanidine amine (メ チ Le Le グ ァ Na ミ Application); acetoguanamine (ァ セ ト グ ァ Na ミ Application); benzo guanamine; the amber guanamines; guanamines or derivatives thereofs such as CTU-guanamines etc.]; contain amino 1; 2; 3-triazines (5-position; 4; the 5-position; 4; 5; go up by 1 of amino replacement 6-positions etc.; 2, the 3-triazine; 4-amino-benzene-1,2; 3-triazine etc.); contain amino 1; 2,4-triazines (3-position; the 5-position; 3, go up by 1 of amino replacement 5-position etc.; 2,4-triazine etc.) various aminotriazine classes such as.Amino also can (nitrogen-atoms and carbon atom, particularly carbon atom) replace on the appropriate location of triazine ring.Amino number has no particular limits, and can be about 1～4, particularly 1～3 (for example 1～2).

Wherein, preferably contain the aminotriazine compound, especially preferably contain amino 1,3,5-triazines class.(b) have the amino nitrogenous ring compound and the salt of oxygen acid

Can use the nitrogenous ring compound identical with amino nitrogenous ring compound with aforementioned (a).

Also can form salt with oxygen acid with amino nitrogenous ring compound with the nitrogen-atoms position (imido grpup) that constitutes ring, but general preferred with at substitution in ring at least one aminoly form salt with oxygen acid.Have under the situation of a plurality of amino, also amino that can be all forms salt with oxygen acid.A plurality of in addition identical or different nitrogenous compounds (nitrogenous compound of aforementioned nitrogenous ring compound or other band amino) can form salt with a polyacid, can form the double salt of polyacid.

(oxygen acid)

Oxygen acid comprises nitric acid, chloric acid (perchloric acid, chloric acid, chlorous acid, hypochlorous acid etc.), phosphoric acid (non-condensed phosphoric acid that exemplifies in the aforementioned secondary calcium phosphate salt item and condensed phosphoric acid etc.), sulfuric acid (non-condensation sulfuric acid such as permonosulphuric acid, sulfuric acid, sulfurous acid; Condensation such as peroxy-disulfuric acid, pyrosulfuric acid sulfuric acid etc.), boric acid (non-condensation boric acid such as orthoboric acid, metaboric acid; Condensation such as tetraboric acid, boric anhydride boric acid etc.), chromic acid, metaantimmonic acid, molybdic acid, wolframic acid etc.

Preferred oxygen acid comprises phosphoric acid ((many) phosphoric acid), sulfuric acid, boric acid.

(phosphoric acid salt of the nitrogenous ring compound that band is amino)

The phosphoric acid salt of the nitrogenous ring compound that band is amino can be enumerated, the phosphoric acid salt of the nitrogenous triaizine compounds that band is amino, for example non-condensed phosphate (melamine salt of non-condensed phosphoric acids such as ortho-phosphoric acid trimeric cyanamide, phosphonic acids trimeric cyanamide; The melam salt of corresponding aforementioned melamine salt, melem salt, mellon salt, guanamines salt etc.), polyphosphate [Tripyrophosphoric acid melamine class such as the triphosphate of melamine pyrophosphate salt (melamine pyrophosphate, the two trimeric cyanamides of tetra-sodium), corresponding these melamine pyrophosphate salt, tetraphosphate; The melam salt of corresponding aforementioned Tripyrophosphoric acid melamine salt, melem salt, mellon salt, guanamines salt etc.] etc.In addition, polyphosphate also can contain and derives from the vitriolic sulphur atom.Also have, also can use the triazolium salt of corresponding aforementioned triazine salt etc.

The trimeric cyanamide melam melem double salt etc. that polyphosphate also comprises Tripyrophosphoric acid trimeric cyanamide melam melem double salt, metaphosphoric acid trimeric cyanamide melam melem double salt and contains the polyacid (polyacid that also contains sulphur atom, Sauerstoffatom etc. except phosphorus atom) of aforementioned sulphur atom.The details of these double salt can be opened flat 10-306081 communique with reference to the spy, the spy opens flat 10-306082 communique etc.

(vitriol that has amino nitrogenous compound)

The vitriol that has amino nitrogenous compound can be enumerated, the vitriol that has amino triaizine compounds, for example condensation vitriol [the non-condensation sulfuric acid melamine class such as sulfurous acid trimeric cyanamide of sulfuric acid melamine class (sulfuric acid trimeric cyanamide, the two trimeric cyanamides of sulfuric acid, sulfuric acid amidino groups trimeric cyanamide etc.), corresponding sulfuric acid trimeric cyanamide; The melam salt of corresponding aforementioned non-condensation sulfuric acid melamine salt, melem salt, mellon salt, guanamines salt etc.)], condensation vitriol [the melam salt of pyrosulfuric acid melamine class (pyrosulfuric acid trimeric cyanamide, the two trimeric cyanamides of pyrosulfuric acid etc.), corresponding pyrosulfuric acid melamine salt, melem salt, mellon salt, guanamines salt etc.] etc.In addition, can also use the triazolium salt of corresponding aforementioned triazine salt.

In addition, the sulfuric acid trimeric cyanamide can be made by for example special method of opening flat 8-231517 communique record etc.Pyrosulfuric acid two melams can be by for example A.C.S.Symposium Series No.425 " Fire and Polymers ", the 15th chapter, 211～238 pages of (American ChemicalSociety, Washington D.C., 1990), the spy opens method that flat 10-306082 communique puts down in writing etc. and makes.

(borate of the nitrogenous ring compound that band is amino)

The borate of the nitrogenous ring compound that band is amino can be enumerated, the borate of the triaizine compounds that band is amino, for example non-condensation borate [orthoboric acid salt such as the melam salt of orthoboric acid melamine salt orthoboric acid melamine salts such as () orthoboric acid one to three trimeric cyanamides, corresponding aforementioned melamine salt, melem salt, mellon salt, guanamines salt; The metaborate of corresponding aforementioned orthoboric acid salt], multi-borate [condensation boric acid melamine salt (boric anhydride trimeric cyanamide, tetraboric acid trimeric cyanamide etc.), the melam salt of corresponding aforementioned melamine salt, melem salt, mellon salt, guanamines salt] etc.The borate of trimeric cyanamide can be opened method that flat 11-79720 communique puts down in writing etc. and made by for example special clear 54-47750 communique, spy opened.

Aforementioned oxysalt can be separately or with the two or more uses that combine.

The nitrogenous ring compound that band is amino and the ratio of oxygen acid have no particular limits, for example the former/latter's (mol ratio)=1/20～20/1, preferred 1/10～10/1 (for example 1/5～10/1), particularly about 1/2～8/1.Nitrogenous ring compound have no particular limits for example 10/1～1/2, preferred 5/1～1/1, particularly about 4/1～1/1 with the equivalence ratio of the formed salt part of amino and oxygen acid.

(c) the nitrogenous ring compound of band amino and the salt of organic phosphoric acid

The amino nitrogenous ring compound of band can use the nitrogenous ring compound of the band amino that exemplifies in aforementioned (a) item.

Organic phosphoric acid can be enumerated, the part ester of the non-condensed phosphoric acid that exemplifies in the aforementioned secondary calcium phosphate salt item (phosphoric acid (ortho-phosphoric acid etc.), phosphonic acids etc.) and the phosphonic acids that is replaced by organic group or phospho acid etc.As long as organic phosphoric acid has the salifiable position of nitrogenous ring compound shape that at least one can be amino with band.

Phosphoric acid ester (organic ortho-phosphoric acid) comprises the phosphoric acid one or the diester of alcohols (monohydroxy-alcohol or polyvalent alcohol, monohydric phenol or polyatomic phenol).Aforementioned alcohols comprises C such as methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, Stearyl alcohol _1-20Alkyl one alcohols (C particularly _1-10Aliphatics one alcohol); Ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, season C such as pentanediol, glycerol, tetramethylolmethane _1-10How pure aliphatics is; Nitrilo three methyl alcohol etc. are with heteroatomic C _2-10How pure aliphatics is; C such as cyclopentanol, hexalin _5-8An alicyclic alcohol (preferred C _5-6Cycloalkanol); C such as ring pentanediol _5-8Alicyclic diol (preferred C _5-6The cycloalkanes glycol); Phenol, alkylphenol (for example p-or m-cresols, 3, one to three C such as 5-xylenol, trimethylammonium phenol, t-butylphenol, p-octyl phenol, nonyl phenol _1-20Alkylphenol), monobasic phenols such as aryl phenol (for example phenyl phenol, benzylphenol, isopropyl benzene phenol), naphthols, hydroxyl hexichol; Monobasic aralkyl alcohols such as benzylalcohol, styroyl alcohol (C particularly _7-20Aralkyl one alcohols); The aromatic nucleus glycol of carbon numbers about 6～20 such as Benzenediol (Resorcinol, Resorcinol, m-xylylene-glycol, p-xylylene-glycol etc.), naphthylene glycol etc.

These phosphoric acid ester comprise one or two C such as methyl phosphorodithioate, dibutylphosphoric acid ester _1-10Alkyl phosphate; The C of ethylene glycol Monophosphate, pentaerythritol diphosphate etc. _2-10One to four phosphoric acid ester of aliphatic polyol; One phenyl phosphate ester, toluene monooxygenase base phosphoric acid ester, xylene monooxygenase base phosphoric acid ester, single trimethylphenyl phosphoric acid ester, diphenyl phosphoester, two tolyl phosphoric acid ester, bis-xylene base phosphoric acid ester, two trimethylphenyl phosphoric acid ester etc. can have substituting group (C _1-4The phosphoric acid ester of monobasic phenols alkyl etc.) (for example also can have C _1-4One or two C of alkyl _6-14Aryl phosphate ester); Penylene bisphosphate etc. also can be with substituting group (C _1-4One or bisphosphate of polyatomic phenol alkyl etc.) (for example also can be with C _1-4The C of alkyl _6-14Arylene base one or bisphosphate) etc.], alkyl-aryl phosphate ester [C such as aminomethyl phenyl phosphoric acid ester _1-10Alkyl C _6-14Aryl phosphate ester (preferred C _1-6Alkyl C _6-10Aryl phosphate ester) etc.] etc.

Organic phospho acid comprises phosphonic acids one ester of corresponding aforementioned phosphoric acid ester, the organic phospho acid that is replaced by organic group (organic groups such as aliphatic alkyl, alicyclic alkyl, aromatic hydrocarbyl) with the direct bonded hydrogen atom of phosphonic phosphorus atom, organic phospho acid one ester of aforementioned alcohols etc.

Aforementioned organic phospho acid comprises aliphatic phosphonic acids [alkyl phosphonic acids such as methyl-phosphorous acid, ethylphosphonic acid, propyl phosphonous acid, butyl phosphonic acids; 1-hydroxyl (1,1)-ethylidene-1, one or bisphosphonates of aliphatic diols such as 1-di 2 ethylhexyl phosphonic acid; Phosphono C such as phosphonoacetic acid, 3-phosphono propionic acid _1-10The substituting group be with (hydroxyl, carboxyl, ester group etc.) of the phosphono carboxylic-acid of aliphatic carboxylic acid or its carboxylicesters (carboxylic acid esters of phosphono carboxylic acids such as phosphonoacetic acid ethyl ester, 3-phosphono ethyl propionate etc.) etc. etc. by C _1-10Alkyl substituted phosphonic acids (preferred C _1-6Alkyl substituted phosphine acid); C such as ethylene di 2 ethylhexyl phosphonic acid _1-10The alkylene base di 2 ethylhexyl phosphonic acid; Nitrilo three (methylene phosphonic acid) etc. has the heteroatomic phosphonic acids that is replaced by aliphatics multivalence group etc.], aromatic series phosphonic acids [C such as phenyl-phosphonic acid, tolyl phosphonic acids _6-10Arylphosphonic acid; Phosphono C such as phosphono phenylformic acid _7-15The phosphono carboxylic acid of aromatic carboxylic acid or its carboxylicesters (carboxylic acid esters of phosphono aromatic carboxylic acid such as phosphono ethyl benzoate etc.) etc.; The had substituting group (C of penylene base di 2 ethylhexyl phosphonic acid etc. _1-4Alkyl etc.) phosphonic acids that has been replaced by aromatic series multivalence group etc.] etc.Aforementioned in addition organic phospho acid also can be the phosphonic acids (polyvinyl phosphonic acids etc.) that has combined with polymkeric substance.

Organic phospho acid one ester comprises the ester that aforementioned organic phospho acid and the alcohols that exemplifies form in aforementioned phosphoric acid ester item, for example C such as methyl-phosphorous acid monomethyl ester _1-6Alkyl phosphonic acid one C _1-6Alkyl ester; The diester of phosphono carboxylic acid (C such as ethoxy carbonyl methyl-phosphorous acid one ethyl ester, ethoxy carbonyl ethylphosphonic acid one ethyl ester _2-6Alkoxy carbonyl C _1-6Alkyl phosphonic acid one C _1-6Alkyl ester etc.); C such as methyl-phosphorous acid one phenylester _1-6Alkyl phosphonic acid one C _6-10Aryl ester etc.; C such as phenyl-phosphonic acid one methyl esters _6-10Arylphosphonic acid C _1-6Alkyl ester; C such as phenyl-phosphonic acid one phenylester _6-10Arylphosphonic acid one C _6-10Aryl ester etc.In addition, aforementioned phosphonic acid ester also can be annular phosphonate (9, the assorted phenanthrene of 10-dihydro-10-hydroxyl-10-oxo-9-oxa--10-phosphine etc.).

Organic phospho acid comprise the organic phospho acid that combine organic group (alkyl such as aliphatic alkyl, alicyclic alkyl, aryl radical) on the phosphine atom of phospho acid.These organic phospho acid can be enumerated, and corresponding aforementioned replacement phosphonic replaces phospho acid, for example methylethyl phospho acid, diethyl phospho acid etc. one or dialkyl phosphinic acid; Phosphinico-carboxylic acid [phosphinico-two C such as phosphinico-oxalic acid _1-6Aliphatic carboxylic acid; C such as 3-(methyl acid phosphate subunit) propionic acid _1-6Alkylphosphonic acid carboxylic acid subunit-one C _1-6C such as aliphatic carboxylic acid, 3-(phosphenylic acid subunit) propionic acid _6-10Aryl phosphoric acids subunit-one C _1-6The carboxylicesters of aliphatic carboxylic acid, these phosphinico-carboxylic acids etc.; C such as phenyl phosphinic acid _6-10Arylphosphinic acid; Phosphinico-one or two C _6-10Aryl carboxylic acid or its carboxylicesters; C such as aminomethyl phenyl phospho acid _1-6Alkyl C _6-10Arylphosphinic acid; Hydroxyl phospho acid oxide compound (1-hydroxyl dihydro phosphine oxide, the positive phosphine oxide of 1-hydroxyl etc.) etc.

Aforementioned organophosphate can also can use arbitrary salt with the formed salt position of part or all the nitrogenous ring compound formation salt amino with band.Such organophosphate can be enumerated, and contains the salt of amino triaizine compounds, for example the melamine salt of organophosphate (tetramethylolmethane bisphosphonates trimeric cyanamide, tetramethylolmethane bisphosphonates two trimeric cyanamides etc.), C _1-6The melamine salt of alkyl substituted phosphine acid, C _1-6Melamine salt (the 1-hydroxyl (1 of one or bisphosphonates of aliphatic diol, 1)-ethylidene-1,1-di 2 ethylhexyl phosphonic acid two trimeric cyanamides, 1-hydroxyl (1,1)-ethylidene-1,1-di 2 ethylhexyl phosphonic acid four trimeric cyanamides etc.), the phosphonic melamine salt [nitrilo three (methylene phosphonic acid) four melamine salts, nitrilo three (methylene phosphonic acid) six melamine salts etc.] and the C that have replaced with heteroatomic aliphatics multivalence group _6-10Arylphosphonic acid trimeric cyanamide (phenyl-phosphonic acid trimeric cyanamide, phenyl-phosphonic acid two trimeric cyanamides etc.), phosphinico-carboxylic acid melamine salt (aryl phosphoric acids subunit carboxylic acid melamine salts such as 3-(phosphenylic acid subunit) propionic acid trimeric cyanamide, 3-(phosphenylic acid subunit) propionic acid two trimeric cyanamides); Melam salt, melem salt, mellon salt, the guanamines salt of corresponding aforementioned melamine salt; And the double salt of corresponding aforementioned melamine salt such as tetramethylolmethane bisphosphonates trimeric cyanamide melem etc.In addition, also can use the triazolium salt of corresponding aforementioned triaizine compounds salt.These organophosphates can separately or be used in combination of two or more.

The preparation method of the organophosphate of the nitrogenous compound (the particularly amino triaizine compounds of band) that these bands are amino has no particular limits, for example can solution or dispersion liquid (aqueous solution of water system, water-acetone mixed stocker, water-ethanol mixed stocker etc. or suspension liquid etc.) by will containing aforementioned nitrogenous compound and organic phosphoric acid stir, mix, the throw out separation that generates, exsiccant method etc. are made in suitable temperature (for example about 50～100 ℃).

Ratio with amino nitrogenous ring compound and organic phosphoric acid has no particular limits, for example the former/latter's (mol ratio)=1/5～5/1, preferred 1/2～4/1, more preferably about 1/1～2/1.

(d) salt of amino nitrogenous ring compound of band and hydroxyl nitrogenous ring compound

The amino nitrogenous ring compound of band exemplifies the nitrogenous ring compound of the band amino that exemplifies in aforementioned (a) item.

Hydroxyl nitrogenous ring compound comprises by at least one hydroxyl and is the compound that the heteroatomic heterocycle of ring constitutes with at least one nitrogen-atoms.Aforementioned heterocycle can exemplify the heterocycle of the amino nitrogenous ring compound of corresponding aforementioned band.Preferably contain azo-cycle with preceding identical, for a plurality of nitrogen-atoms being 5 or 6 yuan of unsaturated azo-cycle, particularly triazines etc. of containing of the constituting atom of ring.

Triaizine compounds can exemplify, the triaizine compounds of the hydroxyl of the triaizine compounds that exemplifies in the nitrogenous ring compound item of corresponding aforementioned band amino.Hydroxyl also can be gone up at the suitable position (nitrogen-atoms and carbon atom, particularly carbon atom) of triazine ring and replace.The number of hydroxyl has no particular limits, and is about 1～4, particularly 1～3 (for example 2～3).Preferred hydroxyl triaizine compounds is tricyanic acid or derivatives thereofs such as hydroxyl 1,3,5-triazines class, particularly tricyanic acid, isocyanuric acid, cyanurodiamide, cyanuramide etc.

The salt of nitrogenous ring compound that band is amino and hydroxyl nitrogenous ring compound comprises, the salt of triazines and tricyanic acid or derivatives thereof, for example melamine salt of tricyanic acid such as tricyanic acid melamine salt; The melam salt of corresponding melamine salt, melem salt, guanamines salt (for example tricyanic acid guanamines salt, tricyanic acid acetylguanamine salt, tricyanic acid benzo guanamine salt etc.) etc.

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

The ratio of nitrogenous ring compound that band is amino and hydroxyl nitrogenous ring compound has no particular limits, for example the former/latter's (mol ratio)=1/2～3/1, preferred about 1/1～2/1.

(e) Tripyrophosphoric acid acid amides

The Tripyrophosphoric acid acid amides can be enumerated the macromolecular compound of amide containing attitude nitrogen, and this macromolecular compound is obtained by following method, be about to the phosphoric acid class that exemplifies in the aforementioned oxygen acid item and have-N=C=N-or-N=C (N＜) ₂Shown in unitary compound (cyanamide derivative etc.) in the presence of as the urea of wedding agent and/or Ureaphil, burn till, condensation obtains.Aforementioned phosphoric acid can use the part ester (ammonium polyphosphate, Ureaphil etc.) of non-condensed phosphoric acid (ortho-phosphoric acid, metaphosphoric acid etc.), Tripyrophosphoric acid, phosphoric acid etc., aforesaid cyanamide derivative can use the triazines (particularly 1 of trimeric cyanamide etc., 3,5-triazines), various amidine compounds such as dicyanodiamide, guanidine, guanylurea.The Tripyrophosphoric acid acid amides can be used in combination separately or with more than multiple.The Tripyrophosphoric acid acid amides for example can be opened flat 7-138463 communique with reference to the spy.Such Tripyrophosphoric acid acid amides can be made by the method for records such as public clear 51-39271 communique of spy and special public clear 53-2170 communique etc.The Tripyrophosphoric acid acid amides that obtains by the condensation reaction of ammonium polyphosphate and trimeric cyanamide can commodity in use name " ス ミ セ-Off PM " (Sumitomo Chemical (company) manufacturing) commodity etc.

(f) carbamide compound

Carbamide compound comprises non-annularity carbamide compound and ring compound.

(non-annularity carbamide compound)

The non-annularity carbamide compound comprises that N-that substituting groups such as urea, alkyl replace replaces urea [N-C such as N-methyl body, N-ethyl body for example _1-6Alkyl body, alkylene two ureas (C such as MDU for example _1-6Alkylene two ureas etc.) etc. non-annularity uride compound [C such as oxaluric acid], _2-6The ureido-acid of dicarboxylic acid, Ureidoacetic acid etc. contain urea groups C _1-6Monocarboxylic acid, urea groups Succinic Acid etc. contain the C of urea groups _2-6The monoureid of dicarboxylic acid or their derivative (acid amides, ester etc.) etc.; C such as allantoic acid _2-6The diureide of carboxylic acid etc.], acyclic urea condensation body [condenses of polymer, urea and the aldehyde cpd of the dipolymer of urea (for example biuret, two ureas etc.), urea etc.] etc.

(ring-type carbamide compound)

The ring-type carbamide compound if with at least one urea unit be ring the formation unit, have no particular limits, can be any monocyclic compound, and the condensed ring of aromatic hydrocarbon ring, crosslinked ring etc.The ring-type ureas can be enumerated ring-type monoureid, ring-type diureide etc.In addition, the ring-type ureas also comprises the cyclic thiourea class of corresponding aforementioned ring-type urea etc.

The ring-type monoureid can exemplify, alkyleneurea [methylene urea, ethylene-urea, crotonylidene urea C such as (CDU) _1-10Alkyleneurea (preferred C _1-6Alkyleneurea) etc. alkene support urea (C such as vinylene urea, cytosine(Cyt)], _2-10Alkene support urea etc.) alkynes support urea [C _2-10Alkynes support urea (preferred C _2-6Alkynes support urea) etc.], arylene urea (3-imido isatin etc.), uride (the parabanic acid of dicarboxylic acid, cholestrophane, malonyl urea, 5, the 5-vesperal, the nitro malonyl urea, dialuric acid, alloxanic acid, alloxantin, isocyanuric acid, uramil, purpuric acid etc.) uride (uridylic of β-aldehydic acid, methyl uracil (thymus pyrimidine), dihydro-pyrimidin, urazole, benzoyleneurea etc.), uride (the glycolylurea of α-alkyd, 5, the 5-T10,1,1-methylene two (5, the 5-T10), hydantoinses such as wallantoin etc.), or their derivative etc.

The ring-type diureide can exemplify, for example the diureide [1,1-methylene two (5, the 5-T10), wallantoin etc.] of uric acid, 3-methyl-uric acid, urea groups malonyl-support urea, acetylene diureine (glycoluril), α-alkyd; Diureide of two ureas such as p-diurea, dicarboxylic acid (alloxantin, purpuric acid etc.) or their derivative.

The cyclic thiourea class can exemplify ethylene thiourea, sulphur malonyl urea, two sulphur urazoles, 2-thiohydantoin, two 2-thiohydantoins etc.

In addition, in the compound that exemplifies in the aforementioned hydroxyl nitrogenous ring compound item, also can use the enol body with urea serves as to constitute unitary compound (being that tautomer has the unitary compound of urea, for example cyanurodiamide, cyanuramide etc.) etc.

These carbamide compounds can be used alone or in combination of two or more.Preferred carbamide compound is ring-type urea, particularly alkyleneurea, ring-type diureide etc.

(B3) boron-containing compound

Boron-containing compound can be enumerated metal-salt, borophosphoric acid of boric acid etc.

Boric acid is except non-condensation boric acid such as orthoboric acid, metaboric acids; Also can enumerate alkali formula boric acid etc. beyond the aforementioned boric acid that exemplifies such as condensation boric acid such as pyroboric acid, tetraboric acid, five boric acid and eight boric acid.In addition, also can use basic metal (sodium, potassium etc.) etc. as metal, but preferably use alkaline-earth metal (magnesium, calcium etc.), transition metal (manganese, iron, cobalt, nickel etc.), periodic table of elements 2B family metal (zinc, cadmium etc.) polyvalent metal.

Borate metal salt is generally moisture salt, for example can enumerate non-condensation borate [the non-condensation borates of alkaline-earth metal such as orthoboric acid calcium, calcium metaborate; Transition metal condensation borates such as orthoboric acid manganese, cupric metaborate; The non-condensation borate (particularly metaborate) of periodictable 2B family metals such as zinc metaborate, metaboric acid cadmium etc.], condensation borate (alkaline-earth metal condensation borates such as tetraboric acid three magnesium, pyroboric acid calcium; The condensation borate of periodictable 2B family metals such as transition metal condensation hydrochlorate, zinc tetraborate, tetraboric acid cadmiums such as tetraboric acid manganese, hypoboric acid nickel etc.); Alkali formula borate (the alkali formula borate of periodictable 2B family metals such as alkali formula zinc borate, alkali formula cadmium borate etc.) etc.In addition, also can use corresponding these boratory boric acid hydrogen salts (for example orthoboric acid hydrogen manganese etc.) etc.Particularly, preferred alkaline-earth metal or periodictable 2B family metal borate (non-condensation or condensation borate), particularly zinc borate class.

Zinc borate can the commodity in use name " FIRE BREAK シ リ-ズ (for example ZB, 290,415,500 etc.) " (U.S. ボ ラ ッ Network ス (company) manufacturing) but, the commodity of lime borate commodity in use " UBP " (キ Application セ ィ マ テ ッ Network (company) manufacturing) by name etc.

(B4) silicon-containing compound

Silicon-containing compound can be enumerated silicoorganic compound, inorganic silicon compound etc.

Silicoorganic compound comprise (gathering) organo-siloxane.(gathering) organo-siloxane comprises, single organo-siloxane and single polymers (for example polydimethylsiloxane, polyphenyl methyl siloxane etc.) or multipolymer etc. such as dialkylsiloxane (for example dimethyl siloxane etc.), alkylaryl siloxanes (phenyl methyl siloxanes etc.), diaromatic siloxane.In addition, (gathering) organo-siloxane also can use and have substituent modification such as epoxy group(ing), hydroxyl, carboxyl, amino, ether (gathering) organo-siloxane (for example modified silicone etc.) etc. on exposed terminated groups or the main chain.Aforementioned (gathering) siloxanes comprises that also the spy opens 2001-40219 communique, spy and opens 2000-159995 communique, spy and open flat 11-158363 communique, spy and open (gathering) organo-siloxane etc. that flat 10-182832 communique, spy are opened record such as flat 10-139964 communique.In addition, (gather) but the organo-siloxane commodity etc. of commodity in use name " Si パ ゥ ダ-(for example DC4-7051, DC4-7081, DC4-7105, DC1-9641 etc.) " (eastern beautiful ダ ゥ コ-ニ Application グ シ リ コ-Application (company) make), trade(brand)name " XC99-B5664 " (the シ リ of Toshiba コ-Application (company) manufacturing) also.

Inorganic silicon compound comprises tectosilicate (for example zeolite etc.), page or leaf phosphoric acid salt (for example rock, montmorillonite, beidellite, nontronite, hectorite, vermiculite, halloysite, water silicon sodium stone, Network ニ マ ィ ト, Li type fluorine taincolite, Na type fluorine taincolite, Li type tetrasiuicic fluoromica, Na type tetrasiuicic fluoromica etc. take off in talcum, kaolinite, mica, class) etc.

Aforementioned zeolite is not particularly limited, and can use aluminosilicate is that zeolite, aluminosilicophosphate are zeolite, for example specially open the zeolite that flat 7-62142 communique put down in writing [least unit crystal grain is zeolite (A type, X type, Y type, L type, β type and ZSM type zeolite, the mordenite type zeolite of the crystal type aluminosilicate of alkali and/or alkaline-earth metal; Natural zeolites such as chabazite, mordenite, faujusite etc.) etc.] etc.But in addition zeolite also commodity in use name " ゼ ォ ラ system シ リ-ズ ", " HSZ シ リ-ズ " (eastern ソ-(company) manufacturing), trade(brand)name " ゼ ォ ス -シ リ-ズ " (Japanese chemical industry (company) is made, the commodity of trade(brand)name " ZEOLYST シ リ-ズ " (Zeolyst International (company) manufacturing) etc.

(B5) metallic compound

Metallic compound can be enumerated metal hydroxides, metal oxide etc.Be preferably selected from the compound that contains the metallic element beyond silicon or the boron, periodictable 2A family metal (Mg, Ca etc.), transition metal (periodictable 3A family metal such as Sc especially; Periodictable such as Ti, Zr 4A family metal; Periodictable 5A family metals such as V; Periodictable 6A family metals such as Mo; Periodictable 7A family metals such as Mn; Periodictable the 8th family's metals such as Fe, Co, Ni; Periodictable 1B family metals such as Cu etc.), the metal hydroxides or the metal oxide of at least a metal in periodictable 2B family metal (Zn etc.), periodictable 5B family metal (Sb etc.), aluminium and the tin.

Such metal hydroxides for example can be enumerated aluminium hydroxide, magnesium hydroxide, nickeliferous magnesium hydroxide (for example " Off ァ ィ Application マ グ SN etc. ", stannic hydroxide, zirconium hydroxide, alkali formula zinc, the hydrotalcite of テ ィ-ェ system ジ-(company).In addition, metal oxide can be enumerated for example molybdenum oxide, Tungsten oxide 99.999, titanium oxide, zirconium white, stannic oxide, cupric oxide, zinc oxide, aluminum oxide, nickel oxide, ferric oxide, manganese oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, four weisspiessglanzs, antimony pentaoxide, sodium antimonate etc.

Aforementioned component (B) (fire retardant (B)) can be used alone or in combination of two or more.Preferred ingredient (B) is P contained compound (B1) especially, closes nitrogen compound (B2).

[usage ratio of fire retardant]

Fire retardant of the present invention, because with secondary calcium phosphate salt (A) and at least a component (B) and the polyphenylene oxide as required that are selected from P contained compound, nitrogenous compound, boron-containing compound, silicon-containing compound and metallic compound is resin combination, so even interpolation also can be given high flame retardant resistance to far-ranging base resin (thermoplastic resin etc.) on a small quantity.With respect to the ratio of the fire retardant of base resin as long as just have no particular limits without detriment to the characteristic of resin, with respect to base resin 100 weight parts, fire retardant is about 0.1～300 weight part (for example 1～300 weight part), preferred 10～300 weight parts, further preferred 20～250 weight parts (for example 30～200 weight parts).

As the polyphenylene oxide of base resin be resin (polyphenylene oxide be resin separately, polyphenylene oxide is resin and polyester based resin and uses etc.) with by the flame retardant combination use of secondary calcium phosphate salt (particularly anhydrous in fact secondary calcium phosphate salt) and phosphoric acid ester (particularly condensed phosphoric acid esters) formation the time, the flame retardant resistance of resin can be more effectively improved, oozing out of fire retardant can also be reduced simultaneously.At this moment, even the ratio of fire retardant is for being about 0.1～100 weight part, preferred 1～80 weight part (particularly 1～50 weight part) with respect to base resin 100 weight parts on a small quantity, for example, also fire-retardantization effectively, with respect to phosphoric acid ester P contained compound 100 weight part polyphenylene oxide such as (condensed phosphoric acid esters) be the ratio of resin be 10～200 weight parts, preferred 20～150 weight parts, more preferably about 30～100 weight parts.

The ratio of secondary calcium phosphate salt (A) can be in the scope that can give flame retardant resistance be suitably selected in the fire retardant, with respect to total amount 100 weight parts of component (B) (P contained compound, nitrogenous compound, boron-containing compound, silicon-containing compound, sulfocompound, metallic compound) be 1～1000 weight part, preferred 5～500 weight parts, more preferably about 10～300 weight parts.

[arborescens flame retardant]

Flame retardant resin composition of the present invention also can further contain the arborescens flame retardant.Such arborescens flame retardant is included in the aromatic resin (C) that the resin (C1), the polyarylate that have hydroxyl and/or amino aromatic nucleus on main chain or the side chain are resin (C2), aromatic epoxy resin (C 3).

(C1) on main chain or side chain, has the resin of hydroxyl and/or amino aromatic nucleus

Have the resin of aromatic ring to exemplify on the main chain, for example lacquer has the resin of aromatic nucleus can exemplify aromatic vinyl resin with resol, aralkyl resin on the side chain.

(1-1) lacquer resol

Lacquer has the repeating unit shown in the following formula (10) with resol,

(in the formula, R ²¹～R ²³Can be identical or different, expression hydrogen atom, alkyl or aryl, s is the integer more than 1).

Alkyl and aryl can be enumerated aforementioned R ⁵～R ⁷The C that exemplifies in _1-20Alkyl (C particularly _1-12Alkyl), C _6-20Aryl and substituted aryl (C particularly _1-4Alkyl substituting aromatic base).

Lacquer is obtained by phenols and aldehydes reaction usually with resol (particularly random lacquer resol).Phenols can be enumerated monohydric phenol that exemplifies in the phosphoric acid ester item in the aforementioned nitrogenous compound (B2) etc.These phenols can use one or more to be used in combination.

Aldehydes can be enumerated for example aromatic aldehydes such as fatty aldehyde such as formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, phenylacetic aldehyde etc.Preferred aldehydes can be enumerated formaldehyde etc.Also can use the condenses of formaldehyde such as trioxane, paraformaldehyde in addition.The ratio of phenols and aldehydes for the former/latter=1/0.5～1/1 (mol ratio) about.

The condensation reaction of phenols and aldehydes is carried out in the presence of acid catalyst usually.Acid catalyst can be enumerated for example organic catalyst (for example hydrochloric acid, sulfuric acid, phosphoric acid etc.), organic catalyst (p-toluenesulphonic acids, oxalic acid etc.) etc.

In addition, also just can use/secondary than being that height more than 1 is just coating with lacquer with resol as lacquer resol.Lacquer with the methylene base of resol and the combination of the hydroxyl of various aromatic nucleus have (i) normotopia combine with normotopia (ii) normotopia combine with secondary position (iii) second month in a season and the second month in a season bonded situation.

If bonded methylene bond number is that Mp, normotopia and secondary position bonded methylene bond number are M between the secondary position ₀Bonded methylene bond number is M between p, the normotopia ₀, then just/secondary than being expressed from the next.

Just/secondary ratio=[M ₀+ (1/2) M ₀P]/[Mp+ (1/2) M ₀P]

For example by ¹³The methylene bond number that C-NMR spectrum records, just can calculate/secondary ratio according to following formula.

Particularly as lacquer resol.Preferred just use the/secondary than be more than 1, for example 1～20 the lacquer about (particularly 1～15) with resol, be that so-called height is just coating with lacquer and uses resol.

Just/secondary than being that lacquer more than 1 for example can be synthesized by following method with resol, (1) in the presence of at least a catalyzer that is selected from metal-salt, metal oxide, metal hydroxides and amine compound or after further addition-condensation reaction, add acid catalyst, make the method that phenols and aldehydes react [for example the spy opens clear 55-90523 communique, spy and opens that clear 57-51714 communique, spy are opened clear 59-80418 communique, the spy opens clear 62-230815 communique, No. 4113700 specification sheets of United States Patent (USP) etc.]; (2) in non-polar solvent (for example alicyclic hydrocarbon such as aromatic hydrocarbons such as dimethylbenzene, toluene, benzene, hexanaphthene etc.), add the method [for example the spy opens flat 6-345837 communique, Macromol.Chem.182,2973 (1981) etc.] of depressing, make phenols and aldehydes reaction; (3) under the catalyst-free, strict control manufacture method and condition, method [for example the spy opens flat 10-195158 communique, the spy opens flat 10-204139 communique etc.] that phenols and aldehydes are reacted; (4) make method that metal phenol salts such as the magnesium bromide of phenol, the magnesium that methylates and aldehydes react [for example No. 4097463 specification sheets of United States Patent (USP), Macromolecules, 17,19 (1984) etc.] etc. in above-mentioned non-polar solvent.The ratio of phenols and aldehydes for the former/latter=1/0.3～1/1 (mol ratio) about.

Metal salt catalyst for example can be enumerated the polyvalent metal salt of organic acid (for example sulfonic acid such as aliphatic carboxylic acids such as acetate, naphthenic acid, oxalic acid, methylsulfonic acid etc.) (for example Zn, Mg, Mn, Cd, Ca, Co, Pb, Cu, Ni, the salt of Al etc.).Metal oxide and metal hydroxides for example can be enumerated polyvalent metal oxides, multivalent metal hydroxides (for example Zn, Mg, Mn, Cd, Ca, Co, Pb, Cu, Ni, the oxide compound of Al etc., oxyhydroxide etc.) etc.Amine compound can be enumerated for example fatty amine (for example dimethyl amine, diethylamide etc.).These catalyzer can use in independent or two or more mixing.

Even height is just coating with lacquer with aforementioned catalyzer such as resol kish salt, metal oxide, metal hydroxidess and also can use, but the preferred amount that reduces residual catalyst of handling by washing etc.The height that is obtained by aforementioned (3) method is just coating with lacquer with resol because do not use catalyzer in addition, does not therefore need to remove catalyzer, so be that preferred height is just coating with lacquer and uses resol.

In addition, also can use aforementioned phenols and dihydroxy-benzene class, aphthols, bisphenols (for example aforementioned Z ¹And Z ²The bisphenols that exemplifies in), the cocondensation compound of cocondensation components such as alkyl benzene (for example toluene, ethylbenzene, dimethylbenzene, sym-trimethylbenzene etc.), phenyl amines, furfural class, ureas and triazines (for example urea, tricyanic acid, isocyanuric acid, trimeric cyanamide, guanamines, acetylguanamine, benzo guanamine etc.) terpene hydrocarbon, laccol class, rosin based.Particularly the aminotriazine lacquer through the triazines modification is preferred cocondensation compound with resol.Such aminotriazine lacquer with resol can by with phenols, triazines and formaldehydes the existence of basic catalyst (ammonia, Trimethylamine, trimethanolamine etc.) and/or an acidic catalyst (oxalic acid etc.) or non-in the presence of the method [for example DIC Technical Review No.3, p47 (1997), spy open flat 8-253557 communique, the spy opens flat 10-279657 communique etc.] of cocondensation make.The aminotriazine lacquer can commodity in use name " Off ェ ノ ラ ィ the ト " (commodity of big Japanese ink chemical industry (company) with resol.

In addition, also can use and to coat with lacquer with the part or all of phenol hydroxyl of resol (random lacquer is just coating with lacquer with resol and height and using resol) with being selected from phosphorus compound (phosphoric acid for example, phosphorous acid, organic phospho acid, phosphoric acid class and their acid anhydrides such as organic phospho acid, halogenide, salt, ester (particularly aliphatic ester) etc.), and boron compound (boric acid (boric acid for example for example, organic boronic, boric acid class and their acid anhydrides such as organic borinic acid, halogenide, salt, ester etc.) (for example phosphoric acid modification coats with lacquer and uses resol the modification lacquer after at least a modification with resol, boric acid modified lacquer is with resol etc.).Lacquer is modified as phosphoric acid ester or boric acid ester usually with the hydroxyl of resol.

Also have, the modification after also can using the part or all of hydrogen atom that will coat with lacquer with the phenol hydroxyl of resol (random lacquer is just coating with lacquer with resol and height and using resol) with metal ion, silyl or organic group (alkyl, alkyloyl, benzoyl group etc.) modification (or replacement) is coated with lacquer and is used resol.

Preferred lacquer can be enumerated with resol, phenol formaldehyde (PF) lacquer resol, alkylphenol formaldehyde resin (for example, t-butylphenol formaldehyde coats with lacquer with resol, p-octyl phenol formaldehyde resin) and their cocondensation compound and their mixture.

Number-average molecular weight is not particularly limited can be by 300～5 * 10 with resol (random lacquer is just coating with lacquer with resol and height and using resol) for lacquer ⁴, preferred 300～1 * 10 ⁴, more preferably the scope about 300～8000 (special 300～5000) is selected.

(1-2) aralkyl resin

The aralkyl resin that uses among the present invention can use the resin with the structural unit shown in the following formula (11).In addition, aralkyl type resin, for example phenol phenylbenzene aralkyl type resin, phenol penylene aralkyl type resin, the phenol diphenyl ether aralkyl type resin that also can use the spy to open to put down in writing in the 2000-351822 communique as aforementioned aralkyl resin, contain naphthylene aralkyl type resin (naphthols aralkyl type resin etc.), phenol anthracene aralkyl type resin etc.

(Ar represents aromatic group in the formula, Z ⁵And Z ⁶Identical or different, expression alkylene base, R ²⁴Expression hydrogen atom or alkyl.X represents hydroxyl, amino or N-substituted-amino).

The aromatic group that Ar represents can be enumerated the aromatic group, for example penylene base (o-penylene base, m-penylene base, p-penylene base etc.), naphthylene base of carbon number 6～20 etc., preferred penylene base (particularly p-penylene base).

Z ⁵And Z ⁶The alkylene base of expression can be enumerated aforementioned Z ¹And Z ²Alkylene base (the C that exemplifies in _1-4Alkylene base, particularly C _1-2Alkylene base).R ²⁴The alkyl of expression can be enumerated aforementioned R ⁵～R ⁷The C that exemplifies in _1-20Alkyl (C particularly _1-4Alkyl).

The N-substituted-amino that X represents comprises one or two C _1-4Alkylamino, for example dimethylamino, diethylamino.

As the aralkyl resin, use the phenol aralkyl resin of X for hydroxyl more.Preferred phenol aralkyl resin comprises Z ⁵And Z ⁶For methylene base, Ar are penylene base, R ²⁴For hydrogen atom, have with the p-dimethylbenzene substituted phenol shown in the following formula (12) for repeating unitary resin.

The aralkyl resin generally can obtain by the compound shown in the following formula (13) and the reaction of phenols or phenyl amines.Use phenols can obtain phenol aralkyl resin, use phenyl amines can obtain aniline aralkyl resin,

Y-Z ⁷-Ar-Z ⁸-Y (13)

(in the formula, Y is alkoxyl group, acyloxy, hydroxyl or halogen atom.Ar, Z ⁷And Z ⁸As hereinbefore).

The alkoxyl group of Y representative comprises C such as methoxyl group, oxyethyl group, propoxy-, butoxy in the formula (13) _1-4Alkoxyl group.Acyloxy comprises the acyloxy of carbon numbers about 2～5 such as ethanoyl.Halogen atom comprises ammonia, bromine, iodine etc. in addition.

The compound of following formula (13) expression can exemplify xylylene-glycol C _1-4Alkyl oxide aralkyl ethers, p-xylylene-α α '-acyl-oxygen aralkyl classes such as diacetate esters, p-xylylene-α α '-aralkyl glycolss such as glycol, p-xylylene-α α '-dichloride, p-xylylenes-α α '-aralkyl halogenide classes such as dibromide such as (p-xylylene-glycol dme, p-xylylene-glycol diethyl ether etc.).

Phenols can be enumerated phenol or the alkylphenol that exemplifies in the phosphoric acid ester item of for example aforementioned nitrogenous compound (B2).These phenols can use a kind or be used in combination of two or more.

The arylamine class for example can be enumerated arylamine, alkylarylamine (C such as Tolylamine, xylidene(s), octyl group arylamine, nonyl arylamine for example _1-20Alkylarylamine) and N-alkylarylamine (N for example, N-dimethyl arylamine, N, N-C such as N-diethyl arylamine _1-4Alkylarylamine).These arylamine classes can be used a kind or be used in combination of two or more.

The ratio of the compound of following formula (13) and phenols or arylamine class for for example the former/latter=1/1～1/3 (mol ratio) about, about preferred 1/1～1/2.5 (mol ratio).

The reaction of the compound of formula (13) and phenols or arylamine class can be carried out in the presence of catalyzer, also can carry out in the presence of catalyst-free.For example use the situation of aralkyl ethers, can in the presence of catalyzer, react, use the situation of aralkyl halogenide class, can in the presence of catalyst-free, react as the compound of formula (13) as the compound of formula (13).Catalyzer can be enumerated, for example friedel-crafts catalysts such as dimethyl sulfate, diethyl sulfuric acid, tin chloride, aluminum chloride.

Previous reaction can be carried out in the presence of solvent exists or be solvent-free in addition.Temperature of reaction for example is about 50～250 ℃, preferred about 100～230 ℃.Also have, use under the situation of aralkyl halogenide class as reactant, the also comparable said temperature of temperature of reaction is low, for example also can be about 50～150 ℃, particularly about 70～130 ℃.

In addition, in the previous reaction except phenols and/or amine also can with following component and usefulness, promptly aldehydes (except aforementioned lacquer with also having benzaldehyde etc. the aldehyde that exemplifies in the resol item), hydroxy-benzoic acid class (for example, p-hydroxy-benzoic acid; P-hydroxy-benzoic acid alkyl esters such as p-methyl hydroxybenzoate, p-nipagin A etc.), Hydroxybenzenes (dihydroxy-benzene, trihydroxybenzene etc.), aphthols (for example 1-naphthols, beta naphthal, 1,6-dihydroxy naphthlene, 2,7 dihydroxy naphthalene, hydroxynaphthoic acid, hydroxynaphthoic acid alkyl ester etc.), bisphenols is (except aforementioned Z ¹And Z ²In also have Bisphenol F, bisphenol S, bis-phenol-sulfone etc. beyond the bisphenols that exemplifies), arylamine class, furfural class, aforementioned lacquer be with cocondensation components such as the alkyl benzene that exemplifies as the copolymerization component in the resol item, ureas and triazines.

In addition, as the aralkyl resin also can use at least a portion X representative hydroxyl or amino by be selected from aforementioned lacquer with at least a modification of the phosphorus compound that exemplifies in the resol item, boron compound and epoxy compounds (epoxy chloropropane etc.) modification aralkyl resin (for example phosphoric acid modification phenol aralkyl resin, epoxide modified phenol aralkyl resin, phosphoric acid modification arylamine aralkyl resin, boric acid modified phenol aralkyl resin, boric acid modified arylamine aralkyl resin etc.).The common correctability of the hydroxyl of aralkyl resin is phosphoric acid ester, boric acid ester or glycidyl ether, and amino correctability usually is phosphoamide or boric acid acid amides.

The softening temperature of the aralkyl resin that obtains like this for for example about 40～160 ℃, preferred about 50～150 ℃, more preferably about 55～140 ℃.

Also can harden or modification to the aralkyl resin as required in addition.Sclerosis or modification can promptly utilize the methylene of polyamine (urotropin etc.) crosslinked by customary way usually, utilize the epoxy cross-linking etc. of epoxy compounds (encircling epoxide) to carry out more.

Also have, the aralkyl resin also can carry out modified rubber as required.Modified rubber can carry out chemical modification by synthetic rubber, polyolefine rubber such as (polyisobutene, polyethylene etc.).

(1-3) aromatic vinyl resin

Aromatic vinyl resin for example can use has the unitary resin of ground structure shown in the following formula (14),

(in the formula, R ²⁵Expression hydrogen atom or C _1-3Alkyl, R ²⁶Expression aromatic ring, t are 1～3 integer).

Preferred C in the formula (14) _1-3Alkyl can be enumerated methyl.Aromatic ring can be enumerated in addition, for example C such as benzene, naphthalene nucleus _6-20Aromatic ring.In addition, aromatic ring also can have substituting group (hydroxyl for example; Aforementioned R ⁵～R ⁷The alkyl that exemplifies in; The alkoxyl group that exemplifies in the aforementioned Y item etc.).

Also organic group (protecting group) protections such as available metal ion, silyl or alkyl, alkyloyl, benzoyl group of the hydrogen atom of hydroxyl in the formula (14).

The resin that is obtained by these derivatives has for example structure unit shown in the following formula (15),

(in the formula, R ²⁵As hereinbefore.R ²⁷For be selected from-OH ,-OSi (R ²⁸) ₃And-(M is metallic cation, OR to OM ²⁸And OCOR ²⁸, R ²⁸For having the alkyl or aryl of 1～5 carbon atom) group.Also have, u is 1～3 integer.)。

Before in the formula M can be any of monovalence metallic cation (sodium, lithium, potassium etc.) or diatomic base great soil group metallic cation (magnesium, calcium etc.) or transition-metal cation.

The substituent R of preceding formula ²⁷Can be in arbitrary position of normotopia, off normal or burnt position.Except substituent R ²⁷Outward, the side aromatic ring also can be by C _1-4Alkyl replace.

Aromatic ethylene base system resin comprise corresponding aforementioned structure unit (14) the aromatic vinyl monomer with hydroxyl separately multipolymer or with other the multipolymer etc. of co-polymerized monomer.

Aromatic vinyl monomer comprises, for example aromatic vinyl monomer of hydroxyls such as vinyl phenol, dihydroxy-benzene ethene, hydroxyl naphthols etc.These aromatic vinyl monomers can be used alone or in combination of two or more.

Other co-polymerized monomer can be enumerated, for example (methyl) acrylic monomer [(methyl) vinylformic acid, (methyl) acrylate ((methyl) vinylformic acid C such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-ethylhexyl acrylate for example _1-18Alkyl ester; Hydroxyl monomers such as (methyl) vinylformic acid 2-hydroxyl ethyl ester; (methyl) glycidyl acrylate etc.), (methyl) acrylamide, (methyl) vinyl cyanide etc.], styrenic monomers (vinylbenzene for example, Vinyl toluene, alpha-methyl styrene, chloro-styrene, vinyl naphthalene, vinyl cyclohexane etc.), polymerizability polyvalent carboxylic acid (fumaric acid, toxilic acid etc.), the maleic anhydride imines that contracts is monomer (the maleic anhydride imines that contracts, the N-alkyl maleic anhydride imines that contracts, the N-phenyl maleic anhydride imines etc. that contracts), diene monomer (isoprene, 1, the 3-divinyl, 1, the 4-hexadiene, Dicyclopentadiene (DCPD) etc.), ethene base system monomer (for example, vinyl-acetic ester, vinyl esters such as propionate; Vinyl ketones such as methyl vinyl ketone, methyl isopropenyl ketone; Vinyl ethers such as vinyl isobutyl ether, methoxy ethylene; Nitrogenous vinyl monomers such as N-vinylcarbazole, N-ethenyl pyrrolidone, N-vinyl imidazole etc.).These co-polymerized monomers can use one or two or more kinds.

The ratio of vinyl monomer and co-polymerized monomer for example is 10/90～100/0 (weight %), preferred 30/70～100/0 (weight %), more preferably about 50/50～100/0 (weight %).

Preferred aromatic vinyl resin is vinyl phenol list polymers (polycarboxylated styrene), particularly p-vinyl phenol list polymers.

The number-average molecular weight of aromatic ethylene base system resin has no particular limits for example can be 300～50 * 10 ⁴, preferred 400～30 * 10 ⁴, more preferably 500～5 * 10 ⁴About scope select.

(C2) polyarylate is a resin

Polyarylate is the compound that resin can use the structural unit with following formula (16) expression,

[-O-Ar-OC(O)-A ²-C(O)-] (16)

(Ar represents aromatic group, A in the formula ²Expression aromatics, alicyclic or aliphatic group).

Such polyarylate is that resin can utilize ester-interchange method (for example acetin method, phenyl ester method etc.), chloride of acid method, direct method or addition polymerization method etc., the manufacturings such as use melt phase polycondensation, solution polymerization process or interfacial polymerization as polyesterification reaction.

Polyarylate is that resin can and obtain by the reaction of the many alkoxide components of aromatic series and poly carboxylic acid component (aromatic multi-carboxy acid's component, aliphaticpolycarboxylic acid component, ester ring type poly carboxylic acid component etc.).The poly carboxylic acid component contains aromatic multi-carboxy acid's component usually at least.

The many alcohol of aromatic series (monomers) use glycol such as monocyclic aromatic diol, polycycle aromatic diol or their reactive derivatives [for example the ester (acetic ester etc.) of the salt (sodium salt, sylvite etc.) of the many alcohol of aromatic series, the many alcohol of aromatic series, through the many alcohol of aromatic series (trimethyl silyl things etc.) of silyl protection etc.] usually.

The monocyclic aromatic diol can be enumerated the aromatic ring glycol of carbon numbers about 6～20 such as Benzenediol for example (Resorcino, to biphenol, m-xylylene-glycol, p-xylylene-glycol etc.), naphthalene glycol.

The polycycle aromatic diol can be enumerated two (hydroxyaryl) class (bisphenols), two (hydroxyaryl) paraffinic hydrocarbonss that for example exemplify in aforementioned polycarbonate-based resin item and two (hydroxyaryl) naphthenic hydrocarbon to be also had, 4,4 '-dihydroxyl hexichol, 2,2 '-diphenol, two (hydroxyaryl) carboxylic acid [two-4, two (hydroxyaryl) C such as 4-(hydroxyphenyl) butyric acid _2-6Carboxylic acid etc.] etc.In addition, other polycycle aromatic diol also comprises compound with two (hydroxyaryl) skeleton, aforementioned Z for example ¹And Z ²Two (hydroxyphenyl) ether, two (hydroxyphenyl) ketone, two (hydroxyphenyl) sulfoxide of exemplifying in also have two (hydroxyphenyl) thioether, two (C in addition _1-4Alkyl replaces hydroxyphenyl) paraffinic hydrocarbons [two (3-methyl-4-hydroxyphenyl) methane, two (3-methyl-4-hydroxyphenyl) propane, two (3 for example, 5-dimethyl-4-hydroxyphenyl) methane, two (3,5-dimethyl-4-hydroxyphenyl) propane etc.], terpene hydrocarbon diphenols (for example 1,4-two (C _1-4Alkyl replaces hydroxyphenyl)-the p-terpane etc.) etc.

The many alcohol of these aromatic series can use one or more to be used in combination.

The many alcohol of optimization aromatic comprise bisphenols, two (hydroxyaryl) C for example _1-6Paraffinic hydrocarbons, (for example dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D etc.) etc.

The many alcohol of aforementioned in addition aromatic series also can and be used with aliphatics or the many alcohol of ester ring type.The many alcohol of aliphatics can be enumerated C such as ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, season pentanediol _1-10How pure aliphatics is.The many alcohol of aforementioned in addition aliphatics also comprise 1, and 4-cyclohexanedimethanol etc. has C _3-10How pure the aliphatics of aliphatic series ring is.The many alcohol of ester ring type can be enumerated C such as cyclohexanediol _3-10How pure ester ring type is.

The aromatic multi-carboxy acid can enumerate for example dicarboxylic acid such as monocyclic aromatic dicarboxylic acid, polycycle aromatic dicarboxylic acid or their reactive derivatives [for example aromatic multi-carboxy acid's carboxylic acid halides (aromatic multi-carboxy acid's acyl chlorides etc.), aromatic multi-carboxy acid's ester (alkyl ester, aryl ester etc.), aromatic multi-carboxy acid's acid anhydrides etc.].

Monocyclic aromatic ring dicarboxylic acid comprises for example aryl dicarboxylic acid of carbon numbers about 8～20 such as benzene dicarboxylic acid (phthalic acid, m-phthalic acid, terephthalic acid etc.), naphthalene dicarboxylic acids.Also can replace 1 or 2 C on this external aforesaid benzene dicarboxylic acid and the naphthalene dicarboxylic acids (particularly benzene dicarboxylic acid) _1-4Alkyl.

The polycycle aromatic dicarboxylic acid can be enumerated two (carboxyl aryl) C such as two (aryl carboxylic acid) class, for example diphenyldicarboxylic acid, two (carboxyl phenyl) methane _1-6Paraffinic hydrocarbons; Two (carboxyl aryl) C such as two (carboxyl phenyl) hexanaphthene _3-12Naphthenic hydrocarbon; Two (carboxyl aryl) ketone such as two (carboxyl phenyl) ketone; Two (carboxyl aryl) sulfoxides such as two (carboxyl phenyl) sulfoxide; Two (carboxyl aryl) ethers such as two (carboxyl phenyl) ether; Two (carboxyl phenyl) thioether etc. two (carboxyl aryl) thioether etc.

Preferred aromatic series polyacid component comprises monocyclic aromatic dicarboxylic acid (particularly benzene dicarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid), two (carboxyl aryl) C _1-6Paraffinic hydrocarbons etc.

Aliphaticpolycarboxylic acid (monomer) can be enumerated aliphatic dicarboxylic acid, and (aliphatic dicarboxylic acid that exemplifies in the aforementioned polyamide-based resin item also has C such as oxalic acid, propanedioic acid, Succinic Acid in addition _2-20Aliphatic dicarboxylic acid), and but dicarboxyl methylcyclohexane etc. have C _3-10The dicarboxylic acid of aliphatics ring.

The ester ring type poly carboxylic acid comprises the ester ring type dicarboxylic acid, for example C such as cyclohexane dicarboxylic acid _3-20The ester ring type dicarboxylic acid.

Preferred polyarylate is that resin can enumerate with the bisphenols is the polyester that forms of polyarylate resin, for example bisphenols (dihydroxyphenyl propane, dihydroxyphenyl propane D, Bisphenol F etc.) and the benzene dicarboxylic acids (m-phthalic acid, terephthalic acid etc.) of the many alcohol of aromatic series, bisphenols and two (aryl carboxylic acid) class [two (carboxyl aryl) C such as two (carboxyl phenyl) methane, two (carboxyl phenyl) ethane, two (carboxyl phenyl) propane for example _1-4Alkyl] polyester that forms etc.These polyarylates are that resin can separately or be used in combination of two or more.

In addition polyarylate be resin except using aromatic diol and aromatic dicarboxylic acid also can be as required and with aromatic series triol, aromatic series tetrol [for example 1,1,2,2-four (hydroxyphenyl) ethane etc.], aromatic tricarboxylic acids, aromatic tetracarboxylic acid etc.

In addition, polyarylate is the sealing such as the also available alcohols of end group, carboxylic-acid (particularly monovalence alcohols, monovalence carboxylic-acid etc.) (combination) of resin.The sealing polyarylate is that the monovalence alcohols of resin end group comprises that for example monovalence aryl alcohols (can be by C _1-10Alkyl and/or C _6-10The monovalence phenols that aryl replaces, for example phenol, adjacent,, contraposition has 1～2 C such as methyl _1-4The alkylphenol of alkyl; Adjacent,, contraposition has the aryl phenol etc. of phenyl, phenmethyl, cumyl etc.), univalent alkyl alcohols (C such as methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, Stearyl alcohol _1-20Alkyl one alcohols) univalent aralkyl alcohols (C such as phenylcarbinol, phenylethyl alcohol _7-20Aralkyl one alcohols) etc.

Sealing (combination) polyarylate is that the monovalence carboxylic-acid of resin end group comprises univalent aliphatic series carboxylic acid (acetate, propionic acid, C such as sad _1-20The aliphatics monocarboxylic acid), monovalence ester ring type carboxylic acid (C such as hexahydrobenzoic acid _4-20The ester ring type monocarboxylic acid), the monovalence aromatic carboxylic acid (phenylformic acid, toluylic acid, neighbour,, C such as right-the tert-butylbenzoic acid, p-anisole guanidine-acetic acid _7-20The aromatic series monocarboxylic acid) etc.In addition, aforementioned carboxylic-acid also can be univalent aliphatic series carboxylic acid that toluylic acid etc. replaces through aromatic base (particularly through C _6-20The C that aromatic group replaces _1-10The aliphatics monocarboxylic acid).

Polyarylate is that resin can be that resin beyond the resin, for example polymeric amide, polyester, polycarbonate etc. constitute the polymerization alloy with polyarylate also in addition.Aforementioned polymerization alloy comprises that not only the simple mixing thing also comprises through the polymerization alloy of transesterification reaction or contains the polymerization alloy of compatibilizing agent.

Polyarylate is that the number-average molecular weight of resin for example is 300～30 * 10 ⁴About, preferred 500～10 * 10 ⁴About, more preferably 500～5 * 10 ⁴About.

(C3) aromatic epoxy resin

Aromatic epoxy resin comprises that ether is Resins, epoxy (for example bisphenol-type epoxy resin, novolac-type Resins, epoxy etc.), to have used the amine of aromatic amine component be Resins, epoxy etc.

The bis-phenol that constitutes bisphenol-type epoxy resin is identical with aforementioned two (hydroxyaryl) class.Preferred bisphenol-type epoxy resin can be enumerated two (hydroxyaryl) C _1-6The glycidyl ether of paraffinic hydrocarbons, particularly dihydroxyphenyl propane, dihydroxyphenyl propane D, Bisphenol F etc. etc.Bisphenol-type epoxy resin also comprises the aforementioned bis-phenol glycidyl ether (being phenoxy resin) that molecular weight is big in addition.

The lacquer that constitutes novolac-type Resins, epoxy can be enumerated aforementioned lacquer with the resin that exemplifies in resol (1-1) item with resol, for example alkyl (C for example _1-20C such as alkyl, preferable methyl, ethyl _1-4Alkyl) can the nuclear substituted lacquer of aromatic series with resol (for example phenol-lacquer with resol, cresols-lacquer with resol etc.), with ureas or triazines modification lacquer resol (for example aminotriazine coat with lacquer with resol etc.).Preferred novolac-type Resins, epoxy comprises C _1-2The commutable lacquer of the alkyl glycidyl ether of resol.

Formation amine is that the aromatic amine component of Resins, epoxy can be enumerated monocyclic aromatic amine (arylamine, Tolylamine etc.), monocyclic aromatic diamine (diaminobenzene, xylylene diamines etc.), the amino alcohol of monocyclic aromatic series (hydroxy amino benzene), polycycle aromatic series diamines (diaminodiphenyl-methane etc.), polycycle aromatic series amine etc.

The number-average molecular weight of Resins, epoxy for example is about 200～50,000, preferred about 300～10,000, more preferably about 400～6,000 (for example about 400～5,000).The number-average molecular weight of phenoxy resin for example is about 500～50,000, preferred about 1,000～40,000, more preferably about 3,000～35,000 in addition.

It is that solidifying agent (for example aromatic amines such as aliphatic amide, mphenylenediamine, xylylene diamines such as quadrol etc.), polyaminoamide are that solidifying agent, acid and acid anhydrides are that solidifying agent such as solidifying agent are cured that Resins, epoxy also can use amine.

These arborescens flame retardants can be used alone or in combination of two or more.With respect to the base resin of 100 weight parts, the ratio of arborescens flame retardant for example is 0.1～50 weight part, preferred 1～40 weight part, more preferably about 10～30 weight parts.

[other fire retardant]

In addition, flame retardant resin composition of the present invention is for the fire retardant further giving flame retardant resistance and also can contain other for example sulfur-bearing fire retardant (sulfocompound), pure flame retardant, inorganic flame retardant etc.

Sulfocompound can be enumerated sulfuric ester, also has organic sulfonic acid, thionamic acid, organic thionamic acid and their salt (for example metal-salt, with the salt of aminotriazine compound etc.), ester, acid amides etc. in addition.Organic sulfonate comprises perfluoroalkane hydrocarbon sulfonate alkali or alkali earth metal salt [perfluor C such as perfluoromethane potassium sulfonate, R 116 potassium sulfonate, perfluorinated butane sulfonic acid lithium, perfluorinated butane sodium sulfonate, potassium perfluorobutane sulfonate, perfluorinated butane calcium sulphonate, Perfluorocaprylic Acid potassium sulfonate for example _1-10Paraffinic hydrocarbons azochlorosulfonate acid alkali or alkali earth metal salt etc.], aromatic sulphonic acid alkali or alkali earth metal salt (for example Phenylsulfonic acid potassium, p-potassium toluene sulfonate, sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid potassium etc.), paraffinic hydrocarbons sulfonic acid aminotriazine salt (for example methanesulfonic trimeric cyanamide, methanesulfonic melam, ethane sulfonic acid melam, methanesulfonic melem, methanesulfonic trimeric cyanamide melam melem double salt etc.) etc.

The alcohol flame retardant can be enumerated the polyvalent alcohol, the polyvalent alcohol through esterification, the polyvalent alcohol that is substituted, carbohydrate (monose, polyose etc.) etc. of polyvalent alcohol, oligopolymer.

In addition, aforementioned inorganic flame retardant also comprises expansile graphite, low melting glass (for example special low melting glass, the spy who opens the introduction of 2001-64524 communique opens the glass composition of 2000-313811 communique introduction etc.) etc.

But one or more are used in combination these other fire retardant.

The content of other fire retardants for example can be by about 0.01～50 weight part, about preferred 0.05～30 weight part, particularly the scope about 0.1～20 weight part be selected with respect to the base resin of 100 weight parts.

Flame retardant resin composition of the present invention in addition in order to keep thermotolerance steadily in the long term, also can contain oxidation inhibitor or stablizer.Oxidation inhibitor or stablizer comprise that for example phenol system (Hinered phenols etc.), amine system (hindered amines etc.), phosphorus system, sulphur system, Resorcinol system, quinoline are oxidation inhibitor (or stablizer) etc.

Phenol is that oxidation inhibitor is preferred, Hinered phenols, for example 1,6-hexylene glycol-two C such as [3-(3,5-two-t-butyl-4-hydroxyphenyl) propionic esters] _2-10Alkylene glycol-two [3-(3,5-two-branching C _3-6Alkyl-4-hydroxyphenyl) propionic ester]; Triglycol-two two or three oxygen C such as [3-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionic esters] for example _2-4Alkylene base glycol-two [3-(3,5-two-branching C _3-6Alkyl-4-hydroxyphenyl) propionic ester]; Glycerine three C such as [3-(3,5-two-t-butyl-4-hydroxyphenyl) propionic esters] for example _3-8Alkylene triol-two [3-(3,5-two-branching C _3-6Alkyl-4-hydroxyphenyl) propionic ester]; Tetramethylolmethane four C such as [3-(3,5-two-t-butyl-4-hydroxyphenyl) propionic esters] for example _4-8Alkylene tetrol four [3-(3,5-two-branching C _3-6Alkyl-4-hydroxyphenyl) propionic ester etc.

Amine is that oxidation inhibitor comprises hindered amines, three or four C for example _1-3The Alkylpiperidine or derivatives thereof (methoxyl group, benzoyl oxygen, phenoxy group etc. can replace in the 4-position 2,2,6,6-tetramethyl piperidine etc.), two (three, four or five C _1-3Alkylpiperidine) C _2-20Alkylene dicarboxylic ester [for example malonic ester of two (2,2,6,6-tetramethyl--4-piperidyl) oxalic acid ester, corresponding oxalic acid ester, adipic acid ester, sebate, terephthalate etc.; Two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate], 1,2-two (2,2,6,6-tetramethyl--4-piperidines oxygen) ethane, phenylnaphthalene methylamine, N, N '-phenylbenzene-1,4-phenylenediamine, N-phenyl-N '-cyclohexyl-1,4-phenylenediamine etc.

Phosphorus is that stablizer (or oxidation inhibitor) comprises, for example three isodecyl phosphorous acid esters, three nonyl phenyl phosphites, phenylbenzene isodecyl phosphorous acid ester, phenyl diiso decyl phosphorous acid ester, 2,2-methylene two (4,6-two-t-butyl phenyl) octyl group phosphorous acid ester, 4, the two tridecyl phosphorous acid esters of 4 '-butylidene two (3-methyl-6-t-butyl phenyl), three (branching C _3-6Alkyl phenyl) phosphorous acid ester [for example three (2,4-two-t-butyl phenyl) phosphorous acid ester, three (2-t-butyl-4-tolyl) phosphorous acid ester, three (2,4-two-t-amyl group phenyl) ester etc.], two or three (2-t-butyl phenyl) phenyl phosphites, three (2-cyclohexyl phenyl) phosphorous acid ester, two (C _3-9Alkylaryl) pentaerythritol diphosphites [for example two (2,4-two-t-butyl phenyl) pentaerythritol diphosphites, two (2,4-two-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-two-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites etc.], triphenyl is stablizer (4-phenoxy group-9-α-(4-hydroxyphenyl)-p-cumyl oxygen-3 for example, 5,8,10-four oxa-s-4,9-two phospha spiral shell [5.5] undecanes, three (2,4-two-t-butyl phenyl) phosphoric acid ester etc.), two phosphinates are stablizer (for example four (2,-4,4 '-two penylene two phosphinates etc. 4-two-t-butyl)) etc.Phosphoric acid is that stablizer has branching C usually _3-6Alkyl phenyl (particularly t-butyl phenyl).

Resorcinol is that oxidation inhibitor for example comprises 2,5-two-t-butylhydroquinone etc., and quinoline is that oxidation inhibitor comprises for example 6-oxyethyl group-2; 2; 4-trimethylammonium-1,2-two Resorcinol etc., sulphur are that oxidation inhibitor comprises for example dilauryl thiopropionate, distearyl acyl group thiopropionate etc.

These oxidation inhibitors can separately or be used in combination of two or more.The content of oxidation inhibitor can be by for example selecting with respect to 0.01～5 weight part of base resin 100 weight parts, preferred 0.05～2.5 weight part, the particularly scope about 0.1～1 weight part.

In addition; when using polyester based resin or polycarbonate-based resin as base resin; if add acid phosphorus acids (for example inorganic phosphate or their basic metal or alkaline earth salts etc. such as phosphoric acid, phosphorous acid, phosphonic acids, phospho acid, Tripyrophosphoric acid) or organic phosphoric acid [phosphonic acids (phenyl-phosphonic acid etc.), phospho acid, phosphono-carboxylic acids, nitrogenous phosphoric acid etc.], then can further improve thermostability.

In addition.Flame retardant resin composition of the present invention also can add the anti-agent of dripping (De リ ッ PVC リ Application グ prevents agent) such as fluorine resin.The kindling material when using the anti-agent of dripping to suppress to burn and drip (the De リ ッ プ) of fused solution.Fluorine resin comprises the independent and multipolymer of fluorochemical monomers such as tetrafluoroethylene, a chlorotrifluoroethylene, vinylidene fluoride, R 1216, perfluoroalkyl vinyl ether; The multipolymer of co-polymerized monomers such as aforementioned fluorochemical monomer and ethene, propylene, acrylate.Such fluorine resin can exemplify, for example single polymers such as tetrafluoroethylene, polymonochlorotrifluoroethylene, poly-vinylidene fluoride; Multipolymers such as tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethene-one chlorotrifluoroethylcopolymer copolymer.These fluorine resins can use one or more to mix and use.

Aforementioned fluorine resin also can use granular, and median size for example also can be about 10～5000 μ m, about preferred 10～1000 μ m, more preferably about 10～700 μ m.

The content of fluorine resin is about 0.01～10 weight part, about preferred 0.1～5 weight part, more preferably about 0.1～3 weight part with respect to 100 weight part base resins for example.

Also have, flame retardant resin composition of the present invention also can contain other additives according to the purpose needs.Can enumerate stablizer (UV light absorber, heat-resisting stabilizing agent, weather stablizer etc.), lubricant, parting agent, tinting material, plasticizer, nucleator, modified impact agent, antiseize paste etc. as other additive.

[weighting agent]

Flame retardant resin composition of the present invention in order further to improve physical strength, rigidity, thermotolerance and electrical characteristic etc., can use weighting agent to carry out upgrading.Weighting agent comprises fiber filling agent, non-fiber filling agent (tabular weighting agent, powder shape weighting agent etc.).

Fiber filling agent can be enumerated the organic fiber of glass fibre, fibrous magnesium silicate, carbon fiber, silica fiber, silica alumina fiber, Zirconium oxide fibre, potassium titanate fiber, steel fiber, high-melting-point (for example acrylic resins such as aliphatics or aromatic polyamide, aromatic polyester, fluorine resin, polyacrylonitrile etc.) etc.

Tabular weighting agent in the non-fibrous filler can exemplify, for example glass flake, mica, graphite, various tinsels etc.

Powder shape weighting agent comprises carbon black, silicon-dioxide, quartz powder, glass grain, glass powder, grinds silicate such as (ミ Le De) optical fiber (for example grinding glass optical fiber etc.), Calucium Silicate powder, pure aluminium silicate, kaolin, talcum, clay, diatomite, wollastonite; Metal oxides such as ferric oxide, titanium oxide, zinc oxide, aluminum oxide; Metal carbonate such as lime carbonate, magnesiumcarbonate; Metal-powders such as metal sulfate such as calcium sulfate, barium sulfate, silicon carbide.

Preferred fibrous filler can be enumerated, and glass fibre, carbon fiber, preferred non-fibrous filler can be enumerated powder shape or tabular weighting agent, particularly glass grain, grind optical fiber, kaolin, talcum, mica and glass flake.

In addition, particularly preferred filling comprises having high strength inflexible glass fibre.

When using weighting agent, the ratio of weighting agent is in the flame retardant resin composition, for example about 5～60 weight %, about preferred 5～50 weight %, more preferably about 5～35 weight %.

When these weighting agents used, it was gratifying using astringent matter or surface treatment agent as required.These astringent matters or surface treatment agent comprise functional compound.The aforementioned functional compound can be enumerated epoxy based compound, silane based compound, titanic acid ester based compound, preferred epoxy based compound, particularly bisphenol A type epoxy resin, novolac-type Resins, epoxy etc.

Weighting agent also can carry out convergence process or surface treatment by aforementioned astringent matter or surface treatment agent.For the treatment time, can in absorb fillers, handle, also can before interpolation, anticipate.

In addition, and the functional surface treatment agent of usefulness or the consumption of astringent matter, be below the 5 weight %, about preferred 0.05～2 weight % with respect to weighting agent.

The fire retardant that the present invention uses, the carbonization of resin surface in the time of can promoting to burn is so can carry out fire-retardantization of height to resin.Use in addition combines secondary calcium phosphate salt (A) and at least a compound (B) that is selected from P contained compound, nitrogenous compound, boron-containing compound, silicon-containing compound and metallic compound, even it is a small amount of, Fireretardant thermoplastic resin effectively surperficial frosting and thermotolerance can not occur simultaneously and reduce yet.In addition, owing to use secondary calcium phosphate, can significantly reduce carrying capacity of environment, also be favourable at economic aspect.

[preparation method of flame retardant resin composition]

Flame retardant resin composition of the present invention also can be powder body mixture or molten mixture, can be by thermoplastic resin and fire retardant and the anti-agent of dripping as required, other additives etc. are mixed by conventional process.For example can adopt (1) each component to be mixed mixing with single pole or two bar forcing machine, as to extrude, be modulated into small pieces aftershaping method; (2) different small pieces (masterbatch (マ ス -バ ッ チ)) are formed in modulation, then these small pieces are measured in accordance with regulations mixing (dilution), moulding, obtain having the moulding product that regulation is formed; (3) with 1 or each composition more than 2 kind be fed directly into method in the shaper etc.In addition, when modulation is used for the composition of moulding product, as the powder body (for example part or all of polyester based resin powder body after crushed) with base resin mix with other components (fire retardant etc.), melting mixing, the dispersion that then helps improving other components.

Also have, consider from the angle of handling, non-resin shape component (secondary calcium phosphate salt, P contained compound, nitrogenous compound, boron-containing compound, silicon-containing compound, metallic compound etc.) and resin-like components (base resin, arborescens flame retardant (aromatic resin) etc.) are carried out melting mixing, and modulating masterbatch with this is very easily.When particularly using red phosphorus as P contained compound, the situation of modulation masterbatch is in the majority.In addition, when constituting masterbatch, how a part of base resin is used for masterbatch with resin-like components.

Masterbatch can be enumerated, and for example the masterbatch that is made of resin-like components (arborescens flame retardant) and non-resin shape component of (a) masterbatch of being made of part base resin and non-resin shape component, (b), (c) are by the masterbatch of part base resin and resin-like components (arborescens flame retardant) and non-resin shape component formation etc.

In addition, also can to contain various additives, for example fluorine resin, oxidation inhibitor, phosphorus as required be stablizer, weighting agent etc. to aforementioned masterbatch.

The masterbatch that so obtains is mixed with base resin and other component melts as required, can make flame retardant resin composition.

Also have, can use conventional processes such as melting mixing, extrusion moulding, injection moulding, compression molding to make flame retardant resin composition moulding of the present invention, the flame retardant resistance of the moulding product of formation and forming process are all very excellent, so can be used for various uses.For example be applicable to electrical and electronic parts, mechanical part, trolley part, wrapping material or case etc.

Industrial utilizability

Among the present invention, with secondary calcium phosphate salt (A) and at least a compound (B) that is selected from P contained compound, nitrogenous compound, boron-containing compound, silicon-containing compound and the metallic compound formation fire retardant that combines, so needn't use the halogen flame retardant, even also fire-retardantization of resin can be able to be suppressed the reduction of resin properties on a small quantity.In addition, because use secondary calcium phosphate salt as fire retardant, thus there is not carrying capacity of environment fully, also very favourable economically.Can obtain the improved moulding product of flame retardant resistance by such resin combination in addition.

Embodiment

The present invention will be described in more detail to utilize embodiment below, but the present invention is not limited to this embodiment.

Also have, by the flame retardant resistance of following test evaluation resin combination etc.

(flammability test)

According to UL94, estimate incendivity with the thickness 1.6mm of test film.

[resin R]

R-1: polybutylene terephthalate [ジ ュ ラ ネ ッ Network ス, limiting viscosity=1.0, poly-plastics (company) are made]

R-2: polyethylene terephthalate [ベ Le ペ ッ ト EFG10, clock spin (company) and make]

R-3: poly-(2,6-dimethyl-1,4-penylene) oxide compound (limiting viscosity=0.3)

R-4: polycarbonate [パ Application ラ ィ ト L1225, Supreme Being people change into (company) and make]

R-5: polystyrene [ト-ョ-ス チ ロ-Le GP G200C, Japan's vinylbenzene (company) are made]

R-6: R-3 and R-5 (75/25 weight ratio) are extruded hybrid resin after mixing

R-7:12.5 mole % isophthalate modified polybutylene terephthalate [ジ ュ ラ ネ ッ Network ス, poly-plastics (company) are made]

R-8: nylon MXD 6 [レ ニ-6002, the ェ of Mitsubishi Application ジ ニ ァ リ Application グ plastics (company) are made]

R-9:ABS resin [セ PVC ァ Application JD, ダ ィ セ Le chemical industry (company) are made]

R-10:SEBS[Network レ ィ ト Application G1657X, シ ェ Le chemistry (company) are made]

R-11: nylon 66[ボ リ プ ラ Na ィ ロ Application 66, poly-plastics (company) are made]

R-12: polyacetal resin [ジ ュ ラ コ Application M90-44, poly-plastics (company) are made]

[metal-salt]

(secondary calcium phosphate salt)

A-1: anhydrous phosphoric acid calcium monohydrogen phosphate: median size=peaceful chemical industries of about 30 μ m[(company) are made]

A-2: anhydrous phosphoric acid calcium monohydrogen phosphate: the median size=above-mentioned pulverization process thing of about 5 μ m[]

A-3: anhydrous phosphoric acid calcium monohydrogen phosphate: median size=about 100 μ m

(other metal-salts)

A-4: lime carbonate

A-5: tricalcium phosphate

[P contained compound and nitrogenous compound]

(P contained compound)

B1a: Resorcinol two (two-2,6-xylyl phosphoric acid ester) [PX200, big eight chemical industry (company) are made]

B1b: Resorcinol two (two-2,6-xylyl phosphoric acid ester) [PX201, big eight chemical industry (company) are made]

B1c: Resorcinol two (diphenyl phosphoester) [レ ォ Off ォ ス RDP, aginomoto Off ァ ィ Application テ Network ノ (company) make]

B1d; Bisphenol-A two (diphenyl phosphoester) [Off ァ ィ ロ-ス Off レ ッ Network ス BDP, ァ Network ゾ ノ-ベ Le (company) is made]

B1e: phosphazene compound [3～4 yuan of ring-type phenoxy phosphazenes]

B1f: red phosphorus [ノ-バ ェ Network セ Le 140, phosphorus chemistry industry (company) are made]

B1g: ethyl-methyl phospho acid aluminium

Open the manufacture method modulation of the aluminium salt of the ethylmethylphosphiniacid acid that the embodiment of flat 11-60924 communique introduces according to the spy.

B1h: phosphoric ester amides [SP-703, four countries change into industry (company) manufacturing]

B1i; Red phosphorus [ノ-バ ェ Network セ Le F5, phosphorus chemistry industry (company) are made]

(nitrogenous compound)

B2a: trimeric cyanamide cyanurate [MC610, daily output chemical industry (company) are made]

B2b: Tripyrophosphoric acid trimeric cyanamide [PMP100, daily output chemical industry (company) are made]

B2c: Tripyrophosphoric acid melam [PMP200, daily output chemical industry (company) are made]

B2d:CTU-guanamines [aginomoto Off ァ ィ Application テ Network ノ (company) manufacturing]

B3a: contain hydrate zinc borate [Firebrake ZB, Dupont (company) are made]

B4a: talcum [woods changes into (company) and makes]

B4b: zeolite [ゼ ォ ラ system A-4, eastern ソ-(company) make]

B5a: magnesium hydroxide [キ ス マ 5E, consonance chemistry (company) are made]

B5b: hydrotalcite [DHT-4A, consonance chemistry (company) are made]

[arborescens flame retardant C]

C-1: novolac-type resol [ス ミ ラ ィ ト レ ジ Application PR53195, Sumitomo デ ュ レ ズ (company) make]

C-2: novolac-type resol [ス ミ ラ ィ ト レ ジ Application PR53647, Sumitomo デ ュ レ ズ (company) make]

C-3: aminotriazine lacquer resol [Off ェ ノ ラ ィ ト KA-7054, big Japanese ink chemical industry (company) are made]

[oxidation inhibitor D]

D-1: tetramethylolmethane-four [3-(3,5-two-t-butyl-4-hydroxyphenyl) propionic ester] [ィ Le ガ ノ ッ Network ス 1010, チ バ ガ ィ ギ-(company) make]

[phosphorus is stablizer E]

E-1: two (2,6-two-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites [ァ デ カ ス Block PEP36, rising sun electrochemical industry (company) are made]

E-2: four (2,4-two-t-butyl phenyl)-4,4 '-two penylene two phosphinates [サ Application De ス Block P-EPQ, サ Application De (company) are made]

E-3: monocalcium phosphate

E-4: SODIUM PHOSPHATE, MONOBASIC 2 hydrates

[the anti-agent F that drips]

F-1: tetrafluoroethylene

[weighting agent G]

G-1: glass fibre (chopped strand of diameter 10 μ m, long 3mm)

G-2: glass fibre (chopped strand of diameter 13 μ m, long 3mm)

Embodiment 1～45 and comparative example 1～30

In the ratio shown in table 1～table 6 (weight part) said components is mixed, carry out mixing extruding, resin composition modulation with forcing machine.These resin combinations are tested with the moulding product with the injection moulding preparation, estimated incendivity.The results are shown in table 1～table 6.

Table 1

		Embodiment
																	1	2	3	4	5	6	7	B	9	10	11	12	13	14	15
		Resin R	R-1	100	100	100	100	60	100	100	70	70	70	70	70	70																70
R-2																				40										70
			R-3								30	28	28	28	28	23																28
R-4																								2	2	2	2		2	2
			R-5													7
R-6																													28
			Phosphoric acid hydrogen metal-salt A		A-1 40	A-1 40	A-1 40	A-1 40	A-1 40	A-1 5	A-1 5	A-1 10	A-1 8	A-1 15	A-1 15	A-2 8															A-2 8	A-1 8	A-3 4
Other fire retardant
			Fire retardant B	B1	B1a 75		B1a 40	B1a 35	B1a 35	B1b 20	B1a 35	B1a 30	B1a 15	B1a 30	B1c 30	B1a 15															B1a 15	B1a 15	B1a 15
B2		B2a 75															B2a 40	B2a 35	B2b 35	B2a 10			B2a 15			B2a 15	B2c 15	B2a 15	B2a 15
				Flame retardant C							C-1 15	C-2 20
Oxidation inhibitor D	D-1	0.3	0.3														0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
				Phosphorus is stablizer E	E-1	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3														0.3
E-2																										0.3	0.3	0.3
					The anti-agent F that drips	F-1			1.0	1.5	1.5	0.5	1.0	1.0	1.0	1.0													1.0	1.0	1.0	1.0	1.0
Weighting agent G	G-1	40	40	40													90	90		65			60	60	60	60	60	60
					The UL94 combustion test		V-1	V-2	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0													V-0	V-0	V-0	V-0	V-0

(numeric representation weight part in the table)

Table 2

		Comparative example
													1	2	3	4	5	6	7	8	9	10	11
		Resin R	R-1	100	100	100	100	100	100	100	70	70												70	70
R-2
			R-3								30	28											28	28
R-4																				2	2	2
			R-5
R-6
			Phosphoric acid hydrogen metal-salt A
Other fire retardant															A-4 40	A-5 40
			Fire retardant B	B1	B1a 75		B1a 40	B1a 40	B1a 40	B1b 20	B1a 35	B1a 30											B1a 15	B1a 30	B1a 15
B2		B2a 75											B2a 40	B2a 40	B2a 40	B2a 10			B2a 15		B2a 15
				Flame retardant C							C-1 15	C-2 20
Oxidation inhibitor D	D-1	0.3	0.3										0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
				Phosphorus is stablizer E	E-1	0.3	0.3	0.3	0.3	0.3	0.3	0.3										0.3	0.3	0.3	0.3
E-2
					The anti-agent F that drips	F-1			1.0	1.0	1.0	1.0									1.0	1.0	1.0	1.0	1.0
Weighting agent G	G-1	40	40	40									40	40		65			60	60
					The UL94 combustion test		HB	HB	HB	HB	HB	V-2									V-1	HB	HB	HB	V-1

(numeric representation weight part in the table)

Table 3

		Embodiment
																					16		17		18		19	20		21	22	23	24	25	26	27	28	29	30
		Resin R	R-1	70		68										70		70	100	100																				100	70
R-2																									70	70		68	68	68		70
			R-3	23		22		22		28	23		22	22	22
R-4																					2		2		2			2	2	2			30				30
			R-5	7		8		8			7		8	B	8
R-7																							68
			R-8													30	30
Phosphoric acid hydrogen metal-salt A		A-1 20																			A-1 20		A-1 20		A-1 15	A-1 15		A-1 10	A-1 15	A-1 15	A-1 7	A-1 15	A-1 10	A-1 10	A-1 5	A-1 5	A-1 5
				Other metal-salt
Fire retardant B	B1	B1a 25																			B1a 25		B1a 25		B1a 25	B1a 25		B1a 25	B1d 25	B1e 25	B1a 25	B1a 25	B1f 5	B1f 5	B1g 25	B1g 20	B1g 25
				B										B4a 5			B2c 8																						B2c 5
	Flame retardant C																																	C-2 10
Oxidation inhibitor D					D-1	0.3		0.3		0.3		0.3	0.3		0.3	0.3	0.3	0.3	0.3	0.3																		0.3	0.3	0.3	0.3
	Phosphorus is stablizer E																				E-3 0.3		E-3 0.3		E-3 0.3			E-4 0.3	E-4 0.3	E-4 0.3	E-1 0.3	E-1 0.3	E-1 0.3	E-1 0.3	E-1 0.3	E-1 0.3	E-1 0.3
The anti-agent F that drips					F-1	1.0		1.0		1.0		1.0	1.0		1.0	1.0	1.0	1.0	1.0	1.0																		1.0	1.0	1.0	1.0
	Weighting agent G	G-2	60																		60		60		60	60		60	60	60	60	60	50	50	50	50	50
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																		V-0	V-0	V-0

(numeric representation weight part in the table)

Table 4

		Comparative example
								12	13	14	15	16	17
		Resin R	R-1	68	68	68	70							70	100
R-2
			R-3	22	22	22
R-4	2							2	2		30
			R-5	8	8	8
R-7
			R-8				30
Phosphoric acid hydrogen metal-salt A
		Other metal-salt
Fire retardant B	B1							B1a 25	B1d 25	B1e 25	B1a 25	B1f 5			B1g 25
		B
	Flame retardant C
Oxidation inhibitor D			D-1	0.3	0.3	0.3	0.3						0.3		0.3
	Phosphorus is stablizer E							E-3 0.3	E-3 0.3	E-3 0.3	E-1 0.3	E-1 0.3		E-1 0.3
The anti-agent F that drips			F-1	1.0	1.0	1.0	1.0						1.0		1.0
	Weighting agent G	G-2						60	60	60	60	50		50
The UL94 combustion test			HB	HB	HB	HB	V-2						V-1

(numeric representation weight part in the table)

Table 5

		Embodiment
																	31	32	33	34	35	36	37	38	39	40	41	42	43	44	45
		Resin R	R-1							30
R-2																							20
			R-3									50
R-4	75																75	75	75	75	100	70	80
			R-9	25	25	25	25	25
R-10																								50
			R-11										100
R-12																										100	100	100	100	100
			Phosphoric acid hydrogen metal-salt A		A-1 10	A-1 10	A-1 10	A-1 5	A-1 5	A-1 10	A-1 3	A-1 3	A-1 2	A-1 10	A-1 2	A-1 2															A-1 2	A-1 2	A-1 1
Other metal-salt
			Fire retardant B		B1a 10	B1e 10	B1h 10	B1a 10	B1a 10	B4a 5	B1a 7	B1a 7	B1a 15	B1f 10	B1f 13	B1f 13															B1f 13	B1i 13	B1f 10
																	B2a 5	B3a 5		B4a 1	B4a 1				B4b 3	B5a 3	B5b 3	B2d 4
																															B5b 2
Flame retardant C																									C-2 20	C-3 20	C-3 20	C-3 20				C-2 15
			Oxidation inhibitor D	D-1	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3													0.3	0.3	0.3
Phosphorus is stablizer E	E-1	0.3															0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
			The anti-agent F that drips	F-1	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Weighting agent G
			The UL94 combustion test		V-0	V-0	V-0	V-0	V-0	V-1	V-0	V-0	V-0	V-0	V-0	V-0													V-0	V-0	V-0

(numeric representation weight part in the table)

Table 6

		Comparative example
															18	19	20	21	22	23	24	25	26	27	28	29	30
		Resin R	R-1							30	30
R-2
			R-3									50
R-4	75														75	75	75	100	100	70	70
			R-9	25	25	25	25
R-10																						50
			R-11										100
R-12																								100	100	100
			Phosphoric acid hydrogen metal-salt A					A-1 10		A-1 10
Other metal-salt
			Fire retardant B		B1a 10	B1e 10	B1h 10		B4a 5		B1a 7	B1a 7	B1a 15	B1f 10													B1f 13	B1f 13
																			B4a 1
					Flame retardant C																						C-2 20		C-3 20
Oxidation inhibitor D	D-1	0.3	0.3	0.3											0.3	0.3.	0.3	0.3	0.3	0.3	0.3	0.3	0.3	03
					Phosphorus is stablizer E	E-1	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3											0.3	0.3
The anti-agent F that drips	F-1															0.5		0.5	0.5
					Weighting agent G
The UL94 combustion test		V-2	V-2	V-2											HB	HB	HB	V-1	V-1	V-2	V-2	V-1	HB	HB

(numeric representation weight part in the table)

Find out by knowing in the table, compare with the comparative example that lacks secondary calcium phosphate, use secondary calcium phosphate salt (A) and be selected from least a fire retardant (component (B)) of P contained compound, nitrogenous compound, boron-containing compound, silicon-containing compound and metallic compound each embodiment, its excellent in flame retardance as fire retardant.

Claims (18)

1. fire-proof resin composition, it is the fire-proof resin composition that contains base resin and non-halogen flame retardant, and wherein aforementioned non-halogen flame retardant is made of secondary calcium phosphate salt (A) and at least a component (B) that is selected from P contained compound (B1), nitrogenous compound (B2), boron-containing compound (B3), silicon-containing compound (B4) and the metallic compound (B5).

2. according to the fire-proof resin composition of claim 1, wherein base resin is that to be selected from polyester based resin, ethylene series resin, acrylic resin, phenylethylene resin series, polyamide-based resin, polycarbonate-based resin, polyphenylene oxide be at least a thermoplastic resin in resin, vinyl resin and the polyacetal resin.

3. according to the fire-proof resin composition of claim 1, wherein base resin is selected from 1 for having, 4-hexanaphthene two methylene terephthalate, C _2-4Alkylene terephthalate and C _2-4Unitary homopolymerization of in the alkylene naphthalate at least one or copolyesters.

4. according to the fire-proof resin composition of claim 1, wherein base resin is polybutylene terephthalate or is the copolyesters of principal constituent with mutual-phenenyl two acid bromide two alcohol ester.

5. according to the fire-proof resin composition of claim 1, wherein secondary calcium phosphate salt (A) is anhydrous in fact.

6. according to the fire-proof resin composition of claim 1, wherein P contained compound (B1) is for being selected from least a in phosphoric acid ester, phosphoric ester amides, phosphazene compound, organic phospho acid compound, organic phosphinic compounds, (many) phosphoric acid salt and the red phosphorus.

7. according to the fire-proof resin composition of claim 1, wherein P contained compound (B1) is for being selected from least a in condensed phosphoric acid esters, (many) phosphoric acid salt and the stabilization red phosphorus.

8. according to the fire-proof resin composition of claim 1, wherein nitrogenous compound (B2) is for being selected from amino nitrogenous ring compound (a), with the salt (b) of amino nitrogenous ring compound and oxygen acid, with the salt (c) of amino nitrogenous ring compound and organic phosphoric acid, at least a with in salt (d), Tripyrophosphoric acid acid amides (e) and the carbamide compound (f) of amino nitrogenous ring compound and hydroxyl nitrogenous compound.

9. according to the fire-proof resin composition of claim 1, wherein boron-containing compound (B3) is the metal-salt of boric acid.

10. according to the fire-proof resin composition of claim 1, wherein silicon-containing compound (B4) is (gathering) organo-siloxane or zeolite.

11. according to the fire-proof resin composition of claim 1, wherein metallic compound (B5) is metal hydroxides or metal oxide.

12. according to the fire-proof resin composition of claim 1, wherein base resin at least by polyester based resin and polyphenylene oxide resin constitute, fire retardant is made of secondary calcium phosphate salt (A) and condensed phosphoric acid esters (B1).

13., wherein contain fire retardant 0.1～300 weight part with respect to base resin 100 weight parts according to the fire-proof resin composition of claim 1.

14., in the described fire retardant, contain the secondary calcium phosphate salt (A) of 5～1000 weight parts with respect to component (B) 100 weight parts according to the fire-proof resin composition of claim 1.

15., wherein further contain at least a aromatic resin (C) that is selected from resin (C1), polyarylate resin (C2) and the aromatic epoxy resin (C3) that on main chain or side chain, has hydroxyl and/or amino aromatic ring according to the fire-proof resin composition of claim 1.

16., contain further wherein that to be selected from hindered phenol be that oxidation inhibitor, phosphorus are at least a in stablizer, fluorine resin and the weighting agent according to the fire-proof resin composition of claim 1.

17. prepare the method for fire-proof resin composition, wherein the base resin of claim 1 mixed being prepared with the fire retardant of claim 1.

18. formed body, its fire-proof resin composition by claim 1 forms.